Nanoparticles and nanomaterialsS
Organized nanostructures and nano-objects: fabrication, characterization and applications V
The symposium broadly covers the scientific and technological aspects of synthesis, physical/chemical characterization and application of organic, inorganic and hybrid nanomaterials with special emphasis on the multiscale organization and self-assembly of ordered structures, in view of their integration into functional devices.
Semiconductor, dielectric, or metallic nanostructures have been predicted as technological boost in various fields including nano-electronics, optoelectronics, photonics, magnetism, phononics, plasmonics, advanced sensing and photovoltaics. The capability to control size, shape, bulk composition and doping of these nanostructures as well as their interface is crucial to tailor their properties.
The integration of these elemental building blocks into functional devices hinges critically on precise control of their spatial arrangement at the nano-scale i.e., density and relative positioning, both in plane and in depth. The ability to fabricate and organize ordered arrays of nano-objects on the solid substrates or and in the bulk is the key to support the technological development of new device concepts with predictable functional characteristics. The systematic control and the homogeneity of arrangement of each building block in the organized array are crucial for their exploitation both in conventional and in quantum devices.
Following very successful symposia organized in 2012, 2014, 2016, and 2018, this symposium intends to draw on previous experience. In particular, a special focus on multiscale fabrication, organization and self-assembly, area selective deposition, hybrid organic-inorganic approaches, is requested by the scientific community working in the field of nanotechnology. The symposium will provide the opportunity to present insights into advanced nano-structures and nano-device architectures at different stages of research and development.
The symposium is open to all experimental and theoretical contributions to the topic of organized nano-structures; the control of their composition and structural parameters in relation to their properties and functionalities. Thus, the symposium is conceived as a multidisciplinary platform that gathers researchers coming from academia and industry and promotes interactions among scientists and engineers working on all the aspects of semiconductor, metallic or dielectric nano-structures, ranging from fundamental physics and material science to the technological implementation and the final application in functional devices.
Hot topics to be covered by the symposium:
- Top-down and Bottom-up synthesis of nanostructures on surface and in volume
- Area selective deposition and hybrid organic-inorganic approaches (SIS and VPI)
- Doping issues in nanostructures
- Self and induced organization of nanostructures (including BCP-, DNA-, LC- based nanofabrication)
- Synthesis and properties of chiral nanomaterials
- Advanced methodology to control synthesis, positioning, shape, size in nanostructures
- Nanostructures for novel logic or memory device and for neuromorphic or quantum architectures
- Nanostructures for energy applications: photovoltaic and thermoelectric
- Nanostructures for advanced sensing, photonic, phononic, and plasmonic applications
Confirmed invited speakers:
- Gregor HLAWACEK, Helmholtz-Zentrum Dresden-Rossendorf, DE, Materials modification with Focused Ion Beams
- Carlo RICCIARDI, Politecnico di Torino, IT, Emergent Behavior in Neuromorphic Nanowire Networks
- Vincent CONSONNI, Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, FR, The Issues of Polarity and Residual Doping in ZnO Nanowires Grown by Chemical Bath Deposition for Piezoelectric Devices
- Yves HUTTEL, Instituto de Ciencia de Materiales de Madrid, ICMM-CSIC, ES, Gas assisted growth of nanoparticles: the case of gold nanoparticles
- Bartlomiej GRACZYKOWSKI, Adam Mickiewicz University, Poznan, PL, Engineering of mechanical and acoustic properties of polymer colloidal crystals
- Morgan STEFIK, University of South Carolina, US, Persistent Micelle Templates Reveal Nanoscale Cause-and-Effect One Variable at a Time
- Tamar SEGAL-PERETZ, Technion - Israel Institute of Technology, IL, Fabrication by design of hybrid organic-inorganic nanostructures with sequential infiltration synthesis
- Oleg GANG, Columbia University, US, DNA guided self-assembly (TBC)
- Yaping DAN, Shanghai Jiao Tong University, CN, Self-assembled molecular monolayers for delta-doping by pulsed laser annealing
- Robert STYLE, ETH Zürich, CH, Elastic control of phase separation
Further invited talks will be selected from outstanding submitted oral contributions.
- Paolo PELLEGRINO, Universitat de Barcelona, ES
- Stefan GULDIN, University College London, UK
- Guilhem LARRIEU, LIMMS/CNRS-IIS, FR/JP
- Chang-Yong NAM, Brookhaven National Laboratory, US
- Federico FERRARESE LUPI, INRIM, IT
- Juergen BRUGGER, EPFL, CH
- Stefano BRIVIO, CNR, IT
- Wilfred G. VAN DER WIEL, University of Twente, NL
- Johannes HEITMANN, TU Bergakademie Freiberg, DE
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S1 : TBD
Authors : Huttel, Y.*(1), Zhao, J.(2,3), Mayoral, A.(4,5), Martínez, L.(1), Johansson, M.P.(6), Djurabekova, F.(2).
Affiliations : (1) Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC), Madrid, Spain (2) Department of Physics and Helsinki Institute of Physics, University of Helsinki, Finland (3) Department of Electrical and Electronic Engineering, Southern University of Science and Technology, Shenzhen, China. (4) Institute of Nanoscience and Materials of Aragon (INMA), Spanish National Research Council (CSIC) and Laboratorio de Microscopias Avanzadas (LMA), University of Zaragoza, Spain. (5) Center for High-Resolution Electron Microscopy (CℏEM) School of Physical Science and Technology, ShanghaiTech University, China. (6) Department of Chemistry, University of Helsinki, FI-00014 Helsinki; CSC−IT Center for Science, Espoo, Finland.
Resume : The growth of clusters and nanoparticles in gas-phase represent a fascinating opportunity for fundamental studies and novel applications. In the last decade, increasing studies have reported the effect of injecting traces of gases during the synthesis process, evidencing their clear impact on the shape, size and chemical composition of resulting nanoparticles. Here, we report on the effect of traces of water vapour on the growth of gold nanoparticles (< 10 nm diameter). In particular we show the formation of core−satellite gold nanoparticle structures grown by magnetron sputtering inert gas condensation. Combining high-resolution scanning transmission electron microscopy and computational simulations, we reveal the adhesive and screening role of H2O molecules in formation of stable complexes consisted of one nanoparticle surrounded by smaller satellites. A single layer of H2O molecules, condensed between large and small gold nanoparticles, stabilizes positioning of nanoparticles with respect to one another during milliseconds of the synthesis time. The lack of isolated small gold nanoparticles is explained by Brownian motion that is significantly broader for small-size particles. It is inferred that H2O as an admixture in the inert gas condensation opens up possibilities of controlling the final configuration of the different noble metal nanoparticles.
Authors : Bruno, L.(1,2), Scuderi, M.(3), Priolo, F.(1,2) & Mirabella, S.(1,2)
Affiliations : (1) Dipartimento di Fisica e Astronomia “Ettore Majorana”, Università di Catania, via S. Sofia 64, 95123 Catania, Italy; (2) CNR-IMM, via S. Sofia 64, 95123 Catania, Italy; (3) CNR-IMM, VIII strada 5, 95121 Catania, Italy.
Resume : A low-cost, effective, and environmentally friendly method for the synthesis of Au and AuPd nanoparticles via a chemical reduction method with ascorbic acid (AA) was proposed. Moreover, a novel electrochemical sensor based on mono- and bi-metallic nanoparticle decoration of Ni-based nanostructures (synthesized by chemical bath deposition) was fabricated and used for detection of glucose. The morphology and structure of Au and AuPd nanoparticles, and Ni nanoporous film were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), while the amount of noble metal nanoparticles on the surface of Ni nanostructures was quantitatively analyzed through Rutherford Backscattering Spectrometry (RBS). Electrochemical performances have been investigated through electrochemical analyses: cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS). Decorated electrodes show high peak currents than bare ones and a shift in oxidation peaks, which can be ascribed to a more efficient electron transport and improved catalytic properties due to the presence of mono- and bi-metallic nanoparticles. Chronoamperometric (CA) analyses were performed in order to detect different concentrations of glucose. Decorated samples possessed a highly sensitive electrochemical response toward glucose, with a low detection limit of 3 μM and a sensitivity of 2.75 mA mM^−1 cm^−2. Synergistic effects between Au and Pd and the coupling of noble metal nanoparticles with Ni nanofoam play an important role to exhibit superior sensitivity towards the detection of glucose. These results confirmed the assumption that integrating catalytic metal nanoparticles on a wide band gap metal oxide semiconductor can provide unique sensing property to detect specific electroactive products. It is expected that the proposed method can be used for the synthesis of other metal nanostructures with distinguished electrocatalytic abilities and used for enhanced and direct sensing applications.
Authors : Claudia Iriarte-Mesa [a], Estelle Juère [a,b], Doris Marko [c], Giorgia Del Favero [c], Freddy Kleitz [a]*
Affiliations : [a] Department of Inorganic Chemistry − Functional Materials, Faculty of Chemistry, University of Vienna, Austria; [b] Trinity Biomedical Science Institute, Trinity College Dublin, Dublin, Ireland; [c] Department of Food Chemistry and Toxicology, Faculty of Chemistry, University of Vienna, Austria
Resume : Despite more than a century of research to achieve oral delivery insulin, the current clinical reality remains unchanged in terms of therapeutic administration, due to the challenge of overcoming gastrointestinal barriers. It has been recently reported by our group that with the use of dendritic mesoporous silica nanoparticles (DMSNs) together with a protein-based excipient, succinylated ß-lactoglobulin (BL), pH-responsive tablets could prevent the premature gastric release and degradation of encapsulated insulin. However, there are still open issues related to colloidal stability, control of release rate, permeation enhancement and mucoadhesion, which need to be addressed before reaching in vivo tests. To this aim, we focus our studies on the examination of the influence of surface chemistry/charge and colloidal stability of DMSNs on the loading efficiency and insulin release performances. For this, DMSNs (130 nm; pore size: 7.0 nm) were functionalized with polyethylene glycol (PEG, 2 kDa) and a phosphonate-silane, trihydroxysilylpropyl methylphosphonate (THMP), introduced through different post-grafting strategies.[3,4] The functionalized DMSNs (DMSNs-PEG and DMSNs-PO3) exhibited an enhanced colloidal stability in aqueous and saline media (PBS) over a wide pH range. Different formulations for oral administration were prepared by mixing BL with pure and functionalized DMSNs containing insulin (20 % w/w) and preliminary release tests were performed with simulated body fluids. Compared to a DMSNs-free formulation, encapsulated insulin was even more protected and the release was lowered down to acceptable threshold (less than 10 %) at pH 1.2, while at pH 7.4 controlled release could be reached for 24 h. The analysis of the released insulin confirmed that drug confinement into the pores of the hybrid DMSNs did not affect the peptide structure. The ability of DMSNs to be internalized by intestinal cells was tested using non transformed human epithelial colon cells (HCEC) through live cell imaging and benchmarking the biological activity of insulin uptake with respective cell metabolic status. REFERENCES  Y. Xiao, Z. Tang, J. Wang, C. Liu, N. Kong, O. C. Farokhzad, W. Tao, Angew. Chemie - Int. Ed. 2020, 59, 19787–19795.  E. Juère, R. Caillard, D. Marko, G. Del Favero, F. Kleitz, Chem. - A Eur. J. 2020, 26, 5195–5199.  C. Von Baeckmann, R. Guillet-Nicolas, D. Renfer, H. Kählig, F. Kleitz, ACS Omega 2018, 3, 17496–17510.  M. Bouchoucha, M. F. Côté, R. C-Gaudreault, M. A. Fortin, F. Kleitz, Chem. Mater. 2016, 28, 4243–4258.
Authors : Milan E.(1), Trupp L.(2), Cressoni C.(1), Torres-Martínez, A.(3), Pérez G.(3), Galindo F.(3), Miravet J.F.(3), Vurro F.(4), Marzola P.(4), Dal Grande M.(1), Lucchini G.(1), Speghini A.*(1), Julián-López B.(2)
Affiliations : (1) NRG, Department of Biotechnology, University of Verona and INSTM, RU Verona, Strada Le Grazie 15, I-37134 Verona, Italy. *: email@example.com (2) Institute of Advanced Materials, Universitat Jaume I, Avda. Sos Baynat s/n, 12071, Castelló, Spain (3) Departament of Inorganic and Organic Chemistry, Universitat Jaume I, Avda. Sos Baynat s/n, 12071 Castelló, Spain (4) Department of Computer Science, University of Verona and INSTM, RU Verona, Strada Le Grazie 15, I-37134 Verona, Italy
Resume : The development of multifunctional nanomaterials for theranostics (the diagnosis and therapy of a pathological condition, as cancer) is a hot topic in Nanomedicine. To this aim, the combination of inorganic nanoparticles (NPs) with suitable organic molecules attributes multiple functionalities in the resulting hybrid nanostructures. In this communication, we studied the encapsulation of upconverting lanthanide doped fluoride NPs (e.g. NaYF4:Yb,Er/Tm/Nd) and iron oxide NPs (SPIONs) in a polymer hydrogel, in order to develop nanosized materials acting as efficient contrast agents for both optical and Magnetic Resonance Imaging (MRI), and producing hyperthermia by using oscillating magnetic fields or optical radiations in the near infrared (NIR) region. Both fluoride and iron oxide NPs were prepared with hydrophobic coatings by thermal decomposition techniques. A two steps strategy was considered to encapsulate the different NPs in the nanogel. First, a macroscopic gel incorporating both the kinds of NPs is formed through a rapid temperature change of the dispersing solution. Then, nanogels of size of few hundreds of nanometers are obtained through ultrasonication. Upconversion and Stokes emissions of the nanogels were measured upon laser excitation in the NIR (e.g. at 800 or 980 nm). Optical thermometry was also exploited for local temperature measurements. The performance of the nanogels as MRI contrast agents was evaluated by acquiring T1 and T2 map sequence to measure their longitudinal and transversal relaxivity. Preliminary tests of hypertermia showed a notable heating efficiency of the nanogels. References Mandl GA, Cooper DR, Hirsch T, Seuntjens J, Capobianco JA. Perspective: Lanthanide-doped upconverting nanoparticles. Methods Appl Fluoresc., 2019; 7 (1) 012004. Felip-León C, Guzzetta F, Julián-López B, Galindo F, Miravet JF. Multimodal light-harvesting soft hybrid materials: Assisted energy transfer upon thermally reversible gelation. J Phys Chem C., 2017; 121 (39) 21154-21159. Gerosa M, Grande MD, Busato A, Vurro, F, Cisterna B, Forlin E, Gherlinzoni F, Morana G, Gottardi M , Matteazzi P, Speghini A, Marzola P Nanoparticles exhibiting self-regulating temperature as innovative agents for Magnetic Fluid Hyperthermia. Nanotheranostics., 2021; 5 (3) 333-347.
Authors : M. Censabella, V. Iacono, A. Scandurra, K. Moulaee, G. Malandrino, G. Neri, F. Ruffino, S. Mirabella
Affiliations : M. Censabella Dipartimento di Fisica e Astronomia “Ettore Majorana”, Università di Catania, via S. Sofia 64, 95123 Catania, Italy CNR-IMM via S. Sofia 64, 95123 Catania, Italy; V. Iacono Dipartimento di Fisica e Astronomia “Ettore Majorana”, Università di Catania, via S. Sofia 64, 95123 Catania, Italy CSFNSM - Centro Siciliano di Fisica Nucleare e Struttura della Materia, Via S. Sofia 64 95123 Catania; A. Scandurra Dipartimento di Fisica e Astronomia “Ettore Majorana”, Università di Catania, via S. Sofia 64, 95123 Catania, Italy; K. Moulaee Department of Engineering, University of Messina and INSTM Research Unity, C.da Di Dio, I-98166, Messina, Italy; G. Malandrino Dipartimento di Scienze Chimiche, Università di Catania, and INSTM UdR Catania, Viale A. Doria 6, I-95125 Catania, Italy; G. Neri Department of Engineering, University of Messina and INSTM Research Unity, C.da Di Dio, I-98166, Messina, Italy; F. Ruffino Dipartimento di Fisica e Astronomia “Ettore Majorana”, Università di Catania, via S. Sofia 64, 95123 Catania, Italy CNR-IMM via S. Sofia 64, 95123 Catania, Italy CSFNSM - Centro Siciliano di Fisica Nucleare e Struttura della Materia, Via S. Sofia 64 95123 Catania; S. Mirabella Dipartimento di Fisica e Astronomia “Ettore Majorana”, Università di Catania, via S. Sofia 64, 95123 Catania, Italy CNR-IMM via S. Sofia 64, 95123 Catania, Italy CSFNSM - Centro Siciliano di Fisica Nucleare e Struttura della Materia, Via S. Sofia 64 95123 Catania;
Resume : CuO is one of the most widely studied p-type oxide semiconductor, thanks its peculiar properties, such as catalytic activity, high stability under gas exposure, antibacterial activity, optoelectronic properties. Therefore, CuO nanostructures (CuO Ns) find widespread applications in many fields: optoelectronics, solar energy cells, catalysis, energy storage and gas sensing. In particular, CuO Ns have received great attention by scientific community for applications as chemoresistive gas sensors. Indeed, its semiconductor nature allow to change its electrical resistance in presence of gas. In addition, the nanostructured form improves the sensor’s properties in terms of response speed, sensitivity and selectivity. Anyway, the success of such technologies implies knowledge and control over the nanostructures’ properties (shape, sizes, structure and crystallinity) and consequently the development of simple, versatile, low-cost techniques for their production allowing such a fine control. To meet these requirements, we present a laser-based synthesis method for a controlled production of CuO Ns. In particular, by employing pulsed laser ablation in liquid environment and an annealing process at 400°C, we have produced ligand-free CuO Ns with desired size, composition and shape. After a complete optical (UV-Vis), structural (XRD), morphological (SEM) and chemical (XPS, EDX) and characterization, we used CuO Ns to fabricate a chemoresistive gas sensor working at room temperature. Under Nitric Oxide (NO) gas exposure, CuO Ns-based sensor changes its resistance, showing good performances in sensitivity, selectivity, stability, low limit of detection and fast response/recovery time. In particular, at a temperature of 50°C, we found response time of 2 s, good reproducibility of the tests and good response in humidity conditions. The peculiar shape and size (20 nm thin needles) of CuO Ns obtained by the laser synthesis are promising for chemoresistive gas sensor.
Authors : Qilin Zou*(1), Clément Roux(2), Robert Mauricot(1), Marc Verelst(1) & Christophe Coudret(2)
Affiliations : (1)CEMES-CNRS, Université de Toulouse, UPS, France (2)IMRCP, Université de Toulouse, UPS, CNRS, France
Resume : In recent decades, biomedical imaging technologies have been exploited for early disease detection and diagnosis.1 Several imaging modals, such as, computed tomography (CT), magnetic resonance imaging (MRI), photoacoustic imaging (PAI), positron-emission tomography (PET), single-photon-emission computed tomography (SPECT), and optical imaging (OI) have played important roles in observation of the structures and functions of biological systems, and providing important information concerning the pathogenesis, progression and treatment of diseases such as cancer.2 Multimodal bioimaging, is one technique which combines various components into one platform or applies one component armed with multiple image capacities, has been extensively studied. In our previous studies3-4, we have demonstrated the potential multimodal (OI, MRI, and CT) bioimaging of lanthanide-doped Gd2O2S nanoparticles. However, there are still challenges on Gd2O2S such as improved synthesis method, reduced size (<20 nm), and surface modification. In our work, we proposed a versatile strategy for synthesizing 15 types of rare earth oxysulfide nanoparticles with size from 3 to 11 nm. To acquire multi modal capacities (NIR-II luminescence, magnetic and CT performances), we further synthesized a series of Nd-doped Gd2O2S nanoparticles with a mean size of 6 nm. Under 808 nm laser irradiation, we measured the photoluminescence emission spectra of Gd2O2S:x%Nd (x=10, 20, 40, 60, 100) nanoparticles and then optimized the doping level at 60%Nd. To render nanoparticles hydrophilic, a ligand exchange method was proposed, in which PVP molecules displaced hydrophobic oleic acid layer of the surface of Gd2O2S:60%Nd nanoparticles. Cytotoxicity study of as-prepared PVP-coated Gd2O2S:60%Nd nanoparticles was carried out. Magnetic and CT performances were evaluated when mixing the PVP-coated Gd2O2S:60%Nd nanoparticles with gelatine solution. Last but not the least, NIR bioimaging, MRI, and CT imaging were implemented and it demonstrated the feasibility of multimodal bioimaging of ultrasmall RE2O2S nanoparticles. In short, these findings pave an avenue for the bio-applications of rare earth oxysulfide nanoparticles. References 1. Weissleder, R.; Pittet, M. J., Imaging in the era of molecular oncology. Nature 2008, 452, 580-589. 2. Rosenkrans, Z. T.; Ferreira, C. A.; Ni, D.; Cai, a. W., Internally Responsive Nanomaterials for ActivatableMultimodal Imaging of Cancer. Adv. Healthcare Mater. 2021, 10, 2000690. 3. Santelli, J.; Lechevallier, S.; Baaziz, H.; Vincent, M.; Martinez, C.; Mauricot, R.; Parini, A.; Verelst, M.; Cussac, D., Multimodal gadolinium oxysulfide nanoparticles a versatile contrast agent for mesenchymal stem cell labeling. Nanoscale 2018, 10, 16775-16786. 4. Santelli, J.; Lepoix, C.; Lechevallier, S.; Martinez, C.; Calise, D.; Zou, Q.; Moyano, S.; Cussac, D.; Verelst, M.; Mauricot, R., Custom NIR Imaging of New Up-Conversion Multimodal Gadolinium Oxysulfide Nanoparticles. Part. Part. Syst. Charact. 2021, 38, 2000216.
Authors : Jin Zhang, Ondřej Veselý, Zdeněk Tošner, Michal Mazur, Maksym Opanasenko, Mariya Shamzhy
Affiliations : Department of Physical and Macromolecular Chemistry & Charles University Center of Advanced Materials, Faculty of Science, Charles University in Prague, Hlavova 8, 12843 Prague, Czechia
Resume : A discovery of ADOR synthetic protocol (Assembly – Disassembly – Organization – Reassembly) applicable for germanosilicate zeolites is an important milestone in materials design, which empowered the synthesis of previously unknown “isoreticular” zeolites with tunable building units (i.e., -d4r-, -s4r-, -O-) connecting crystalline layers. Two processes operating at disassembly step – deconstructive “de-intercalation” and reconstructive “rearrangement” – were proven to determine the structure of thus formed ADORable zeolites. Although being desirable for regulation of products characteristics, independent management of the key ADOR processes remained elusive so far . Herein, we report on controlling primary ADOR steps and present the first example of “cycled” structural transformation of interlayer units (d4r → s4r → d4r) in germanosilicate UTL zeolite under “slow de-intercalation”/“fast rearrangement” conditions. Alternatively, firstly described “slow de-intercalation” mode of ADOR enables the preparation of already known OKO, *PCS, IPC-7 zeolites via gradual reduction of interlayer units in UTL (d4r → d4r/s4r → s4r → s4r/-O-) – mechanism, opposing to conventional synthesis based on “rearrangement” process (-O- → s4r/-O- → s4r…). To control the rates of disassembly and rearrangement processes within ADOR synthesis approach, UTL germanosilicate was subjected to hydrolysis in low-water high-volume alcohol solutions of different concentrations with/without addition of Al as a source of framework-building element. Our time-resolved PXRD, MAS NMR and physisorption studies reveal the following plausible mechanism of UTL→Al-IPC-2→Al-UTL transformation in Al-containing water-methanol environment was proposed: 1. slow hydrolysis of Ge–O(Si) linkages resulting in distortion of UTL framework (1 min – 1h ); 2. removal of progressively leached germania from the pores and incorporation of Al via healing the formed silanol nests. Resulting Al-poor IPC-2 zeolite (1 h – 1 days) is characterized by low crystallinity; 3. Al incorporation along with self-organization of zeolite layers (1 – 12 days) leading to higher crystallinity of resultant Al-enriched IPC-2 zeolite; 4. Al-assisted rearrangement process continuing at suppressed disassembly and resulting in reconstruction of S4R interlayer linkages in Al-IPC-2 to D4R units characteristic of UTL zeolite (12 – 60 days). The results of this study show “slow disassembly” mode of ADOR is perspective for adjusting pore architecture of germanosilicate zeolites toward increasing their micropore size, never achieved in classical ADOR mechanism, while introducing catalytically active Al acid sites. The research highlights the potential of this technique for further design of the already predicted but yet inaccessible members of ADORable zeolites family. References:  M. Opanasenko, M. Shamzhy, Y. Wang, W. Yan, P. Nachtigall, J. Čejka, Angew. Chem. Int. Ed. 59 (2020) 19380–19389
S2 : TBD
Authors : Vincent Consonni
Affiliations : Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, F-38000 Grenoble, France
Resume : Owing to its wurtzite structure and low formation energy of shallow donors, ZnO both exhibits polar and piezoelectric properties along with a usually high density of free electrons . In contrast to ZnO single crystals and films, the effect of polarity in nanorods has been much less investigated despite its crucial importance for piezoelectric devices, where a mix of O- and Zn-polar objects in the arrays cancels out the piezoelectric potential. While ZnO nanorods grown by vapor phase deposition techniques are systematically Zn-polar, they can be of either O- or Zn-polarity when grown by chemical bath deposition . This low-cost and low temperature process compatible with the fabrication of flexible devices offers a great opportunity to select the polarity of ZnO nanorods and to get a deep knowledge of its effect on many properties. In this context, we review the issue of the polarity in ZnO nanorods by focusing on its effect on the nucleation and growth mechanisms, defect incorporation and residual doping, and electrical contact . A special emphasis is placed on the residual doping of ZnO nanorods involving hydrogen-related defects , as an important aspect in piezoelectric devices where the screening effect by the free charge carriers should be reduced as much as possible.  J. Zúñiga-Pérez et al. Applied Physics Reviews 3, 041303 (2016).  V. Consonni et al. ACS Nano 8, 4761 (2014).  V. Consonni et al. Nano Energy 83, 105789 (2021).  J. Villafuerte et al. The Journal of Physical Chemistry C 124, 16652 (2020).
Authors : G. Di Mari (1,2), L. Bruno (1,2), G. Malandrino (3), G. Franzò (2), S. Mirabella (1,2), E. Bruno (1,2)
Affiliations : (1) Dipartimento di Fisica e Astronomia, Università degli Studi di Catania, Via S. Sofia 64, 95123, Catania, Italy; (2) CNR-IMM, Via S. Sofia 64, 95123, Catania, Italy. (3) Dipartimento di Scienze Chimiche, Università degli Studi di Catania, INSTM UdR Catania, Viale A. Doria 6, 95125, Catania, Italy
Resume : ZnO based nanostructures have a huge variety of applications and represent a green choice due to its material abundance and biocompatibility. Thanks to its large band gap (3.37 eV), high excitonic binding energy, and excellent charge carrier transports properties, ZnO presents an intense UV luminescence, while a smaller visible emission is obtained in nanostructures, typically ascribed to surface defects . Many different shapes have been produced by sophisticated and costly techniques as well as by means of cheap methods. With exception of nanoparticles and nanorods, a cost-effective mass production of ZnO nanostructures is still challenging since a good reproducibility is typically obtained at the cost of a low throughputs. Here we focus on the controlled synthesis of ZnO nanostars by Chemical Bath Deposition (CBD). Nanostars appear as self-assembled bundles of crystalline ZnO nanostrips (sized 1oo per 1000 nm, with thickness smaller than 40 nm) with clear hexagonal symmetry on the assembly plane (building 6-point stars). Large amounts of these novel nanostructures are produced in aqueous solution, and characterized by X-Ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-dispersive X-Ray Spectroscopy (EDS), Rutherford Backscattering Spectrometry (RBS), Photo- and Cathodo-Luminescence spectroscopy (PL and CL), and photoconductivity measurements in order to evidence their structural electrical and optical properties, as pristine and after thermal annealing. The different preparative parameters, such as reaction time, bath temperature, concentrations and addition order of precursor solutions were deeply investigated to drive the ZnO precipitation towards differently shaped nanostructures. A very intense visible emission is obtained and related to the high surface-over-volume ratio of these nanostructures.  E. G. Barbagiovanni, R. Reitano, G. Franzò, V. Strano, A. Terrasi, and S. Mirabella, Nanoscale, 2016, DOI: 10.1039/C5NR05122C
Authors : Zhaojun Zhang1, Klara Suchan2, Jun Li2, Crispin Hetherington3, Alexander Kiligaridis2, Eva Unger2, Ivan G. Scheblykin2, Jesper Wallentin1*
Affiliations : 1 Synchrotron Radiation Research and NanoLund, Department of Physics, Lund University, Box 124, Lund, 22100, Sweden. 2 Chemical Physics and NanoLund, Department of Chemistry, Lund University, Box 124, Lund, 22100, Sweden. 3 Centre for Analysis and Synthesis and NanoLund, Department of Chemistry, Lund University, Box 124, Lund, 22100, Sweden.
Resume : Metal halide perovskite nanowires (NWs) arrays have shown excellent performance in various optoelectronic applications.1, 2 Here, we report a low temperature solution growth of vertically aligned CsPbBr3 NWs arrays with excellent stability, using anodized aluminum oxide (AAO) templates. The potential application of these CsPbBr3-NWs/AAO composite as X-ray scintillator is also investigated.3 The NW diameter (10-250 nm) and the length (tens of nm to few μm) can be independently controlled. With decreasing diameter, the CsPbBr3 NWs show a gradual photoluminescence blue-shift from 250 nm to 10 nm and crystal structure change from orthorhombic to cubic phase below 20 nm. This is the first observation of physical confinement induced phase transition for CsPbBr3. The physical confinement of the CsPbBr3 NWs in the AAO gives a remarkable stability to long term air storage. Any significant degradation of these structures is not observed within 4 months, despite storing the sample in ambient air. Additionally, the CsPbBr3-NWs/AAO composite shows strong and stable X-ray scintillation signal even under continuous X-ray long time exposure, which makes it promising for applications in X-ray scintillation. The growth method proposed in this work should be viable for a wide range of metal halide perovskite materials. The demonstrated stability makes the vertically aligned CsPbBr3-NWs a promising foundation for a wide range of applications in many fields of optoelectronics.
Authors : 1- Mehrnaz Modaresialam Zeinab Chehadi Jean-Claud Benoit Luc Favre Marco Abbarchi David Grosso
Affiliations : Université Aix-Marseille Institue IM2NP
Resume : The purpose of our work is to develop methods to elaborate nanostructured metasurfaces by combining sol-gel chemistry and Nano Imprint Lithography (soft-NIL), which are of relevant scientific and technological interest as they inscribe themselves in the general trend of developing affordable and time-saving processes, using biocompatible and non-toxic materials. Firstly, we showcase the elaboration of new efficient antireflection coatings made of water-repellent methylated silica nipple-dimple nano-architectures (pillars and holes). The interest of these results relies on the possibility to drastically reduce reflection in a broad spectral interval and within a broad acceptance angle of the incident light, rendering them adapted to photovoltaic glass cover protections. Moreover, it transverse refractive index gradient created by tapered nipple-dimple pillars between 1.2 and 1.26. Total transmission for double-face nano-imprint wafers reaches 96~97% in the visible range, it is limited by specular reflection and mostly by the intrinsic diffusion of the glass substrateFurthermore, these nano-materials feature a high chemical, thermal and mechanical stability. Secondly, a highly sensitive optical gas sensor was elaborated based on TiO2 nanopatterns embedded in a thin microporous hybrid-SiO2 sensitive coating. The measured sensing performances are sensitivity S up to 4500 nm / RIU, reflectivity variation up to R* = 17 R / RIU, FOM up to 12, for a specific wavelength, which is compatible with sub-ppm gas detection by simple specular reflection.
Authors : Subila Balakrishnan, Eran Edri*
Affiliations : Post Doctoral Research Scholar; Senior Lecturer Department of Chemical Engineering Ben Gurion University of Negev, Israel
Resume : Metal trichalcogenides and chalcohalides establishes a class of semiconducting materials with a quasi-one dimensional crystal structure. These low-symmetry semiconductors have shown favourable optoelectronic properties for photovoltaic and photo electrocatalysis: an optical bandgap in the visible-NIR region, and a relatively small electron affinity. However, there are limited synthetic strategies for nanostructured chalcohalides. Here we report a facile route for transformation of Sb2Se3 to SbSeI nanorods. The Sb2Se3 nanorods acted as template to form small diameter SbSeI nanorods. The aspect ratio of SbSeI nanorods could be varied by changing the aspect ratio of the template. A detailed investigation of the transformation process reveal favourable thermodynamics and proceeds through a topotactic mechanism that may be suitable for other trichalcogenide-chalcohalide transformations. These ID materials show good charge transport and a bang gap (Eg) of 1.7 eV, which are suitable for photocathodes for hydrogen evolution reaction.
Authors : Tadas Paulauskas,1 Vaidas Pačebutas,1 Jan Devenson,1 Bronislavas Čechavičius,1 Mária Čaplovičová, 2 Xiaoyan Li,3 Mathieu Kociak,3 Arūnas Krotkus1
Affiliations : 1 Center for Physical Sciences and Technology, Saulėtekio al. 3, Vilnius, Lithuania 2 STU Centre for Nanodiagnostics, Slovak University of Technology, Vazovova 5, Bratislava, Slovakia 3 Laboratorie de Physique des Solides, University of Paris, 91400 Orsay, France
Resume : The bismide GaAs1-xBix alloy has experienced an extensive amount of research and represents the emerging class of bismuth-containing group III-V semiconductors. Incorporation of large Bi atoms into the lattice produces perturbations mainly to the valence band states, which leads to the bandgap bowing, as well as large spin-orbit band splitting. The interest in this alloy arises from its potential and already implemented applications in near- to mid-infrared range optoelectronics,− lasers, photodetectors, solar cells. The distribution of alloyed atoms in semiconductors often deviates from the expected random distribution and can have significant effects on the properties of the materials. Previous studies of the spontaneous atomic ordering of bismides focused primarily on their atomic and microstructure analysis. The study presented here examines the influence of the CuPt-type ordering on GaAsBi optoelectronic properties, and is the first study that reports the optical anisotropy in GaAsBi alloys. Atomic and bulk-scale structural, chemical, as well as optical study of the dilute GaAs1-xBix alloys was carried out. The optical anisotropy was revealed in samples grown on exact and offcut (001) GaAs substrates via polarized photoluminescence and transmittance spectra, as well as by birefringence and linear dichroism measurements. The observed polarization dependence in all the optical measurements agreed with theoretical predictions for the CuPt ordering. No polarization anisotropy was observed in the bismide sample composed of anti-phase domains grown on (001) Ge, in which the polarization effects are predicted to cancel. Sample surface and bulk characterization techniques, including SEM, AFM, XRD, and cross-sectional STEM, were employed to exclude other possible sources of structural anisotropies that may cause these optical effects. Atomic-scale HAADF and EDX analysis of Bi atom distribution and XRD suggests that the ubiquitous CuPtB ordering is responsible for the optical anisotropy. Further work will be needed to clarify the magnitude of the ordering-induced valence-band splitting in GaAsBi alloys and to better understand the reasons for such pronounced effects at dilute Bi concentrations. Polarization anisotropy is an important factor to consider for future development of GaAsBi-based lasers and photodetectors. These findings elucidate spontaneous ordering effects in GaAsBi and encourage its further investigations.
Authors : Swati Mamgain, Aswani Yella
Affiliations : Indian Institute of Technology Bombay, Mumbai, India 400614
Resume : Recently, all-inorganic perovskite nanocrystals emerged as an efficient material for optoelectronic applications. However, the presence of trap states at the surface hinders their optical and electrical properties. Along with this, the NCs are surrounded by organic ligands, which prevent the effective injection of charge carriers in the devices. So, to integrate these NCs into the devices, it is essential to address the issues mentioned above. Herein, we report the post-synthetic treatment of CsPbBr3 NCs with phenethylammonium bromide. This treatment results in highly stable and luminescent CsPbBr3 NCs with an increase in photoluminescence quantum yield (PLQY) from 69.1% to 92.4% without changing the shape and size of NCs. Time-resolved photoluminescence decay traces and ultrafast transient absorption measurements confirm the removal of defect states after the treatment, which are responsible for the non-radiative recombination of charge carriers. Additionally, this treatment efficiently removes ligands from NCs surface while sustaining their colloidal stability. Finally, photodetectors were fabricated by using pristine as well as phenethylammonium bromide treated CsPbBr3 NCs. The treated CsPbBr3 NCs based photodetector shows a high on-off ratio with fast response time as compared to a very weak photoresponse of pristine CsPbBr3 photodetector. This work provides a simple but effective way to make high-quality NCs for optoelectronic applications.
S3 : TBD
Authors : Wiktor Lewandowski
Affiliations : Faculty of Chemistry, University of Warsaw, 02-093 Warsaw, Poland
Resume : Stimulated by recent visionary works, much interest has been revived toward the construction of chiral nanoarchitectures showing enantiospecific interactions with optical fields. Such materials are desirable for the construction of next-generation optoelectronic devices. Unfortunately, the challenge of applying chiral plasmonic structures in the industry lies in developing low-cost, high yield, highly stable nanomaterials with precisely controlled structural parameters. In our laboratory, we developed a versatile, organic chemistry-based platform for the creation of helical, ordered nanomaterials that can enantiospecifically absorb (and potentially emit) circularly polarized light , Figure 1. Our approach relies on the melting of a composite: an organic, liquid-crystalline template that exhibits chiral morphology with chemically compatible nanoparticles . On a freezing, the organic material forms helical filaments, while nanoparticles are selectively pushed to the edges of the filament. The helical arrangement of nanoparticles allows for the coupling of their properties and translates to chiral optical properties of the composites . Our research shows that combining expertise in the design and synthesis of organic materials (serving as templates or nanoparticle ligands), with expertise in nanoparticle synthesis, leads to the ability to arrange nanoparticles into desired morphologies [1,4]. Acknowledgements REINFORCE project (agreement no. First TEAM2016?2/15) carried out within the First Team program of the Foundation for Polish Science cofinanced by the European Union under the European Regional Development Fund. References  M. Bagi?ski, et al. Advanced Materials 1904581, 2020.  W. Lewandowski, et al. Advanced Materials 32:1905591, 2020.  P. Szustakiewicz, et al., ACS Nano 14:12918?12928, 2020.  M. Bagi?ski, et al. ACS Nano 15:4916?4926, 2021.
Authors : Shuqian Zhang
Affiliations : Shanghai Jiao Tong University
Resume : Surface enhanced Raman scattering (SERS) has attracted much research attention for the analysis and trace detection in the materials involving food safety, medical care and environmental pollution with high sensitivity and nondestructive data acquisition. In this work, we fabricated a gyroid-structured Au-Ag bimetal plasmonic material GSPMMs@Au by incorporating gyroid-structured silver periodic metallic materials (GSPMMs) with Au nanoparticles (NPs). By controlling the galvanic reaction time, we found that a highest surface plasmonic resonance enhancement can be acquired with the deposition time of 50 s (GSPMMs@Au50). Finite-difference time domain simulation results proves that the plasmonic coupling between the Au-Ag interface dramatically enhances the SERS performance. The SERS detection limit of bis(2-ethylhexyl) (DEHP) molecules based on GSPMMs@Au50 was 10-17 M, which is the best result among the recently published works. The fabrication method and SPR enhancement mechanism of this GSPMMs@Au bimetal systems can also be applied to other hierarchical metallic plasmonic systems.
Authors : Dorota Grzelak, David Vila Liarte, Wiktor Lewandowski
Affiliations : Faculty of Chemistry, University of Warsaw ul. L. Pasteura 1, 02-093 Warsaw CIC biomaGUNE Basque Research and Technology Alliance (BRTA) Paseo de Miramón 182, Donostia-San Sebastián 20014, Spain
Resume : Liquid crystalline phases exhibiting chiral properties received considerable attention in recent years. Their adaptive behavior and controllable structure makes them interesting for various applications in switchable optoelectronics. Incorporation of plasmonic nanoparticles into these materials enables strong chiral responses in the visible region. In my work I present an achiral liquid crystalline compound, that forms supramolecular, helical nanofilaments. Employing structurally compatible chiral dopants allowed for obtainng thin films with controlable chiral properties. Incorporation of a wide variety of gold nanoparticles of different sizes and morphologies into LC matrix resulted n their self-assembly in a helical manner, which translated on their optical features. Structural analysis of the materials confirmed that helical nanofilaments selectively decorated with nanoparticles were obtained. CD spectra obtained for the films confirmed achieving controled properties of the materials with desired handedness. Additionally, tunable maximum peak position was found for different designs of the nanocomposites.
Authors : A. Colombelli*, M.G. Manera, D. Lospinoso, R. Rella
Affiliations : IMM-CNR Institute for Microelectronic and Microsystems, Unit of Lecce, Campus Ecotekne, Via Monteroni, 73100 Lecce, Italy
Resume : In this work the capabilities of conventional nano-sphere lithography (NSL) technique have been extended to the fabrication of highly periodic arrays of sub-wavelength nano-holes into thin metal film. By combining dry etching processes of self-assembled monolayers of polystyrene colloids with metal physical deposition, the complete transition from increasing size triangular nano-prism to hexagonally distributed nano-holes onto thin metal film have been gradually explored. These highly tunable nano-structured materials exhibit interesting plasmonic properties which can be precisely modulated in a desired spectral region. The unconventional lithographic technique developed in this work is based on a very simple and reproducible bottom-up approach for the preparation of self-assembled monolayers of close-packed polystyrene particles of different size onto a liquid surface. This method enables the creation of highly ordered, colloidal crystals at the air/water interface over macroscopic areas, in the range of several square centimeters. This approach can be easily implemented, allowing the transfer of the assembled monolayers onto almost any kind of surface, thus making the procedure applicable to a broad range of nanoscale research. After the transfer onto a solid substrate, a post-treatment process based on oxygen plasma etching was applied in order to induce a progressive reduction of the spheres diameter and the formation of non-close packed array (NCPA) of PS nanosphere. An interesting approach based on simple optical absorbance measurements has been adopted for rapid and non-invasive inspections of the nano-sphere monolayer after the ion etching process. Enabling an indirect and accurate evaluation of colloids dimension on large area, this approach allows a low-cost and reproducible fabrication of plasmonic materials with specifically modulated optical and geometrical properties. The diameter of the spheres can be reduced in a controllable way to a desired size, while the nanosphere distance remain unchanged to keep constant periodicity within all masked area. The relationships between morphological and optical properties of the realized metal nano-structures have been theoretically and experimentally investigated. In particular, metallic nano-holes arrays have been widely studied to get a basic understanding and optimization of their optical properties, as well as their possible applications in several fields like surface-enhanced Raman scattering (SERS), surface-enhanced fluorescence spectroscopy, and the development of chemical sensors and biosensors.
Authors : Sylwia Parzyszek, Lawera Zuzanna, Bagiński Maciej, Wolska Joanna, Pociecha Damian, Lewandowski Wiktor
Affiliations : University of Warsaw, Faculty of Chemistry, Pasteura 1 St., 02-093 Warsaw
Resume : This work will aim to present liquid crystalline molecules as useful thermotropic templates for inducing and modulating optical properties of semiconductor and metallic nanocrystals (NCs). Three types of NCs: monodisperse, quasi-spherical InP/ZnS quantum dots , CdS small rods, and Au nanoparticles were synthesized and successfully functionalized with mesogenic ligands. The thermotropic organic coating of nanocrystals strongly defines distances to the nearest neighbor and influences optical properties. We have shown that functionalized NCs are able to form long-range ordered, reversibly reconfigurable structures in unary systems (achieving non-close packed symmetries) with the reversible shift of photoluminescence. Moreover, macroscopically oriented semiconductor NCs assemblies exhibit anisotropic fluorescence (FA). As obtained materials are also standing out from previously reported with one order of magnitude higher content of inorganic nanocrystals (w/w). In the next step, we introduced to our systems dimeric, bent-core molecules, forming helical nanofilaments. Due to the chemical compatibility of NCs’s organic coating and helical matrix, quasi-spherical and rod-like liquid crystalline NCs are attached to the helical matrix. We expect that achiral, fluorescent nanocrystals settled on helical nanofilaments will exhibit circularly polarized luminescence (CPL), and can be considered as a macroscopic scale source of CPL . Moreover, the phenomena should be strongly enhanced for rod-like CdS and binary semiconductor/metallic NCs systems.
Authors : Hamon, C.(1), Beaudoin, E.(1), Launois, P.(1) & Paineau, E.*(3).
Affiliations : (1) Université Paris-Saclay, CNRS, Laboratoire de Physique des Solides, 91405, Orsay, France
Resume : Doping liquid crystal (LC) phases with nanoparticles is a fast-growing field with potential breakthroughs due to the combination of the properties brought by the two components. For instance, noble metal nanoparticles NPs provide surface plasmon resonances that can be merged with the characteristic properties of the LC host for applications such as chiral plasmonic metamaterials or dynamic color displays [1-2]. One of the main challenges remains the long-term stability of the hybrid system, requiring complex functionalization of the nanoparticles at the expense of their self-assembly properties. We demonstrate a simple but robust method to dope LC phases of charged inorganic nanotubes by noble-metal NPs (Au, Ag, Pt & Pd) without the use of molecular additives . UV-visible spectroscopy confirm the stabilization of metallic nanoparticles on nanotubes over months. Meanwhile, the spontaneous formation of liquid-crystals phases induced by the nanotubes is observed, even after surface modification with metallic NPs. Small-angle X-ray scattering experiments reveal that the average interparticle distance in the resulting hybrids can be easily modulated by controlling electrostatic interactions. Potential application of our hybrids is illustrated for the preparation of transparent polymer nanocomposites films with a high degree of alignment.  M. Bagiński et al., Adv Mater, 2020, 32, 1904581  F. Neubrech et al., Sci Adv, 2020, 6, eabc2709  C. Hamon et al., JPCL, 2021, accepted
Authors : M.M. Majewska,b* E. Cruickshank,a K. Anderson,a J. M. D. Storey,a C.T. Imrie,a A. Makal, b D. Pociecha,b E. Gorecka,b
Affiliations : a. Department of Chemistry, School of Natural and Computing Sciences, University of Aberdeen, Meston Building, Aberdeen AB24 3UE (UK). b. Faculty of Chemistry, University of Warsaw, ul. Zwirki i Wigury 101, 02-089 Warsaw (Poland).
Resume : We present fascinating properties of a new series of bent core odd-membered mesogenic dimers. That group of materials, despite being achiral, has strong tendency to form helical structures, and here, for the first time we observed up to three of those in a single homologue series. Namely, helical nematic (NTB) phase for short homologues and its helical smectic equivalent (SmCTB) for longer ones. Finally, all these materials at room temperature exhibit filament B4 helical phase which is very rarely reported for dimeric molecules. We also show that this material has potential for morphology control through surface interactions. Structure and morphology of the compounds was studied using atomic force microscopy (AFM), scanning electron microscopy (SEM) as well as circular dichroism spectroscopy (CD). The presence of little-studied thio-linkage in terminal chain, which influences molecular birefringence, makes these molecules attractive for optical applications like liquid crystal lasers and lenses. The versatile properties present in a single group of homologues, show promise of broad applicability in optics, photonics and as a study case for better understanding of chirality, symmetry breaking and relationship between structure and properties in liquid crystals.
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S4 : TBD
Authors : Shannan Chang and Yaping Dan
Affiliations : Shanghai Jiao Tong University
Resume : Delta doping was traditionally formed by molecular beam epitaxial (MBE).[1,2] Here, we present a delta doping technique by self-assembled molecular monolayer annealed with nanosecond pulsed lasers. A monolayer of PCl3 was first self-assembled onto the patterned device layer of silicon-on-insulator (SOI) wafers. Xray photoelectron spectroscopy (XPS) indicates that the self-assembly leads to P atoms binding with Si in form of P(OSi)3. To prevent evaporation of P and possible external contamination, a 50nm thick SiO2 layer was deposited to cover the monolayer by atomic layer deposition (ALD) before a nanosecond excimer laser was applied to anneal the samples. A solid-to-liquid phase transition occurred as the laser power increases. A 20nm-thick crystalline silicon was epitaxially grown on the post-annealing samples after the SiO2 layer was removed in HF. Secondary ion mass spectrometry shows that most of dopants were driven into silicon by the pulsed laser annealing. For samples maintaining in solid phase but on the phase transition border, a high concentration (>1020 cm-3) of phosphorus dopants accumulate within a few atomic layers at the interface, forming a delta doping at atomic scale. Hall effect measurements indicate that only 30% of dopants in the delta-doping sample are electrically active. Further investigation is under way to address this issue. In short, the self-assembled molecular monolayer doping combined with pulsed laser annealing technique provides a new pathway for delta doping, which may find important applications in some niche area such as solar cells in which a delta doping is required to increase energy efficiency at the short wavelength solar spectrum. References  N. L. Mattey, M. Hopkinson, et al, Thin Solid Films 184 (1990) 15-19.  K. Ploog, Journal of Crystal Growth 81 (1987) 304-313.  J. Day, S. Senthilarasu, T. K. Mallick, Renewable Energy 132 (2019) 186-205
Authors : M. Perego, F. Caruso, E. Mascheroni, E. Arduca, R. Mantovan, S Kuschlan, K. Sparnacci, D. Antonioli, V. Gianotti, R. Chiarcos and Michele Laus
Affiliations : IMM-CNR Agrate Unit, Via C. Olivetti 2, I-20864 Agrate Brianza, Italy. Università del Piemonte Orientale ?A. Avogadro?, Viale T. Michel 11, I-15121, Alessandria, Italy
Resume : Deterministic doping of semiconductors represents a difficult challenge in advanced nano-electronic devices and alternative technologies for nanoscale doping of semiconductors are highly desirable. In this talk, we will present our recent results on the doping of silicon substrate by polymers terminated with a phosphorus containing moiety, benchmarking this alternative doping technology against conventional doping approaches. Some years ago, Ho et al. proposed the so-called monolayer doping (MLD) approach based on the formation of a self-assembled monolayer (SAM) of dopant-containing molecules on the semiconductor surface.[1-4] In particular, SAMs formed by diethyl 1-propylphosphonate (DPP) were widely studied highlighting the self-limiting behavior of the grafting process  and the limited incorporation of C and O impurities in the first monolayers of the Si crystal lattice. DPP was envisioned as an efficient dopant carrier for generating P dopant sources over deglazed and non-deglazed Si substrates. In our work a diethylphosphate moiety placed at one end of polymer chains was used to graft these macromolecules on an activated Si substrate forming a brush layer. The total dose of P deposited onto the non-deglazed Si substrate correlated with the degree of polymerization of the P terminated polymers. An efficient protocol was proposed to remove the polymeric chain by O2 plasma without affecting the tethered P-containing moieties on the surface. Repeated grafting/ashing cycles led to a cumulative increase, at constant steps, in the dose of P atoms.[8,9] The release of P atoms from the dopant source and subsequent diffusion through the SiO2 matrix into the Si substrate were investigated,  achieving high activation rates (80%) of injected P atoms. Integration of this technology with advanced lithographic technologies envisioned the possibility to move toward deterministic doping of semiconductors. In conclusion, a simple and low-cost bottom-up approach, based on polymers terminated with P containing moieties is proposed showing potential for the development of a mild technology for efficient doping of semiconductors.  J. C. Ho et al., Nat. Mater., 2008, 7, 62?67.  R. C. Longo et al., Adv. Funct. Mater., 2013, 23, 3471?3477.  J. Fu et al., AIP Adv., 2019, 9, 125219.  X. Gao, et al., Nat. Commun., 2018, 9, 118.  E. Arduca et al., Nanotechnology, 2016, 27, 075606.  Y. Shimizu et al., Nanoscale, 2014, 6, 706?710.  V. Gianotti et al., J. Anal. Appl. Pyrolysis, 2017, 128, 238?245.  M. Perego et al., ACS Nano, 2018, 12, 178?186.  M. Perego et al., J. Mater. Chem. C, 2020, 8, 10229.  M. Perego et al., J. Mater. Chem. C, 2021, 9, 4020.
Authors : Abhishek Kumar (1), Aurélie Lecestre (1), Jonas Müller (1), Guilhem Larrieu (1),
Affiliations : (1) LAAS-CNRS, Univ. de Toulouse, INP, 7 Avenue du Colonel Roche, F-31400 Toulouse, France
Resume : As the size of MOS transistors is being scaled down to few nanometers, the gate-all-around transistor has become the most promising candidate for devices according to the International Roadmap for Devices and Systems [IRDS]. Vertical integration offers great promises, by moving from planar to real tri-dimensional circuit design. Junction-less architecture, where the nanowire (NW) channel is homogenously highly doped, simplifies the fabrication of the device, in particular the S/D region engineering. The focus of the paper is the engineering of free-standing homogenous doped nanostructures compatible with high performance of vertical nano-transistors. The nanostructure patterning is based on a large-scale top-down approach, including (i) nanomask structuration by e-beam lithography of a negative tone resist (ii) anisotropic plasma etching to transfer the mask into the Si substrate (iii) sacrificial wet oxidation to smooth the sidewall and decrease the NW dimension. Three configurations of samples have been studied: (S1) highly doped Si wafers (3E19 boron/cm3), (S2) localized high doped wells (3E19 boron/cm3) on high resistive (HR) wafer made by localized ion implantation and (S3, S4) HR Si wafer. The doping level does not affect the patterning of the nanostructures, but increases their oxidation rate, which is larger in highly doped samples (20 % for 50 nm of diameter, 19 % for 20 nm of diameter). Moreover, the NW patterning on localized implantation wells shows the formation of large structural defects in these areas (size = 0.4 µm, density = 1 defect/µm2) which follows the crystalline orientation of the substrate. The size of the defects is increased after oxidation, larger than 0.8 µm in width and 0.5 µm in depth. To go further, (S4) is a localized implantation, in the same condition as S3 but made after the NW patterning, which does not generate any defects and shows a perfectly defect-free surface. Finally, vertical scaled gate-all-around transistors (Gate length = 18 nm) have been fabricated on the doped nanowires obtained on S1 and S4. Both configurations show very high drive current but S4 exhibits a poor Ion/Ioff ratio (1 decade) with a high off current in comparison to S1 (Ion/Ioff ratio up to 5 decades). It is speculated that a radial dopant segregation at the NW surface occurs when the dopant implantation followed by the activation annealing at high temperature are performed after the NW patterning. This study gives some new inputs on the patterning of highly doped nanowires from basic science but also some guidelines from an integration scheme point of view.
Authors : Stefano Kuschlan (1), Michele Perego (1), Gabriele Seguini (1), Michele Laus (2), Valentina Gianotti (2), Riccardo Chiarcos (2)
Affiliations : (1) Institute for Microelectronics and Microsystems, CNR, Italy; (2) East Piemonte University, Italy.
Resume : Self-assembled monolayers (SAM) of molecules have a broad range of application: from biosensors to solar cells and thin-film transistors. SAMs of dopant containing molecules have been proposed as a mild and simple alternative to ion implantation in order to obtain conformal doping of 3D complex nanostructures. The control on the amount of dopant can be achieved varying the steric encumbrance of the molecules. Using chains of PS or PMMA with a narrow polydispersity and terminated with a P containing moiety it is possible to control the amount of P deposited onto a SiO2 surface and, iterating this process, it is possible to further increase the P deposited, in the range from 2 x1013 to 3 x1014 atoms/cm2 . A subsequent thermal treatment is used to inject and activate the dopants in the Si substrate . Integration with advanced lithographic technique could provide the possibility to control the lateral distribution of the dopants over the substrate at the nanoscale. Periodic distributions of dopants could be used to realize artificial crystal lattices  or, taking advantage of the non-uniform dopant distribution, novel devices for non-conventional computational tasks . In this work P terminated PS homopolymers are combined with self-assembled block copolymer (BCP) thin films of polystyrene-b-polymethylmethacrylate (PS-b-PMMA) to demonstrate the capability to modulate P distribution over the substrate at the nanoscale. Upon deposition and grafting of the P terminated molecules over the substrate, a PS-b-PMMA BCP thin film is deposited by spin-coating on top of the sample and annealed at high temperature (250°C) to promote a phase separation and create an array of out of plane hexagonally packed PMMA cylinders with diameter of 25 nm inside a PS matrix. After the selective removal of the PMMA cylinders, a 5 nm thick layer of SiO2 is evaporated to create a protective capping on top of the exposed areas. Finally, the remaining PS nanostructure and the non-protected P terminated moieties are removed using piranha solution, resulting in an array of SiO2 disks on top of nanometer wide areas with high concentration of P. The effective amount of P over the surface is evaluated by means of TOF-SIMS and XPS analysis. Upon injection of P atoms into the underlying Si substrate, the distribution of active dopants is evaluated via sheet resistance and Hall effect measurements to study the effect of the periodic modulation of P on charge transport in the Si substrate.  M. Perego et al., ACS Nano, vol. 12, no. 1, pp. 178–186, 2018  M. Perego et al., J. Mater. Chem. C, vol. 8, no. 30, pp. 10229–10237, 2020  S. Yue et al., Phys. Rev. B, vol. 102, no. 20, pp. 1–5, 2020  T. Chen et al., Nature, vol. 577, no. 7790, pp. 341–345, 2020
Authors : A.Valdenaire, M. Stoffel, X. Devaux, E. André, C. Carteret, A. Bouché, M. Vergnat, H. Rinnert
Affiliations : Université de Lorraine, CNRS, IJL, F-54000 Nancy-France ; Université de Lorraine, CNRS, IJL, F-54000 Nancy-France ; Université de Lorraine, CNRS, IJL, F-54000 Nancy-France ; Université de Lorraine, CNRS, LCPME, F-54000 Nancy-France ; Université de Lorraine, CNRS, LCPME, F-54000 Nancy-France ; Université de Lorraine, CNRS, IJL, F-54000 Nancy-France ; Université de Lorraine, CNRS, IJL, F-54000 Nancy-France ; Université de Lorraine, CNRS, IJL, F-54000 Nancy-France
Resume : Group IV-V based semiconductor alloys have recently gained a renewed interest due to their lamellar structure. This property may open the route toward novel 2D group IV-V materials, which are expected to exhibit original electronic and optoelectronic properties. In the case of 2D-SiP, an indirect to direct bandgap transition has been predicted when moving from the bulk to the corresponding 2D material. While some theoretical works are available on 2D-SiP, there is still no report concerning the synthesis of 2D-SiP by mechanical exfoliation of SiP thin films. In this work, we investigate Si:P thin films obtained by co-evaporation in ultra-high vacuum. The films were prepared by co-evaporation of Si from an e-beam gun and P from a GaP decomposition source. The microstructural properties were investigated by energy filtered transmission electron microscopy (EFTEM), scanning transmission electron microscopy (STEM), energy dispersive and electron energy loss spectroscopies (EDS and EELS). The thermal crystallization of the films was followed by Raman spectroscopy. When considering Si:P thin films containing 40 at. % of P, we show that annealing at temperatures larger than 950°C leads to the formation of crystalline phases. Density functional theory calculations of the vibrational modes allow us to identify unambiguously the formation of SiP in our films. Both EDS as well as EELS allow us to identify a plasmon signature of the SiP phase. EFTEM characterizations reveal the coexistence of both Si and SiP areas in the films having sizes of a few microns. High resolution transmission electron microscopy imaging gives a clear evidence of the lamellar structure. Finally, EELS measurements allow us to achieve a spatially resolved chemical mapping for both Si and P atoms, which is in good agreement with the expected atomic structure for orthorhombic SiP. Our results are an important first step on the way to obtain 2D-SiP, a promising new material for which a direct bandgap has been predicted.
Authors : N. CHERY (1), V. PAILLARD (1), J. M. POUMIROL (1), M. ZHANG (1), E. SCHEID (2), R. MONFLIER (2), N. MALLET (2), G. LARRIEU (2), S. KERDILES (3), P. ACOSTA-ALBA (3), A.-S. ROYET (3), A. GIBA (4), H. RINNERT (4), C. BONAFOS (1), and F. CRISTIANO (2)
Affiliations : (1) CEMES, 29 Rue Jeanne Marvig, 31055 Toulouse, France (2) LAAS, 7 Avenue du Colonel Roche, 31400 Toulouse, France (3) LETI, 17 Avenue des Martyrs, 38054 Grenoble, France (4) IJL, Campus Artem, 2 allée André Guinier, 54011 Nancy, France
Resume : The appearance of localized surface plasmon resonance in highly doped Si nanocrystals (NCs) has opened a new field of applications for Si . However, doping nano-Si remains a challenge due to self-purification effects . If most of the highly doped Si-NCs are elaborated by bottom up processes , new routes involving top down approaches, as low energy electron lithography of heavily doped ultra-thin SOI wafers, can be appealing. In this case, a prerequisite step consists in the optimization of the top Si layer doping process. In this work, a thorough study of the heavy doping of thin Si films is described. UV nanosecond laser annealing (UV-NLA) is used to achieve an efficient dopant activation . Ultra-thin SOI wafers with 23 nm-thick Si top layers have been implanted with phosphorus at 4 keV to different high doses and the NLA conditions have been optimized by numerical simulations . The recrystallisation processes and P redistribution in the Si layer have been investigated as a function of the laser energy density by STEM-HAADF/EDX. Active dopant concentrations as high as 3 at. % have been measured by Hall effect and deduced from FTIR measurements coupled with Drude model based calculations . Pile-up of P atoms at the surface has been observed together with a complete crystallization and a decrease of sheet resistance for optimized LTA conditions.  D. J. Rowe et al. Nano Lett. 13, 1317 (2013)  I. Marri et al. Prog. Surf. Sci. 92, 375 (2017)  K. Huet et al. MSSP 62, 92 (2017)  A.S. Royet et al. SISPAD (2019)  J.-M. Poumirol et al. ACS Photonics 8, 1393 (2021)
S5 : TBD
Authors : C. BONAFOS1, J. M. POUMIROL1, C. MAJOREL1, N. CHERY1, M. ZHANG1, C. GIRARD1, N. MALLET2, R. MONFLIER2, F. CRISTIANO2, G. LARRIEU2, P. R. WIECHA2, S. KERDILES3, P. ACOSTA-ALBA3, A.-S. ROYET3 and V. PAILLARD1
Affiliations : 1CEMES, 29 Rue Jeanne Marvig, 31055 Toulouse, France; 2LAAS, 7 Avenue du Colonel Roche, 31400 Toulouse, France; 3LETI, 17 Avenue des Martyrs, 38054 Grenoble, France
Resume : The appearance of localized surface plasmon resonance (LSPR) in highly doped Si nanostructures opens a new field of applications, with Si-based plasmonic tunable over a wide infrared range . We present the experimental realization of ordered arrays of phosphorus hyper-doped silicon nanodisks, which exhibit a LSPR. This top-down approach consists at optimizing the doping of thin Silicon On Insulator (SOI) layers, by means of Laser Thermal Annealing, in which dense hexagonal arrays of nanometer size disks are produced by low energy electron beam lithography and reactive ion etching. Active dopant concentration in the bulk SOI as high as 3 at. % have been deduced from Fourier Transform Infra-Red (FTIR) spectroscopy in good agreement with Hall measurements. Intense mid to near-IR LSPR have been measured in FTIR on the doped nanodisks metasurfaces. The plasmon is widely tunable in a spectral window between 2 and 5 μm by simply adjusting the free carrier concentration between 1020 and 1021 cm−3 . Our numerical simulations performed with the Green Dyadic Method (GDM)  show an excellent agreement with the experimental data and provide physical insights on the impact of the nanostructure shape as well as of near-field effects on the optical properties of the metasurface. Our results open highly promising perspectives for integrated all-silicon-based plasmonic devices for chemical or biological sensing or for thermal imaging.  D. J. Rowe et al. Nano Lett. 13, 1317 (2013).  J. M. Poumirol et al. ACS Photonics 8, 5, 1393-1399 (2021)  C. Majorel et al., Optics Communications 453, 124336 (2019).
Authors : (1) S.Guehairia, R. Demoulin, P. Pareige, E. Talbot, (2) F. Gourbilleau, J. Cardin, C. Labbé, (3) M. Carrada
Affiliations : (1) Normandie Univ, UNIROUEN, INSA Rouen, CNRS, Groupe de Physique des Matériaux, 76000 Rouen, France (2) CIMAP, Normandie Univ, ENSICAEN, UNICAEN, CEA, CNRS, CIMAP, 14000, Caen, France (3) CEMES-CNRS, Université de Toulouse, 29 rue Jeanne Marvig, BP 94347, F-31055 Toulouse, France
Resume : Rare-earth (RE) doping of silicon oxide matrix [1-2] have attracted a lot of attention for the development of new photonics applications  and particularly Erbium because of its emission at 1,54 micrometer used in optical fiber. Optical properties of RE-doped Si-based matrix are strongly correlated with the nanostructure . In order to overcome the low solubility of RE in silicon oxide matrix, the control of growth of Erbium silicates phases, which evidenced an intense luminescence [5-6], can be a promising approach. In present work, we have studied the relationship between high doping level of Er in silicon oxide matrix, the atomic scale location of Er atoms, the matrix phases chemistry and luminescence properties on samples with different Er contents and under different annealing processes. These experiments have been performed using photo- and cathodo-luminescence and atom probe tomography. We observe that in both case a similar nanostructure composed of an interconnected erbium silicates and silica phases at the nanoscale. The influence of the annealing process and the Er concentration will be discussed in regard of nanostucturation of the sample and optical properties.  A. Kenyon et al. Semiconductor Science and Technology, 20 (2005) 65  D. Debajyoti et al. Phys. Chem. Chemical Physics,17 (2015) 5063  N. Daldosso et al. Nanosilicon (2008) 314  M. Fujii et al. J. Appl. Phys, 84 (1998) 4525  G. Beainy et al. J. Alloys and Compounds, 755 (2018) 55  R. Lo Savio et al. Appl. Phys. Let., 93 (2008) 021919
Authors : E. Talbot (1), S. Guehairia (1), R. Demoulin (1), P. Pareige (1), D. Muller (2), D. Mathiot (2), H. Rinnert (3)
Affiliations : (1)Normandie Univ, UNIROUEN, INSA Rouen, CNRS, Groupe de Physique des Matériaux, 76000 Rouen, France (2)ICube Laboratory, Université de Strasbourg and CNRS, B.P. 20, 67037 Strasbourg cedex, France (3)Université de Lorraine, UMR CNRS 7198, Institut Jean Lamour, BP 70239, 54506 Vandœuvre-lès-Nancy, France
Resume : Performing effective doping of silicon nanocrystals (Si-ncs) embedded in SiO2 became a relevant subject in order to develop new plasmonic devices. In semiconductors, a perfect control of the charge density allows to tune the spectral position of the Localized Surface Plasmon Resonance. It has been shown that, depending of the elaboration conditions and their environments, P or B doped Si-ncs can exhibit a plasmon resonance. However, in low dimensional systems, the position of the impurity (in the core of Si-ncs, at the Si/SiO2 interface or in the surrounding matrix) can strongly affect these properties. Therefore a precise control of the location of impurities is necessary. In this work, P and B doped Si-ncs embedded in SiO2, elaborated by ion implantation or evaporation, have been investigated using Atom Probe Tomography. This technic allowed us to perform 3D mapping at the atomic scale to investigate the precise location of impurities and the Si clustering characteristics. We evidenced a clear difference on the location of impurities in Si-ncs. On one hand, P atoms are efficiently introduced in the core of every single Si-ncs allowing a high doping of these Si-ncs. On the other hand, B atoms remain in majority in the matrix, at the Si-nc/SiO2 interfaces or in shells surrounding Si-ncs. Finally, photoluminescence measurements highlight that in P as in B doped Si-ncs, these locations of impurities lead to a quenching of the Si-ncs luminescence.
Authors : M. Zhang 1, N. Chery 1, J. M. Poumirol 1, V. Paillard 1, H. Rinnert 2, X. Devaux 2, Alaa El-Din Giba 2, R. Demoulin 3,4, E. Talbot 3, R. Monflier 4, F. Cristiano 4, A. S. Royet 5, P. Acosta-Alba 5, S. Kerdiles 5, T. Hungria 6, F. Gourbilleau 7 and C. Bonafos 1.
Affiliations : 1. CEMES-CNRS, Université de Toulouse, Toulouse, France; 2. Université de Lorraine, CNRS, IJL, F-54000 Nancy, France; 3. GPM-CNRS, Université de Rouen Normandie, Saint Etienne du Rouvray, France; 4. LAAS-CNRS, Université de Toulouse, Toulouse, France; 5. LETI-CEA, MINATEC Campus Université Grenoble Alpes, Grenoble, France; 6. UMS 3623 - Centre de Micro-Caractérisation Raimond Castaing, Toulouse, France; 7. CIMAP, Normandie Université, ENSICAEN, CEA, CNRS, Caen, France;
Resume : As an emerging new class of plasmonic nanomaterials, heavily doped semiconductor nanocrystals (NCs) that possess infra-red Localized Surface Plasmon Resonance (LSPR) tunable with the doping concentration, have recently received great attention . Silicon has been chosen for its compatibility with the CMOS technology. However, doped Si-NCs suffer from oxidation and surface modification, which may negatively impact their plasmonic properties . For this reason, the Si nanostructures fabricated in this work are embedded in an insulating matrix (SiO2) that preserves the NCs from aging. In this work, highly phosphorus (P) doped small Si nanocrystals (3 nm) have been fabricated by sequential low energy ion implantation of Si and P, followed by Rapid Thermal Annealing (RTA). The impact on the P doped Si-NCs formation and optical properties of separating (or not) the NC nucleation from the dopant activation, as well as their thermal budget, have been investigated. The structural characterization by Transmission Electron Microscopy indicates that after P doping and further annealing, the Si-NCs remain crystalline with no effect of the P implant on the NCs average size. STEM-Energy Dispersive Spectroscopy and Atom Probe Tomography both evidence that P atoms (up to 4.2%) are efficiently introduced inside the Si-NCs. Photoluminescence (PL) spectroscopy shows a decrease of the intensity of the PL peak characteristics of Si-NCs after P doping that could be ascribed to Auger recombination, suggesting a partial activation of P inside the NCs . Finally, FTIR measurements evidence for the first time the generation of IR LSPR from the P doped Si-NCs embedded in silica after a specific passivation of Si-NCs surface defects by forming gas annealing.  Luther J M, Jain P K, Ewers T, et al. Nature materials, 2011, 10(5): 361-366.  Kramer N J, Schramke K S, Kortshagen U R. Nano letters, 2015, 15(8): 5597-5603.  Pi X D, Gresback R, Liptak R W, et al. Applied Physics Letters, 2008, 92(12): 123102.
Authors : Zh.V. Smagina (1), V.A. Zinovyev (1), M.V. Stepikhova (3), S.A. Rudin (1), A.V. Peretokin (3,4), A.V. Novikov (3), A.V. Dvurechenskii (1, 2)
Affiliations : 1) Rzhanov Institute of Semiconductor Physics, Siberian Branch of Russian Academy of Sciences, 630090 Novosibirsk, Russia; 2) Novosibirsk State University, 630090 Novosibirsk, Russia; 3) Institute for Physics of Microstructures Russian Academy of Sciences, 603950 Nizhny Novgorod, Russia; 4) Institute of Nuclear Power Engineering and Applied Physics, Alekseev State Technical University of Nizhny, Novgorod, 603155 Nizhny Novgorod, Russia.
Resume : Ge/Si heterostructures with quantum dots (QDs) are considered as one of the most promising systems for creating silicon-based light-emitting devices. For practical applications the precise positioning of QDs is very important. In this work, we present experimental and simulation results on the self-organization of spatially ordered Ge(Si) QDs during heteroepitaxial growth on the pit-patterned SOI (silicon-on-insulator) substrates. The positions of pits were arranged to the square and hexagonal lattices with a varying spacing. It was shown that the location of GeSi QDs subsequently grown on the pit-patterned Si substrates depends on spacing for the both lattice types. In the case of the small spacing GeSi QDs are located mainly inside the pits, while for the larger inter-pit distance the groups of GeSi QDs at the pit periphery is also observed. The effect of QDs growth, first inside the pits, then at their periphery was reproduced by Monte Carlo simulations of Ge heteroepitaxial growth on the pit-patterned Si substrates. We also studied the photoluminescent (PL) properties of structures with GeSi QDs arranged around the pits on SOI substrate. It was found that, at certain parameters of an ordered array of pits (the period of the location of the pits, the pit shape, and depth), a significant increase of the QD luminescence intensity occurs, in same way as in the case of an array of QDs embedded in a photonic crystal (PhC). The array of pits plays the role of a PhC, which is confirmed by the appearance of narrow peaks in the PL spectra, which can be associated interaction of QD emission with the PhC modes. This work is funded by the RSF grant # 21-72-20184.
Authors : I Stavarache, C. Palade, O. Cojocaru, VS Teodorescu, T. Stoica, ML Ciurea
Affiliations : National Institute of Materials Physics, 405A Atomistilor Street, 077125 Magurele, Romania
Resume : GeSi is one of the most studied semiconductor alloy, with applications in microelectronics, optoelectronics and integrated photonics benefiting from tuning electrical and optical properties by varying the nanocrystals (NCs) size, composition and density. GeSi NCs boost the efficiency of light emission and band-edge absorption in GeSi large crystals by quantum confinement. A versatile technique is to embed Ge-rich GeSi NCs (with Ge content from 50% to 100%) in oxides, and this we achieve by magnetron sputtering for layers deposition. GeSi NCs formation is achieved eirher on heated substrates during deposition or by rapid thermal annealing after the deposition process [1,2]. We obtained photodetectors with Ge NCs in SiO2 with high responsivity of 2.42 A/W and 445% quantum efficiency, and 1325 nm cut-off wavelength. We also fabricated sensors with GeSi NCs embedded in SiO2 with significantly improved parameters, i.e. cutoff wavelength that is significantly extended to 1630 nm in SWIR and higher photoresponsivity of 9.35 A/W at 100 K, and even 1345 nm sensitivity limit and 5.23 A/W responsivity at room temperature. We employ DFT for finding bandgap diameter dependence of GeSi NCs for different Ge contents and bigger diameters, these being useful for design and characterization of GeSi NCs-based optical sensors . These results prove the great potential of GeSi NCs-based sensors and photodetectors to be used in discrete and integrated devices. We have developed a sensor application based on the high VIS-SWIR photoresponsive GeSi NCs films, that discriminates between different slippery road conditions, in the frame of M-Era.Net project PhotoNanoP awarded as “Success Story” .  I Stavarache, C Logofatu, MT Sultan, A Manolescu, HG Svavarsson, VS Teodorescu, ML Ciurea, Sci Rep 2020, 10, 3252  I Stavarache, VS Teodorescu, P Prepelita, C Logofatu, ML Ciurea, Sci Rep 2019, 9, 10286  O Cojocaru, AM Lepadatu, GA Nemnes, T Stoica, ML Ciurea, Sci Rep 2021, accepted  C Palade, I Stavarache, T Stoica, ML Ciurea, Sensors 2020, 20, 6395
Authors : M.V. Stepikhova1, A.V. Peretokin1, S.A. Dyakov2, A.V. Novikov1,3, Zh.V. Smagina4, V.A. Zinovyev4, S.A. Rudin4, A.V. Dvurechenskii4
Affiliations : 1 Institute for Physics of Microstructures, RAS, 603950 Nizhny Novgorod, Russia. 2 Skolkovo Institute of Science and Technology, Moscow 121205, Russia. 3 Nizhny Novgorod State University, 603950 Nizhny Novgorod, Russia. 4 Rzhanov Institute of Semiconductor Physics, SBRAS, 630090 Novosibirsk, Russia
Resume : In this report, we discuss the results of experimental studies carried out for two-dimensional photonic crystals realized on Si structures with the self-assembled Ge(Si) nanoislands. These structures seems to be promising for realization of an efficient light-emitting source on Si chip. Si structures with the self-assembled Ge(Si) nanoislands are fully compatible with CMOS technology, could be easily fabricated and belong the emissivity within practically important wavelength range of 1.2–1.6 µm. However, their emission efficiency remains insufficient for device applications. In this report, we will show that this situation can be significantly improved by incorporating Ge(Si) nanoislands into photonic crystals. Making use the interaction phenomena of an active media with the photonic crystal modes, the emissivity of these structures can be increased by more than an order of magnitude. To integrate Ge(Si) nanoislands into photonic crystals, two approaches were considered, which differ by the ordering procedure of Ge(Si) nanoislands inside the photonic crystal. In the first one, Ge(Si) nanoislands were ordered during the growth on a pre-patterned Si substrate, and photonic crystals were formed on the structures with the already ordered nanoislands. In the second one, photonic crystals themselves served as templates for the ordered growth of Ge(Si) nanoislands [1,2]. In both cases, the strong, by more than an order of magnitude, increase of Ge(Si) nanoislands luminescence intensity of has been observed, though for the distinct ordering and photonic crystal parameters. The luminescence features observed in these structures are discussed in terms of the nanoislands – photonic crystal modes interaction phenomena. The specificity of modes involved in the luminescence response of these structures was analyzed by means of the micro-photoluminescence method in directional diagram geometry. This work is funded by the RSF grant # 21-72-20184.  Zh.V. Smagina, V.A. Zinovyev, E.E. Rodyakina et al., Semiconductors, 53(10), 1329 (2019).  A.V. Novikov, Zh.V. Smagina, M.V. Stepikhova et al., Nanomaterials 11, 909, (2021).
S6 : TBD
Authors : Bartlomiej Graczykowski
Affiliations : Faculty of Physics, Adam Mickiewicz University, Uniwersytetu Poznanskiego 2, 61-614 Poznan, Poland.
Resume : Colloidal crystals (CCs) realized by self-assembled polymer nanoparticles are volumetric and low-effort materials that found applications in surface coatings or photonics and phononics for light and hypersound manipulation, respectively. The mechanical properties of CCs result from the elasticity of the nanoparticles as well as interfacial forces between thereof. Typically, self-assembled nanoparticles are weakly bonded. Therefore, the fragility of polymer CCs remains a critical issue as it may result in malfunctioning of the devices and the releasing of micro/nano contaminants into the environment. To date, several approaches have been proposed to make polymer CCs mechanically robust: plasma and chemical assisted treatments, direct UV irradiation, and thermal treatment just below the glass transition temperature. This work discusses uniform mechanical reinforcement and tunability of polystyrene (PS) CCs employing supercritical fluids. This method, termed “cold soldering”, allows structural strengthening at temperatures well below the glass transition, which is especially important for thermosensitive systems. Cold soldering combines two relevant effects: plasticization of particles surface and compressive hydrostatic pressure. It results in permanent physical contact between the nanoparticles and maintains the periodic arrangement of the colloidal crystal. To monitor in-situ the mechanical vibrations of the crystal, we employed Brillouin light scattering. Using this non-destructive, contactless technique, we determined preferential pressure, particle size, temperature, and time range for soldering. References:  V. Babacic et al., J. Colloid Interface Sci., 579, 786 (2020)  B. Graczykowski et al., Nano Lett. 20, 1883−1889, (2020) Acknowledgments: The work was supported by the Polish National Science Centre (UMO-2018/31/D/ST3/03882) and Foundation for Polish Science (POIR.04.04.00-00-5D1B/18).
Authors : O. Rasoga 1, C. Breazu1, M. Socol1, A.-M. Solonaru2, L. Vacareanu2, G. Petre1, N. Preda1, A. Stanculescu 1, F. Stanculescu 3, G. Socol 4, M. Girtan5, A. Doroshkevich6
Affiliations : 1National Institute of Materials Physics, 405A Atomistilor Street, P.O. Box MG-7Magurele, 077125 Romania, 2P. Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487, Iasi, Romania, 3University of Bucharest, Faculty of Physics, 405 Atomistilor Street, P.O. Box MG-11, Magurele, 077125 Romania , 4National Institute for Laser, Plasma and Radiation Physics, Str. Atomistilor, Nr. 409, PO Box MG-36, Bucharest, 077125, Romania, 5Laboratoire LPHIA, Université d’Angers, LUNAM, 2 Bd. Lavoisier 49045, Angers, France, 6Joint Institute for Nuclear Research, 6, Joliot-Curie str., 141980 Dubna, RUSSIA
Resume : The use of nanostructured electrodes represents an alternative for improving the performances of opto-electronic devices because can favor both the manipulation of light through photonic/plasmonic effects and the charge carrier transport and collection through the modification of the electric field and increase in the collection surface of the electrodes. On the other hand, the limitation in the charge carrier injection and transport induced by the reduced diffusion length of exciton and reduced interfacial contact area between donor and acceptor in the classical bi-layer organic heterostructure can be overpassed using as active layer blends of donor and acceptor materials as bulk heterojunctions (BHJs). This paper presents a comparative study on the properties of organic heterostructures with BHJ active layer made of arylenvinylene based polymer with carbazol substituted unit in 2,7 and 3,6 positions as donor and fullerene derivative (C61) or non-fullerene (perylene diimide) as acceptor mixed in the ratio (1:2), deposited by Matrix Assisted Pulsed Laser Evaporation between Al (flat and nanopatterned) and ITO electrodes. The 2D periodic array of cylindrical pillars with a periodicity of 1.1 m and diameter of 400 nm realized with UV Nanoimprint Lithography was covered by the Al layer showing an inflorescence-like morphology. The nano-patterning of the Al electrode is preserved by the blend layer, independently of acceptor type, but the geometry of nano-patterning is slightly modified. The BHJ layers deposited on both flat and nanostructured Al have been characterized by spectroscopic (Reflectance, PL) and microscopic (AFM) methods and the effect of nano-patterning and type of acceptor on the optical and electrical properties has been investigated. The high roughness associated with the preservation of the nano-patterning and the light trapping by multiple scattering of the radiation inside the nanostructures led to lower reflectance of the layers deposited on nanostructured Al. A decrease in the emission intensity has been revealed by the nanostructuring of the Al layer for the heterostructures prepared with non-fullerene acceptor and longer conjugation length polymer (carbazol unit substituted in positions 3,6) donor at excitation both with UV and Vis radiation. The lower emission of the layer containing C61 compared to the layer containing perylene diimide is associated with the quenching of the luminescence. I-V characteristics in dark have revealed an injector contact behavior for all heterostructures Al/BHJ layer/ITO. The nano-patterning of Al electrode caused an increase in current for the heterostructures made both with non-fullerene and fullerene acceptor. The electrical behavior of the herostructures with BHJ layer containing perylene diimide is affected by the donor polymer conjugation length, the best effect of nano-patterning being obtained with a donor from the arylenevinylene based polymer characterized by a lower conjugation
Authors : Dániel Péter Szekrényes, Dániel Zámbó, András Deák
Affiliations : Photonics Department, Centre for Energy Research
Resume : Molecular layers at the surface of nanoparticles are of central importance both for basic and applied research. They determine how they can be process and how they interact with their environment, let it be molecules, other particles or even living matter. In the presentation it is shown how microspectroscopy can be utilised to follow ligand exchange processes by monitoring the chemical interface damping associated plasmon resonance linewidth changes of individual gold nanorods. It is shown, that even for small thiol molecules, the charged nature of the ligands has a profound effect on the outcome of the ligand exchange. By careful control of the thiol molecules, tip-selectively surface modified gold nanorods can be prepared. The in in-situ microscopy approach (the particles are investigated in their native, liquid environment) also offers the possibility to detect the assembly of these individual nanoparticles. By controlling the colloidal interaction of patchy particles’, the targeted preparation of certain nanoparticle arrangements becomes possible, as well as eventual structural rearrangements of the assemblies upon drying can be verified. Acknowledgement: National Research, Development and Innovation Office – NKFIH KH129578, FK128327 Key references: (1) Szekrényes, D. P.; Kovács, D.; Zolnai, Z.; Deák, A. Chemical Interface Damping as an Indicator for Hexadecyltrimethylammonium Bromide Replacement by Short-Chain Thiols on Gold Nanorods. J. Phys. Chem. C 2020, 124 (36), 19736–19742. https://doi.org/10.1021/acs.jpcc.0c04629. (2) Szekrényes, D. P.; Pothorszky, S.; Zámbó, D.; Deák, A. Detecting Spatial Rearrangement of Individual Gold Nanoparticle Heterodimers. Phys. Chem. Chem. Phys. 2019, 21 (19), 10146–10151. https://doi.org/10.1039/C9CP01541H. (3) Pothorszky, Sz.; Zámbó, D.; Deák, T.; Deák, A. Assembling Patchy Nanorods with Spheres: Limitations Imposed by Colloidal Interactions. Nanoscale 2016, 8 (6), 3523–3529. https://doi.org/10.1039/C5NR08014B.scale 2016, 8 (6), 3523–3529. https://doi.org/10.1039/C5NR08014B.
Authors : Cristina Chircov, Alexandru Mihai Grumezescu, Alexandra Catalina Birca, Anton Ficai, Bogdan Stefan Vasile, Ecaterina Andronescu
Affiliations : Department of Science and Engineering of Oxide Materials and Nanomaterials, Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest
Resume : The aim of our research study was to implement a microfluidic platform for the development of amino- and carboxyl-functionalized iron oxide nanoparticles. Specifically, the microfluidic lab-on-chip device which has demonstrated to allow for the modulation of nanoparticle size, shape, crystallinity, and surface charge was further used to investigate its efficiency in controlling nanoparticle functionalization. The lab-on-chip device was assembled by fixing three poly(methyl methacrylate) plates of the same size, using 20 M4 screws (0.5 mm pitch, 4 mm diameter) and tightened at 1.5–2 Nm. The polymeric chips comprising a top layer (with inlets for sample injection and screw orifices for binding), a middle chip (with the cross-junction channel and screw orifices), and a bottom chip (with an outlet and screw orifices) were constructed through a laser cutting machine. The solution containing Fe(II) and Fe(III) precursors and the -NH2 and -COOH functionalization agents at different concentrations were injected through the central inlet. The solution of NaOH 1M used as a precipitating agent was injected through the side channels at 150 mL/h. The dispersions containing the functionalized iron oxide nanoparticles were dripped from the outlet, washed, and dried for 48 h at 40°C. After the synthesis process, the morphology, structure, composition, and functionality of the so-obtained functionalized nanoparticles were determined through scanning electron microscopy and transmission electron microscopy, selected area electron diffraction, X-ray diffraction, energy-dispersive X-ray spectroscopy, Fourier-Transform infrared spectroscopy, and dynamic light scattering. Furthermore, the thermogravimetric analysis was used in order to establish the functionalization degree of the nanoparticles. Results proved that the nanoparticles consisted of a single mineral phase, namely iron oxide, and a dimensional uniformity with sizes lower than 10 nm and uniform spherical shapes were obtained in all nanoparticle samples. Moreover, the thermogravimetric results proved a concentration-dependent functionalization degree for both amino- and carboxyl-functionalized iron oxide nanoparticles. In this manner, we can conclude that the microfluidic lab-on-chip device represents a promising tool that allows for the control of the amino- and carboxyl-functionalization process. Hence, the lab-on-chip device could be further used in nanomaterial-based pharmacological applications, as it permits the modulation of the pharmacokinetics and pharmacodynamics of the envisaged drug delivery systems.
Authors : Thomas Hantschel, Giulia Scamporrino, Masoud Dialameh
Affiliations : imec, Kapeldreef 75, B-3001 Leuven, Belgium
Resume : Nanoscopic sharp tips have become a crucial component and workhorse for carrying out scanning probe microscopy (SPM) measurements with nanometer precision and resolution. A major limitation of common SPM analysis since its invention in the 1980ies has been the need to frequently replace worn-out tips. This manual tip replacement is not only time-consuming (~10 min/tip), costly (20-100 Euro/tip) and cumbersome but it represents also an unwanted interruption of the scanning experiment and is a major roadblock for SPM to tackle new analysis challenges. Therefore, we developed so-called reverse tip sample (RTS) SPM whereby the sample to be measured is fixed to the end of a cantilever beam and the scanning tip becomes part of a tip array chip. In this way, tips can be exchanged quasi on the fly without tip disengagement from the sample surface and thousands of tips are available at the user’s direct disposal. To fully exploit the advantages of the RTS SPM approach, we developed in this work tapered nanoscopic silicon tip structures (~1micron in height) and placed them in the center of silicon pedestals (~5 microns in diameter and ~10 microns in height). The innovative feature of our dry-etch based process is the self-patterning and -alignment of the silicon nano-tip. The fabricated Si tip chips have been used in RTS SPM measurements in contact and non-contact mode whereby measuring with 9 different tips (classical SPM is limited to a single tip only) on the same surface area which strongly improves the overall data statistics and variability. The silicon tips are ultra-sharp (2 nm) and have been evaluated for measurements on nanoparticle coated surfaces and bio structures (DNA). Our presentation explains our self-patterning and -alignment approach in detail, demonstrates fabricated silicon tip chips and highlights the high potential of RTS SPM for enabling new SPM measurements.
Authors : Białek, R.*(1), Vasileiadis, T. (1), Sledzinska, M. (2), Sotomayor Torres, C. M. (2) & Graczykowski, B. (1)
Affiliations : (1) Faculty of Physics, Adam Mickiewicz University, ul. Uniwersytetu Poznańskiego 2, 61-614 Poznań, Poland (2) Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST, Campus UAB, Bellaterra, 08193, Barcelona, Spain * lead presenter
Resume : The nature of elastic waves propagating in a studied specimen depends not only on the material itself but also on its size and shape, especially in nanostructured samples. Periodic structures in nanoscale present many possible applications, such as in transducers of electromagnetic waves into elastic ones at GHz frequencies. As an example, gold linear gratings can be used in such an application. It is crucial to fully understand elastic properties of such structures and the propagation of waves both along and across the stripes prior to using them in a more complex system. Here, we present results of Brillouin light scattering (BLS) experiments performed on gold linear gratings with various periods of the order of a few hundreds of nanometers deposited on silicon wafers. BLS on such non-transparent samples allows characterization of surface acoustic waves, thus those mostly affected by the gold gratings. Obtained phonon dispersion curves exhibit multiple branches and additional zone folding due to the periodicity of the grating. The origin and characteristics of the branches will be discussed with the help of finite element method simulations. Transducing properties of gold gratings can be used in a unique method called pump-BLS, in which pulsed near-IR laser is used to induce elastic waves in the sample, while continuous-wave laser is used for probing using BLS spectroscopy around the gold grating to map wave propagation. Preliminary results from this method will be provided. This work was funded by NCN project No. UMO-2018/31/D/ST3/03882.
Authors : Coline Bretz, Andrea Vaccaro
Affiliations : LS Instruments, 1700 Fribourg, Switzerland www.lsinstruments.ch
Resume : Static (SLS) and Dynamic (DLS) Light Scattering are among the most powerful techniques to study nanostructures. These technologies have been widely employed for more than 30 years, and are still undergoing constant improvement. While SLS and DLS are well-established characterization techniques, several completely new light scattering methods have gained significant traction among material scientists over the past decade. Among these, Diffusing Wave Spectroscopy (DWS) can be used to characterize the viscoelasticity of materials on a wide frequency range using low sample volumes if compared to classical mechanical rheometers. This presentation will feature a review of the scientific fundamentals of the techniques mentioned above, and take a closer look at some of the recent advancements, including Depolarized Dynamic Light Scattering (DDLS) and Modulated 3D Cross-Correlation.  Weitz & Pine, Diffusing-Wave Spectroscopy. In Dynamic Light Scattering; Brown, W., Ed.; Oxford University Press: New York, 652-720 (1993).  Balog & al., Characterizing nanoparticles in complex biological media and physiological fluids with depolarized dynamic light scattering, Nanoscale, 2015, 7, 5991-5997  Block & Scheffold, “Modulated 3D cross-correlation light scattering: Improving turbid sample characterization”, Rev. Sci. Instrum. 81, 123107 (2010).
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S7 : TBD
Authors : Tamar Segal-Peretz
Affiliations : Technion- Israel Institute of Technology
Resume : Sequential infiltration synthesis (SIS) has emerged in the past decade as a powerful technique for growth of inorganic materials within polymers through atomic layer deposition (ALD) chemistry. In SIS, ALD precursors diffuse into the polymer, leading to growth of nanoscale inorganic materials within the polymer volume. Here, I will present our recent research in the field of SIS. We shed light on the atomic growth of metal oxide clusters and particles within polymers using high-resolution transmission electron microscopy and x-ray absorption spectroscopy. We follow SIS growth from the nanoscale to the macroscale, expanding our understanding of SIS mechanism and the role of polymer chemistry and reversible polymer-precursor interactions on SIS growth. These insights are then applied in fabrication by design of homopolymer and block copolymer-templated 3D nanostructures, fibers, and membranes. We fabricate Al2O3-ZnO heterostructure nanorod arrays and core-shell nano-fibers, where simultaneous but spatially-controlled growth of the two metal oxides within the polymer templates is performed via control over the two precursors diffusion time. Block copolymer particles and films template porous metal oxide particles and membranes with uniporous pore size and controlled surface chemistry. These examples highlight the versatility and potential of SIS nanostructure fabrication by design capabilities.
Authors : A. A. Leniart, P. Pula, P. W. Majewski
Affiliations : Department of Chemistry, University of Warsaw
Resume : Solvent evaporation annealing (SEA) is a simple method to enhance block copolymers' self-assembly. The basic concept of this method is to maintain polymer in a more plasticized state by extended solvent evaporation. It can be achieved by both chemical (addition of non-volatile solvents), and physical methods (lowering down the temperature, limiting evaporation surface). When the polymeric film remains in a swollen state for a sufficient time, the ordering progresses in and the grain sizes produced that way are significantly larger than in unprocessed samples. The simplicity of this method leaves plenty of room for further improvements, e.g., the single-step casting of a mixture of polymer and inorganic precursor that incorporates selectively into one of the blocks. It presents an alternative for Sequential Infiltration Synthesis or metallization by immersion in solutions of metal salts. However, the presence of an additional component may negatively influence the ordering kinetics of the block copolymer itself. In current studies, we investigate the kinetics of block copolymer self-assembly in the presence of the additional compound, i.e. metal complexes. We focus on high molecular weight block copolymers (above 100 kg/mol) consisting of polystyrene and polyvinyl pyridine blocks the latter prone to the complexation by a variety of metal precursors. We also run a series of experiments to determine where the Order-Disorder Transition occurs in the presence of another compound. All results were confirmed with image analysis of large-scale high-resolution SEM images. Presented results indicate, that there is a dependence between the quality of final morphology and evaporation rate during the process and precursor loading. Kinetic studies of SEA in the presence of metal precursor pave the way to a universal platform for the rapid and cost-effective production of large-scale inorganic metal and metal oxide nanostructures. The optimization of the process improves the final result and leaves a promising alternative to other methods that provide well-ordered isotropic morphologies.
Authors : Zhenzhen Zhang**, Assaf Simon*, Clarissa Abetz**, Tamar Segal-Peretz*, Volker Abetz**
Affiliations : * Department of Chemical Engineering, Technion, Haifa-3200003, Israel ** Helmholtz-Zentrum Geesthacht, Institute of Polymer Research, Max-Planck-Str.1, 21502 Geesthacht, Germany
Resume : Block copolymers (BCPs) are considered promising materials for various membrane applications ranging from ultra-filtration for water treatment to protein separation due to their ability to self-assemble into highly ordered structures with uniform pore size and high pore density. Typically, the pore’s size and surface interactions are controlled by the BCP chemistry. However, simultaneous control over both properties is difficult to achieve. In particular, controlling the size and functionality of the pores through the BCP chemistry is considered a major challenge. In this study, we aim to tailor the size and chemistry of BCP based ultrafiltration membranes by selectively growing metal oxides inside the pores. Poly (styrene-b-4-vinyl pyridine) (PS-b-P4VP) were used to create ultrafiltration membranes in a process combining self-assembly with non-solvent induced phase separation (SNIPS). This results in one integral but asymmetric membrane, with ordered pores at the top of the membrane and sponge-like mechanically robust support layer at the bottom of the membrane. Sequential infiltration synthesis (SIS), an atomic layer deposition based technique that enables selective growth of metal oxides inside the polar domains of BCP, was used to grow Al2O3 inside the P4VP domains of the BCP films. By incorporating metal oxides in the pores, the pore size can be reduced. By modifying the number of SIS cycles and/or the metal oxide we use, we can achieve control over the pore size while adding new functionality to the membrane, for example anti-fouling properties that ZnO exhibits. Structural characterization was performed by scanning electron microscopy (SEM) to probe the surface structure and analyze the resulting membrane pore size distribution. To confirm the penetration and incorporation of the metal oxide in the membranes, cross sectional SEM and transmission electron microscopy (TEM) was performed. By modifying the SIS process, control over pore size can be achieved. The control over pore size as well as surface chemistry, can allow for overall improved membrane performance.
Authors : Diana Berman, Yunlong She, Daniel Pleshek, Elena Shevchenko
Affiliations : Materials Science and Engineering Department, University of North Texas Center for Nanoscale Materials, Argonne National Laboratory
Resume : Robust and efficient process for synthesis of various composition inorganic coatings with controlled nanoporosity and structure is highly desirable for design of efficient catalytic, purification, and detection systems. Recently, infiltration of a nanoporous polymer template with inorganic precursors using sequential infiltration synthesis (SIS) with inorganic vapor precursors followed by oxidative annealing was proposed as a new and efficient approach to create porous inorganic structures with tunable porosity and composition. The major limitations of the original water-based thermal SIS, though, are the thickness of the patterned structure being limited by vapor penetration depth of the precursors into the polymer template and the SIS material selection restricted by the availability of high vapor pressure precursors. Here, we propose a swelling-based modification to the SIS process that allows to overcome these limitations. We summarize the basics of the multi-step infiltration approach, the structure and properties of the resulting materials, and their functional potential for practical applications. We report ultra-high accessibility of the pores when porous films are prepared via the polymer swelling-assisted SIS. Using a quartz crystal microbalance (QCM) technique, we demonstrate increased solvent absorbing capabilities of highly porous ceramic films as a result of high interconnectivity of the pores in such structures. Our results show that the SIS can be been extended toward preparing conformal coatings, freestanding membranes, and powders consisting of metal or metal oxide nanoparticles embedded in a porous oxide matrix.
Authors : A. Motta*+, C. Wiemer*, G. Seguini* and M. Perego*
Affiliations : *IMM-CNR, Unit of Agrate Brianza, Via C. Olivetti 2, 20864 Agrate Brianza (MB), Italy +Dipartimento di Energia and NEMAS - Center for NanoEngineered Materials and Surfaces, Politecnico di Milano; via Ponzio 34/3, 20133 Milano, Italy
Resume : Sequential Infiltration Synthesis (SIS) process is a very promising process for the manufacturing of organic-inorganic hybrid materials from vapor phase. SIS involves the sequential exposure of the materials to alternating vapor phase organo-metallic precursor and a co-precursor, intercalating appropriate purging cycles of inert gas to remove unreacted molecules or reaction by-products. During the exposure time of precursors in static vacuum, the precursor diffuses into the sample and remains entrapped inside the material. Then the exposure to co-precursor leads to the formation of the desired hybrid materials. SIS is a very complex process that involves physical phenomena and chemical reactions of the precursors inside the polymer matrix. Presently, this process has been applied on several polymer materials incorporating different metal oxide to modify the initial polymer properties such as tensile strength, changing the permeability of membrane and improving conductivity of polymer. However a comprehensive picture of the effective processes taking place during SIS is still missing. This work aims to understand Al2O3 infiltration process in poly(butylene succinate) (PBS) thin films. PBS is a biodegradable polyester, that has excellent processability. Although its commercialisation is mainly devoted to biodegradable packaging, the use of PBS in the biomedical field has recently attracted considerable attention. Infiltration of Al2O3 into the PBS matrix could modify water and oxygen permeability of the polymer film, creating an effective barrier for oxidizing agents. In this research, PBS thin films of different thickness were prepared by spin-coating and infiltrated with Al2O3 at 70°C, varying the number of SIS cycles and TMA pulse time. Finally, plasma treatment was performed to remove the organic phase and to estimate the alumina mass uptake at different process conditions. We performed a systematic analysis of the morphology (SE, SEM and optical microscope) and composition (ToF-SIMS, XPS) of the processed samples. According to the collected data, PBS exhibits an excellent capability to entrap organo-metallic precursors inside the polymer matrix, leading to a very high amount of Al2O3 infiltrated into the polymer matrix at each cycle. In particular, we demonstrate that the amount of incorporated alumina depends on the specific processing conditions and on the initial thickness of PBS films. Accordingly, preliminary information about the diffusion of the TMA inside the polymer matrix has been obtained. In conclusion, we demonstrate for the first time, the possible formation of Al2O3-PBS hybrid materials by SIS process, providing information about the fundamental mechanism driving the infiltration process into this specific polymer.
Authors : Przemyslaw Pula, Arkadiusz A. Leniart, Pawel W. Majewski
Affiliations : Chemistry Department, University of Warsaw, Warsaw
Resume : Fabrication of the state-of-art miniaturized nanostructures present in modern electronics is mainly based on EUV lithography. This approach, however, has almost reached its physical limits and alternative fabrication schemes are sought e.g. by utilization of molecular self-assembly phenomena. Among several classes of molecules that self-assemble, block copolymers (BCPs) form diverse morphologies with desired dimensions matching those required by nanofabrication. Researchers still struggle to find a convenient and fast method for obtaining well-ordered BCP matrices in a controlled way. Frequently, the choice of the BCP ordering method is a matter of compromise between the complexity and the quality of the final morphology. For example, vapor annealing forms fingerprint morphologies at a relatively short time with small effort. On the contrary, more sophisticated methods such as grapho-, chemoepitaxy or photothermal annealing require the construction of more complex setups but eventually provide uniaxial and long-range ordering. Here, we present an approach, called Solvent Evaporation Annealing (SEA), which provides a beneficial combination of simplicity with a good degree of ordering at a reasonable cost. The process requires an addition of a low volatile compound to the traditional BCP casting solution containing a volatile solvent (e.g. toluene). Interestingly, prolongation of a usual coating step, defined by solvent evaporation duration, results in a formation of BCP film morphology with a domain size exceeding several micrometers that is hardly achievable for conventional thermal methods. Ordered BCP films are an intermediate stage for the fabrication of inorganic nanostructures. Further conversion utilizes the universal scheme of selective binding of metal precursor molecules to one of the blocks. Such methods as Sequential Infiltration Synthesis or Aqueous Metal Reduction require initially ordered BCP matrices, thus the conventional process consists of two separate steps. Here, we merged the ordering and conversion of a BCP template in a single step by adding a metallic precursor into the SEA solution. As a result, we successfully infused selectively one of the domains with metal precursors. The simplicity of this method is of great advantage – one requires only a properly composed BCP-salt solution and a coating device. So far, we have successfully obtained metal/metal oxide replicas for several transition metals. We characterized the morphology of patterned nanostructures with SEM as well as their chemical composition with spectroscopic analysis. Additional investigations of principles governing the process will undoubtedly make this approach more convenient in terms of its further widespread applications ranging from optical coatings, nanoelectronic structures to catalytic materials.
Authors : C. de Melo, M. Jullien, F. Rigoni, A. Vomiero, Y. Battie, A. En Naciri, J. Ghanbaja, F. Montaigne, J. F. Pierson, F. Mücklich, D. Horwat
Affiliations : C. de Melo; M. Jullien; J. Ghanbaja; F. Montaigne; J. F. Pierson; D. Horwat, Université de Lorraine, CNRS, IJL, F-54000 Nancy, France ; F. Rigoni; A. Vomiero, Department of Engineering Sciences and Mathematics, Division of Materials Science, Luleå University of Technology, 971 87 Luleå, Sweden Y. Battie; A. En Naciri, LCP-A2MC, Institut Jean Barriol, Université de Lorraine, 1 Bd Arago, 57070 Metz, France F. Mücklich; Department of Materials Science and Engineering, Saarland University, D-66123 Saarbrücken, Germany
Resume : Atomic layer deposition (ALD) has emerged as an important technique for depositing high-quality thin films due to the self-limiting growth mechanism which allows excellent surface coverage and conformal deposition. In particular, area-selective atomic layer deposition (AS-ALD) has gained a lot of attention in recent years due to the possibility of achieving accurate patterns in nanoscale features , which renders the technique compatible with the continuous downscaling in electronic devices. In this work, we present the results on the selective growth of Cu2O and metallic Cu by ALD on ZnO and Al-doped ZnO substrates. It was possible to tune the deposited material (Cu or Cu2O) or to completely inhibit the deposition by controlling the substrate conductivity/density of donor defects . Based on this AS-ALD process, Cu2O/ZnO/Al-doped ZnO micro-junctions were fabricated, with the Cu metallic film acting as back electrode. I-V characteristics of the microjunctions, measured by conductive atomic force microscopy, show a non-linear rectifying behavior typical of a p-n junction, which is promising for low-cost all-oxide transparent microelectronics. Semi-transparent Cu2O/ZnO thin film heterojunctions were also fabricated by ALD and reactive magnetron sputtering. The heterojunctions exhibited a self-powered photo-response under 1-Sun illumination and high transmittance in the visible region of the electromagnetic spectrum, which is highly sought for visible photodetection . Finally, this ALD process also allowed the growth of Cu nanoparticles (NP) on highly-conducting ZnO substrates, owing to the Volmer–Weber island growth mode. The Cu NP exhibit localized surface plasmon resonance, tunable from the visible to the near-infrared regions, as confirmed by spectroscopic ellipsometry. The resulting Cu NP/ ZnO device showed an enhanced photo-response under white light illumination with good responsivity values, fast response times, and stability under dark/light cycles . The significant photocurrent detected for this device is related to the hot electron generation at the NP surface and injection into the conduction band of the ZnO. The possibility of tuning the plasmon resonance together with the photo-responsivity of the device is promising for applications related to photo-detection, photonics and photovoltaics. References  A. J. M. Mackus, A. A. Bol, and W. M. M. Kessels, Nanoscale 6 (2014) 10941.  C. de Melo et al., ACS Appl. Mater. Interfaces. 10 (2018) 37671–37678.  C. de Melo et al., ACS Appl. Nano Mater. 2 (2019) 4358–4366.  C. de Melo et al., ACS Appl. Mater. Interfaces. 10 (2018) 40958–40965.
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S8 : TBD
Authors : Gianluca Milano, Carlo Ricciardi
Affiliations : Istituto Nazionale di Ricerca Metrologica; Politecnico di Torino
Resume : Human brain cognitive functions rely on the emergent behavior of biological neural networks composed of 10^14 – 10^15 synaptic connections. The information processing and memory functionalities are regulated by the changes in the synaptic strength in response to neuron activity (synaptic plasticity), while the high network connectivity provides robustness, adaptability, and fault tolerance to the system. With the aim of emulating working principles of the human brain and its effectiveness, Artificial Neural Networks (ANN) have been developed for the realization of brain-inspired computing systems, outperforming classical computation and even surpassing humans in specific tasks. However, further development of Artificial Intelligence (AI) requires new hardware architectures beyond von-Neumann computing able to implement neuromorphic-type of data processing. In this scenario, memristive devices acting as artificial synapses represent promising building blocks for hardware implementation of ANN. The physical mechanism is related to atomic reconfiguration under proper electrical stimulation, involving nanoionic effects that lead to the formation/rupture of nanofilaments responsible for the variation of the device resistance. Top-down architectures based on crossbar arrays of memristive devices have demonstrated their capability to implement neuromorphic-type of data processing with supervised and unsupervised learning . However, it is hard for such rigid top-down architectures to emulate typical features and topology of biological neuronal circuits, where the principle of self-organization governs both structure and function and provides high connectivity, adaptability through reconnection and rewiring, and long‐range spatiotemporal correlation. As a more biologically plausible alternative, memristive networks consisting of many self-assembled nano-objects have been proposed . The talk will focus on self-organized memristive nanowire (NW) networks, showing that such systems can emulate typical neuromorphic features such as homo and heterosynaptic plasticity, thanks to rewiring and reweighting effects observed in NWs and NW junctions, respectively . Finally, a perspective will be given on the possibility of processing spatiotemporal inputs in multiterminal configuration for in-materia (i.e. hardware) implementation of unconventional neuromorphic computing paradigms, such as reservoir computing.  Xia Q. et al., Nature Materials 18:4, pp 309-323, 2019  Kuncic Z. et al., Advances in Physics: X 6:1, pp 1894234, 2021  Milano G. et al., Advanced Intelligent Systems 2:8, pp 2000096, 2020
Authors : Hyoungwon Park, Jae-Hun Kim, Dustin Vivod, Dirk Zahn, Changkyoo Park, Sang Sub Kim, Marcus Halik
Affiliations : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Department of Materials Science, Interdisciplinary Center for nanostructured Films (IZNF), 91058 Erlangen, Germany; Department of Materials Science and Engineering, Inha University, Incheon 22212, Republic of Korea; Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Computer-Chemie-Centrum and Interdisciplinary Center for Molecular Materials, 91052 Erlangen, Germany; Laser and Electron Beam Application Department, Korea Institute of Machinery and Materials, Daejeon, 34103, Republic of Korea
Resume : Semiconducting metal oxide (SMO)-based gas sensors, which known as a promising gas sensor type, need to improve their gas selectivity toward various gas molecules. In this study, a facile and easy post-modification method is proposed to tuning the gas selectivity by functionalizing the surface of SnO2 nanowires (NWs) with self-assembled monolayer (SAM) molecules. This can be realized by forming specific chemical recognition moieties on the surface of the SnO2 NWs, and they induce the chemical affinity-driven interaction between gas molecules and the functionalized sensors. Gas sensing selectivity was simply modulated as the functionalized SAM molecules changes, which allowed fine-tuning of the gas selective sensor surfaces. The success of SAM modification was analyzed by infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis, whereas selective gas sensing being investigated under various sensing conditions. The selective gas sensing results were also supported by the molecular dynamics simulations. The gas-selective sensing and surface passivation effect was observed for SAM-functionalized SnO2 NW-based gas sensors, and this concept could be generally expanded to other types of SMO-based sensing platforms.
Authors : L. Merle, G. Manai, A. Pham, S. Lecommandoux, P. Demont, C. Bonduelle, S. Tricard, A. Mlayah, J. Grisolia
Affiliations : LPCNO, Université de Toulouse, INSA, CNRS, UPS, 135 Avenue de Rangueil, Toulouse 31077, France; LPCNO, Université de Toulouse, INSA, CNRS, UPS, 135 Avenue de Rangueil, Toulouse 31077, France; LPCNO, Université de Toulouse, INSA, CNRS, UPS, 135 Avenue de Rangueil, Toulouse 31077, France; Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, CNRS, Bordeaux, INP, Pessac, France; CIRIMAT, Université Toulouse - Paul Sabatier, 118 Route de Narbonne 31062 Toulouse; Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, CNRS, Bordeaux, INP, Pessac, France; LPCNO, Université de Toulouse, INSA, CNRS, UPS, 135 Avenue de Rangueil, Toulouse 31077, France; CEMES, Université de Toulouse, CEMES-CNRS, 29 rue Jeanne Marvig, Toulouse 31055, France; LPCNO, Université de Toulouse, INSA, CNRS, UPS, 135 Avenue de Rangueil, Toulouse 31077, France
Resume : Hybrid materials combining metallic nanoparticles (NPs) and polymers has stimulated a large effort to make new optical, electronic and magnetic 1–3 properties emerging. Such composite nanomaterials have the potential of improving the functionality of devices ranging from information storage to microelectronic sensors 4,5. In this context, hybrid nanomaterials combining platinum (Pt) nanoparticles (NPs) and poly(γ-benzyl-L-glutamate) (PBLG) in α helice conformation were investigated by in situ alternative-current impedance spectroscopy as a function of temperature, applied DC bias voltages and PBLG polymerization degree. TEM images of the hybrid materials show a lamellar structure, made possible by Pt, whose organization depends on the degree of polymerization. The corresponding Nyquist’s plots generated from the impedance spectroscopy data show that for each degree of polymerization, a perfect semi-circle typical of an equivalent electrical circuit consisting of parallel resistance R and capacitance C plus a series resistance Rs is observed. The R and C values are obtained using a fitting procedure. This procedure allows determining the relaxation time constant, which is interpreted as the characteristic time of a dipolar relaxation process. Variations of τ with temperature are well described by Arrhenius’s law which allows to extract the activation energy of the relaxation process. We found that the activation energy is around 0.1 eV whatever the DP of the PBLG. It is comparable to the stretching vibration energy of the CN bond in PBLG, which is in favor of a conduction process involving polaronic coupling and hopping. The evolution of the activation energy with applied DC Bias voltage and the polymerization degree reveals a piezo-electric effect induced by the presence of the Pt NPs. This piezo-electric effect is not present in the pure PBLG reference sample and is due to the orientation of the dipoles carried by the α helice and to the lamellar structure of the hybrid Pt-PBLG nanomaterial. We will discuss the obtained results and show that impedance spectroscopy under applied DC bias is able to address the physics of dipole relaxation and charge carrier dynamics in polymer/nanoparticle nanostructured hybrid materials. References: 1. Kao, J., Thorkelsson, K., Bai, P., Rancatore, B. J. & Xu, T. Toward functional nanocomposites: taking the best of nanoparticles, polymers, and small molecules. Chem. Soc. Rev. 42, 2654–2678 (2013). 2. Mei, S., Staub, M. & Li, C. Y. Directed nanoparticle assembly through polymer crystallization. Chem. Eur. J. 26, 349–361 (2020). 3. Yi, C., Yang, Y., Liu, B., He, J. & Nie, Z. Polymer-guided assembly of inorganic nanoparticles. Chem. Soc. Rev. 49, 465–508 (2020). 4. Huynh, W. U., Dittmer, J. J. & Alivisatos, A. P. Hybrid nanorod-polymer solar cells. Science 295, 2425–2427 (2002). 5. Balazs, A. C., Emrick, T. & Russell, T. P. Nanoparticle polymer composites: where two small worlds meet. Science 314, 1107–1110 (2006).
Authors : Petri, E.*(1), Gotti, C (2)(3), Groppi, J. (5), Liguori A. (1), C. Gualandi, C. (1), Focarete, M. L. (1), Silvi, S. (1), Credi, A. (5)(6), Zucchelli, A. (2)(3), Soavi, F. (1), Arbizzani, C. (1).
Affiliations : (1)Alma Mater Studiorum – University of Bologna, Dept. of Chemistry “Giacomo Ciamician”, Bologna, Italy;(3)Alma Mater Studiorum – University of Bologna, Dept. of Industrial Engineering, Bologna, Italy;(4)Alma Mater Studiorum – University of Bologna, Advanced Mechanics and Materials–Interdepartmental Center for Industrial Research (CIRI-MAM), Bologna, Italy; (5)CNR_ISOF, Clan-Center for Light Activated Nanostructures, Bologna, Italy; (6)Alma Mater Studiorum – University of Bologna, Dept. of Industrial Chemistry “Toso Montanari”, Bologna, Italy.
Resume : The emulation of human skeletal muscles has brought to the idea of actuators and several materials have been studied so far, with different contractile mechanism [1, 2]. In order to imitate the natural synchronous contractile mechanism of human muscles, it is necessary to combine: (i) the employment of elastomeric biopolymer with high force-to-weight ratio and flexibility; (ii) a manufacture technique capable to create nano-structured materials; (iii) a motor system simply activated/disactivated by electrochemical stimuli using low voltage . To this aim, the introduction of artificial molecular machine, giving a linear contractile/relaxation movement, in polymeric nanofibers have been envisioned through electrospinning . Electrospinning is a suitable technique to produce bundles of fibers, with hierarchical structure, resembling the skeletal muscle myofibrils and myofibers . In this work, we present and discuss the morphological and mechanical properties of the polymer containing suitable molecular machines, and the electrochemical results by using model molecules of molecular machines. The purpose is to demonstrate that it is possible to integrate molecular machines compounds into polymeric fibers, guarantee the alignment of molecular machines in respect of the fiber axis and electrochemically stimulate the active molecule inside the polymer fibers, thus opening a new scenario in electrochemically responsive soft actuators.  M Wei, Y. Gao, X. Li, M.J. Serpe, Polymer Chemistry, 2017, 8 (1), 17-143.  S.M. Mirvakili, I.W. Hunter, Adv. Materials, 2018, 30 (6), 1704407  M. Franke, A. Ehrenhofer, S. Lahiri, E.-F. M. Henke, T. Wallmersperger, A. Richter, Front. Robot. AI, 2020, 7, 510757  V. Fasano, M. Baroncin, M. Moffa, D. Iandolo, A. Camposeo, A. Credi, D. Pisignano, J. Am. Chem. Soc., 2014, 136, 40,14245–14254.  C. Gotti, A. Sensini, A. Zucchelli, R. Carloni, M.L. Focarete, Appl. Mater. Today 2020, 20, 100772. Acknowledgments This work was supported by the European Union within the Horizon 2020 Research and Innovation Programme (Grant No. 801378 MAGNIFY project https://www.magnifyproject.eu/). All the Partners are acknowledged for the fruitful discussions.
Authors : Raphael Pfattner, Elena Laukhina, Marta Mas-Torrent, Vladimir Laukhin, Concepció Rovira and Jaume Veciana
Affiliations : Institut de Ciencia de Materials de Barcelona (ICMAB-CSIC) Campus UAB, 08193 Bellaterra (Spain) and Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN) ICMAB-CSIC, 08193 Bellaterra (Spain)
Resume : Developing smart materials that can respond to an external stimulus is of major interest in artificial sensing devices able to read information about the physical, chemical and/or biological changes produced in our environment. Additionally, if these materials can be deposited or integrated on flexible, transparent substrates, their appeal is greatly increased. The first [BEDT-TTF = bis(ethylenedithio)- tetrathiafulvalene based quasi-two-dimensional organic superconductor β-(BEDT-TTF)2I3 was first reported back in 1984. Soon it became clear that ion radical salts (IRSs) derived from BEDT-TTF exhibit tune-able electronic band structures; therefore, such molecules are excellent building blocks for engineering a rich and diverse family of organic crystalline metals and semiconductors. Thanks to strong electron−electron and electron−phonon couplings, their anisotropic electronic structures exhibit many fascinating electronic and structural phase transitions, which can be controlled by external stimuli such as light, temperature, strain, pressure, and humidity, among others. Nevertheless, it is necessary to engineer these crystals into a proper material for sensing applications. This is done by forming poly-crystalline layers of IRSs, derived from BEDTTTF-based conductors, in nano-composite bilayer (BL) films. Such systems can be further tuned by choosing the nature of the IRSs enabling high sensitivity towards strain, pressure, temperature or even contact less radiation sensing i.e. bolometers.[2,3] In another very recent example, bilayer films, composed of conducting poly-crystalline layers of two dimensional BEDT-TTF-IRSs, hydroresistive sub-micron sized crystals on top of a polymeric host matrix permit to electrically monitor relative humidity in a stable and fully reversible fashion. At the percolation threshold, fascinating novel optoelectronic properties emerge (Insulator semiconductor-like metal transition). Mechanisms of responses are discussed and correlated with fundamental properties of charge transport in these systems. This sensor platform enables combining high electrical performance of single crystals with processing properties of polymers towards a simple, low-cost and highly sensitive platform for applications in robotics, biomedicine and human health care. References: 1. E. B. Yagubskii, I. F. Shchegolev, V. N. Laukhin, et.al., JETP Lett., (1984), 39, 12. 2. E. Laukhina, R. Pfattner, L. R. Ferreras, et. al., Adv. Mater., (2009), 21, 1-5. 3. R. Pfattner, V. Lebedev, E. Laukhina, et.al., Adv. Electr. Mater., (2015), 1, 1500090. 4. R. Pfattner, E. Laukhina, L. Ferlauto, et.al, ACS Appl. Electr. Mater., (2019), 1, 1781. 5. R. Pfattner, et.al, (2021), submitted.
S9 : TBD
Authors : Gregor Hlawacek
Affiliations : Helmholtz-Zentrum Dresden-Rossendorf, Institute of Ion Beam Physics and Materials Research, Bautzner Landstr. 400, 01328 Dresden, Germany
Resume : Helium Ion Microscopy (HIM) is providing best resolution Nobel gas focused ion beam (FIB) based imaging and nanofabrication capabilities [1, 2]. I will address in particular low on fluence modification of materials properties with only negligible material removal. Examples in the part will include the modification magnetic, superconducting, electrical and optical properties in metals, semiconductors and 2D materials. I will show how the HIM can be used to create arbitrary shaped nano-magnets  and tailor their magnetic properties, with minimal morphological modifications. We use a set of in-situ probes to follow the change of the magnetic properties during irradiation to allow optimized fluence delivery . Similarly, we can use the probes to characterize transistors build from 2D materials and follow the change of their electrical properties during ion beam irradiation. Finally, I will present results from a recent collaboration in which we grew FIBID superconducting tungsten nanowires to study the movement of flux vortices . This work has been supported by the Horizon2020 project npSCOPE (GA: 720964) and the COST Action FIT4NANO (CA19140).  Gregor Hlawacek, Vasilisa Veligura, Raoul van Gastel, and Bene Poelsema. Helium ion microscopy. Journal of Vacuum Science and Technology B, 32(2):020801, 2014.  Gregor Hlawacek and Armin Gölzhäuser, editors. Helium Ion Microscopy. NanoScience and Technology. Springer International Publishing, Switzerland, 2016.  Magnus Nord, Anna Semisalova, Attila Kákay, Gregor Hlawacek, Ian MacLaren, Vico Liersch, Oleksii M. Volkov, Denys Makarov, Gary W. Paterson, Kay Potzger, Jürgen Lindner, Jürgen Fassbender, Damien McGrouther, and Rantej Bali. Strain anisotropy and magnetic domains in embedded nanomagnets. Small, page 1904738, 2019.  Peter Dunne, Ciaran Fowley, Gregor Hlawacek, Jinu Kurian, Gwenael Atcheson, Silviu Colis, Niclas Teichert, Bohdan Kundys, Munuswamy Venkatesan, Jürgen Lindner, Alina Maria Deac, Thomas M. Hermans, J. M. D. Coey, and Bernard Doudin. Helium ion microscopy for reduced spin orbit torque switching currents. Nano Letters, 20(10):7036–7042, 2020.  Pablo Orús, Rosa Córdoba, Gregor Hlawacek, and José María De Teresa. Superconducting properties of in-plane W-C nanowires grown by He+ focused ion beam induced deposition. Nanotechnology, 32(8):085301, 2020.
Authors : Marianna Sledzinska
Affiliations : Catalan Institute of Nanoscience and Nanotechnology, CSIC, BIST Edifici ICN2 08193 - Bellaterra (Barcelona) Spain
Resume : Two-dimensional materials offer a unique platform to study thermal transport in the nanoscale. In this presentation the current understanding of phonon thermal transport will be reviewed, starting from materials with very high thermal conductivity, such as graphene and hBN to transition metal dichalcogenides (TMDs), which show rather moderate thermal conductivity. I will cover our recent efforts on tuning the phonon mean free path and consequently the thermal conductivity in TMDs by various means, such as introducing defects, grain boundaries, changing the thickness or combining different layered materials. We will discuss the case polycrystalline MoS2 and PtSe2 where the grain size, their orientation and distribution play important roles in controlling both the in-plane and cross-plane thermal transport. In the case of single crystal membranes the sample preparation is crucial to eliminate effects of imperfections and contamination focusing on the thickness dependence of the thermal conductance. Finally, the role of the surface and interfaces will be discussed in MoS2–based heterostructures. On the methodological part, the sources of errors in the determination of thermal properties, emerging challenges and outstanding questions concerning phonon transport in TMDCs will be discussed. Work in collaboration with X. Peng, E. Chavez Angel, A. El-Sachat, F. Alzina and C.M. Sotomayor Torres
Authors : Gardella, M.*(1), Bhatnagar, M. (1), Giordano, M.C. (1), Chowdhury, D. (1), Mennucci, C. (1), Mazzanti, A. (2), Della Valle, G. (2), Martella, C. (3), Tummala, P. (3), Lamperti, A. (3), Molle, A. (3), Buatier de Mongeot, F. (1)
Affiliations : (1) Dip. di Fisica, Università di Genova, Via Dodecaneso 33, 16146 Genova, Italy; (2) Dip. di Fisica and IFN-CNR, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy; (3) CNR-IMM Unit of Agrate Brianza, via C. Olivetti 2, Agrate Brianza, I-20864, Italy * lead presenter
Resume : Two-dimensional layered materials belonging to the class of Transition Metal Dichalcogenides (TMDs) have recently emerged as promising active layers for optoelectronics thanks to their tunable bandgap, high optical absorption coefficient and excellent mechanical and transport properties . Two main challenges have to be faced in view of the real world exploitation of TMDs in energy harvesting applications: i) development of large area growth techniques to overcome the limits of current micrometer scale mechanically exfoliated flakes; ii) poor optical absorption due to limited thickness which is reduced at the atomic level. Increasing the effective absorption in ultra-thin films requires for innovative light trapping strategies. To this end, we recurred to Laser Interference Lithography to fabricate large area (cm2) periodically nanostructured substrates to be used as templates for conformal growth of few-layer MoS2 films. Due to the template periodicity, diffractive anomalies emerge at the interfaces of the 2D material, bending and confining light into the corrugated MoS2 layer. As a result, a broadband and tunable absorption enhancement is demonstrated [2-3]. Because of the large area and high throughput achievable, nanostructured TMDs films may have a strong impact in the field of 2D layered nanophotonics, featuring broadband photon harvesting.  ACS Photonics 2017, 4, 2962−2970  ACS Appl. Mater. Interfaces 2021, 13, 13508−13516  Nanoscale, 2020, 12, s24385-24393
Authors : Peng Xiao1,2, Alexandros El Sachat1, Emigdio Chavez-Angel1, Clivia M. Sotomayor Torres1,3, and Marianna Sledzinska1
Affiliations : 1.Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST, Campus UAB, Bellaterra, 08193 Barcelona, Spain 2. Departamento de Física, Universidad Autónoma de Barcelona, Bellaterra, E-08193 Barcelona, Spain 3.ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain
Resume : Molybdenum disulfide (MoS2), one of the most represented TMDs, has been considered as the promising thermoelectric materials for generating electrical energy from temperature gradient, due to the large Seebeck coefficient of ∼50 mV/K and ∼7 mV/K for the monolayer and bulk, respectively. However, the fabrication of MoS2-based thermoelectric devices have not yet been reported. Because of the relatively high thermal conductivity of MoS2 (kMoS2) which increases from ~ 25 W/mK to ~ 100 W/mK when the thickness increases from single layer to bulk, a low thermoelectric figure of merit value of MoS2-based device of 0.5 is expected at room temperature. While the main focus so far has been on the electrical properties of MoS2, less attention has been paid to tuning its thermal conductivity. In this work we have studied two possible ways of reducing kMoS2: reduction of thickness and nano-patterning. The values reported so far on the thermal conductivity of single-crystalline MoS2 show significant spreading, depending on the sample preparation and measurement technique. Therefore, we first systematically studied the kMoS2 of large-area, free-standing single-crystalline membranes using two-laser Raman thermometry. We found that kMoS2 decreased from ~89 W/mk to ~ 27 W/mk to when the thickness decreased from to 40 nm to about 4.5 nm. After the nano-patterning of these membranes, we found the thermal conductivity decreased significantly, over 100 times. The results are discussed together with the theoretically investigated phonon scattering in the system. Our findings open up a possibility for tuning the thermal conductivity in a facile manner to improve the thermoelectric devices based on the layered systems.
Authors : Tobias Hartl, Moritz Will, Pantelis Bampoulis, Davor Capeta, Rajendra Singh, Daniel Scheinecker, Virginia Boix de la Cruz, Luca Bignardi, Paolo Lacovig, Marko Kralj, Jani Kotakoski, Jan Knudsen, Silvano Lizzit, Thomas Michely
Affiliations : II. Physikalisches Institut, Universität zu Köln, Zülpicher Str. 77, 50937 Cologne, Germany; Physics of Interfaces and Nanomaterials, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands, Institute of physics, Bijenička cesta 46, 10000, Zagreb, Croatia; Faculty of Physics, Vienna University, Universitätsring 1, 1010 Vienna, Austria; MAX IV Laboratory and Division of Synchrotron Radiation Research, Lund University, Box 118, 22100 Lund, Sweden; Elettra-Sincrotrone Trieste S.C.p.A., Strada Statale 14 Km 163.5,I-34149 Trieste, Italy;
Resume : Cluster superlattice membranes (CSLMs) consist of a highly regular cluster lattice, grown on a suitable template like graphene or hexagonal Boron-Nitride on Ir(111) , which is embedded in a host matrix material (e.g. amorphous carbon [a-C]). The membrane can be removed from the template and is stable as a free-standing 2D material . A wide variety of cluster materials, the controllable size of the clusters down to the single atom limit, the choice of the template layer and possible host matrix materials make this fabrication process a highly versatile method to tailor the physical properties of this new 2D material. Potential applications for CSLMs can be found in single electron transistors, phase formation and in electro catalysis, where a cluster superlattice consisting of Pt clusters on Gr, embedded in a-C could be used as an electrode. We present, in detail, the fabrication process of such membranes. The cluster superlattices are grown on graphene on Ir(111), and subsequently embedded in a few nanometer thick carbon matrix. XPS and STM reveal that the carbon embedding is conformal to the clusters, anchors them to the graphene and greatly improves their thermal and mechanical stability. We find that removal of the CSLM from the Ir(111) substrate requires a substantial reduction of the binding between template layer and substrate, which can be achieved via annealing at 850 K and assisted by intercalation of Eu at the template/substrate interface. The removal of the CLSM from the substrate is then performed via conventional hydrogen bubbling. TEM was used after the removal to confirm the presence of the cluster superlattice inside the free standing membrane.  Hartl, Tobias, et al., ACS nano, 14(10),13629-13637 (2020).
Authors : Astrid Kupferer*(1,2,3), Alexander Holm (1,2), Andriy Lotnyk (1), Stephan Mändl (1) & Stefan G. Mayr (1,2)
Affiliations : (1) Leibniz Institute of Surface Engineering (IOM), Germany (2) Division of Surface Physics, Felix Bloch Institute for Solid State Physics, Leipzig University, Germany (3) Research Group Biotechnology and Biomedicine, Peter Debye Institute for Soft Matter Physics, Leipzig University, Germany * lead presenter
Resume : Ranging from efficient water splitting surfaces and novel solar cells to smart biosensors: titania nanotube arrays constitute a highly functional material for various applications. Using low-energy ion implantation in the 10 keV – 100 keV range, we show a promising route to modify the material characteristics while preserving the amorphous structure of the nanotube arrays. We report on the interplay of phenomenological effects observed upon implantation of low fluences of a few 10^16 ions/cm^2 in the unique anisotropic and nanoporous structure: sputtering vs. re-adsorption and plastic flow, amorphization vs. crystallization and compositional patterning. Using high-resolution element mappings of transmission electron microscopy measurements, we reveal compositional patterning of oxygen and carbon. Especially, partially connected oxide and carbide domains with sizes of about 10 nm are distributed over the whole nanotube array. Our extensive theoretical treatment corroborates the experimental results. We show that the distinct nanotube environment combined with radiation enhanced diffusivity due to ion implantation and related ballistic contributions provide advantageous conditions for patterning. By applying a generalized version of the Cahn-Hilliard equation combined with driven alloys and corresponding free energy estimates for the amorphous composite, we derive characteristic length scales of pattern formation. Indeed, density functional theory calculations using amorphous TiO2 cells show that dilute-limit mixing enthalpies are augmented for the carbon and oxygen system. Hence, the compositional patterning of carbon and oxygen is expected by enthalpic and entropic arguments. In contrast, a patterning of fluorine and oxygen is energetically unfavorable and not observed. In fact, the nanotubular geometry promotes the patterning due to an increase of relocation lengths compared to bulk materials. As titania nanotubes are a common basis material for advanced devices, these findings pave the way for a manifold of new optimization strategies of optical and electrical nanotube characteristics. Funding by the Heinrich Böll foundation and German BMBF, Project EYECULTURE (FKZ 161A574C) is gratefully acknowledged. References: A. Kupferer, A. Holm, A. Lotnyk, S. Mändl, S.G. Mayr. Adv. Funct. Mater. 2021. Accepted.
S10 : TBD
Authors : Robert W. Style, Alba Sicher, Jin Young Kim, Tianqi Sai, Kathryn A. Rosowski, Eric R. Dufresne
Affiliations : Department of Materials, ETH Zürich, Switzerland
Resume : There are many situations in nature where biology uses phase separation to create complex, structured materials. For example, some birds use phase-separating proteins to create materials with highly ordered microstructure, that give rise to vibrant blue and green colors – without the need for dye molecules. However, it is difficult to replicate biology’s precise control of this process in the lab, as surface tension quickly drives complete separation. Here, I will show how we can gain great control over the phase separation process by the simple addition of a polymer network. Starting with a cross-linked, elastic polymer network swollen by a solvent mixture, we change the temperature or trigger polymerisation to drive demixing. Inclusions nucleate and grow to a stable, uniform size that is tunable by the network cross-linking density. I will explain how we are using this process to replicate structural color, as well as to study various topics such as how soft materials fail, and phase separation inside the cytoplasm of living cells.
Authors : Sophia K. Laney, Tao Li, Martyna Michalska, Francisco V. Ramirez, Mark Portnoi, Junho Oh, Manish K. Tiwari, Iain G. Thayne, Ivan P. Parkin, and Ioannis Papakonstantinou
Affiliations : Sophia K. Laney − Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, London WC1E 7JE, United Kingdom; Tao Li − Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, London WC1E 7JE, United Kingdom; Martyna Michalska − Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, London WC1E 7JE, United Kingdom; Francisco V. Ramirez − Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, London WC1E 7JE, United Kingdom Mark Portnoi − Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, London WC1E 7JE, United Kingdom Junho Oh − Nanoengineered Systems Laboratory, Department of Mechanical Engineering, University College London, London WC1E 7JE, United Kingdom; Manish K. Tiwari − Nanoengineered Systems Laboratory, Department of Mechanical Engineering and Wellcome/EPSRC Centre for Interventional and Surgical Sciences (WEISS), University College London, London WC1E 7JE, United Kingdom; Iain G. Thayne − James Watt School of Engineering, University of Glasgow, Glasgow G12 8LT, United Kingdom Ivan P. Parkin − Department of Chemistry, University College London, London WC1E 7JE, United Kingdom Ioannis Papakonstantinou − Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, London WC1E 7JE, United Kingdom;
Resume : With billions of years of evolution, nature has created a diverse library of structural surface patterns to manipulate a range of interfacial phenomena. The proficiency of natural surfaces to tackle multiple phenomena simultaneously is often the work of complex nanostructure arrays or specific geometric features; and replicating this through synthetic means has been a long-standing challenge within the fabrication community. One such structure that has proved challenging to fabricate but is desired for wide ranging applications, is that of the nanotube. Despite recent progress, fabricating nanotubes with greater complexity (e.g., concentric/binary structures) alongside advanced feature control and large-scale fabrication, remained a synthetic bottleneck. Here, we answer this need and present our work on Spacer Defined Intrinsic Multiple Patterning (SDIMP). Unlike previous atomic layer deposition-assisted patterning, the spacer is applied directly on the pre-patterned target substrate material, serving as an etching mask to generate a multitude of tailored nanotubes. By concept iteration, we further realize concentric and/or binary nanoarrays in silicon, glass, and polymers. To demonstrate the achieved quality and applicability of the structures, we probe how nanotube fine-tuning induces broadband antireflection, and present a surface boasting extremely low reflectance of <1% across the wavelength range 300-1,050 nm. Finally, turning to Slippery Liquid Infused Porous Surfaces (SLIPS), we show the impact of nanostructure morphology on the lubricant retention abilities under dynamic conditions by comparing nanotube, nanohole and nanopillar arrays; revealing a 2-fold improvement of nanotubes when compared to nanopillars.
Authors : Maximiliano Jara Fornerod, Alberto Alvarez-Fernandez, Stefan Guldin
Affiliations : Department of Chemical Engineering, University College London, Torrington Place, London, WC1E 7JE, UK
Resume : Mesoporous thin films are widely used for applications in need of high surface area and good transport properties. A common fabrication process involves the co-assembly of host organic molecules (e.g. block copolymers, surfactants, liquid crystals) with inorganic guest material obtained by sol-gel chemistry. A subsequent calcination in air is applied to remove the organic structure-directing agent. Due the volume contraction associated to solvent evaporation, condensation and template removal, this process often results in the uniaxial film contraction of up to 70% in the direction perpendicular to the substrate, affecting the final porosity, pore shape and pore size. Here, we show that a two-step calcination process, high temperature treatment in argon followed by air calcination, improves various structural parameters of the mesoporous thin films. We use spectroscopy ellipsometry (SE) and environmental ellipsometric porosimetry (EEP) to show that inert processing reduces film shrinkage, resulting in higher porosity and larger pore sizes. Grazing-incidence small-angle scattering (GISAXS) and scanning electron microscopy (SEM) shows that the two-step protocol led to a hexagonally closed-packed mesoporous structure. Finally, we show that inert processing condition is beneficial for applications such as enzymatic storage.
Authors : Oleg Gang
Affiliations : Columbia University, Brookhaven National Laboratory
Resume : The ability to organize functional nanoscale components into the targeted architectures promises to enable a broad range of nanotechnological applications, from designed biomaterials to photonic devices and information processing systems. However, we are currently lacking an adaptable and broadly applicable methodology for the 3D bottom-up nanomaterials fabrication with ability to prescribe a structure of organizations and to integrate different types of components. The talk will discuss our progress in establishing a versatile platform for the fabrication of designed large-scale and finite-size nano-architectures from diverse nanocomponents through the DNA-programmable assembly. The recent advances in creating periodic and hierarchical organizations from inorganic nanoparticles, proteins and enzymes will be presented. The use of the developed assembly approaches for generating functional nanomaterials with nano-optical, electrical, mechanical and biochemical functions will be demonstrated.
Authors : Martyna Michalska1, Sophia K. Laney1, Tao Li1, Mark Portnoi1, Nicola Mordan2, Elaine Allan3, Manish K. Tiwari4,5, Ivan P. Parkin6, Ioannis Papakonstantinou1
Affiliations : 1 Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, Torrington Place, London, WC1E 7JE, UK; 2 Division of Biomaterials and Tissue Engineering, UCL Eastman Dental Institute, Royal Free Campus, University College London, Pond Street, London, NW3 2QG, UK; 3 Department of Microbial Diseases, UCL Eastman Dental Institute, Royal Free Campus, University College London, Rowland Hill Street, London, NW3 2PF, UK; 4 Nanoengineered Systems Laboratory, Department of Mechanical Engineering, University College London, Torrington Place, London, WC1E 7JE, UK; 5 Wellcome/EPSRC Centre for Interventional and Surgical Sciences (WEISS), University College London, London, W1W 7TS, UK; 6 Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK.
Resume : Nature-inspired nanopatterning offers exciting multifunctionality spanning antireflectance and the ability to repel water/fog, oils, and bacteria; strongly dependent upon nano-feature size and morphology [1,2]. Broadly, this multifunctionality is inherent to and bridged by the nanocone structure, yet such patterning in glass (SiO2) – a material of great practical importance – remains a bottleneck due to its high chemical stability alongside structuring at the nanoscale itself, which becomes increasingly challenging to manage as the pattern resolution advances (pitch <100 nm). Here, we demonstrate a novel Regenerative Secondary Mask Lithography process which enables customized glass nanopillars through dynamic nanoscale tunability of the side-wall profile and aspect ratio (>7). Our method is facile and versatile, comprising just two steps. Firstly, we generate sub-wavelength scalable soft etch-masks (55-350 nm) through an example of block copolymer micelles or nanoimprinted photoresist. Secondly, we overcome their inherent durability problem – typically addressed by metal/metal oxide incorporation which adds time and complexity – through our innovative cyclic etching. During this etching, the original mask becomes embedded within a protective secondary organic mask, which is tuned and regenerated, permitting dynamic nanofeature profiling with etching selectivity >1:32. We envision that such structuring in glass will facilitate fundamental studies and be useful for myriad of practical applications – from displays to architectural windows. Providing the highly-tunable nature of our method (size/shape/pitch), we tailor glass features and present excellent broadband omnidirectional antireflectivity, self-cleaning, and unique antibacterial activity towards Staphylococcus aureus.  T. Mouterde, G. Lehoucq, S. Xavier, A. Checco, C. T. Black, A. Rahman, T. Midavaine, C. Clanet and D. Quéré, Nat. Mater., 2017, 16, 658–663.  D. P. Linklater, V. A. Baulin, S. Juodkazis, R. J. Crawford, P. Stoodley and E. P. Ivanova, Nat. Rev. Microbiol., 2021, 19, 8–22.
Authors : Dirk Döhler,1 Andrés Triana,1 Pascal Büttner,1 Florian Scheler,1 Eric S.A. Goerlitzer,2 Johannes Harrer,2 Anna Vasileva,3 Ezzeldin Metwalli,4 Wolfgang Gruber,4 Tobias Unruh,4 Alina Manshina,3 Nicolas Vogel,2 Julien Bachmann,1 Ignacio Mínguez-Bacho 1*
Affiliations : 1. Chemistry of Thin Film Materials, Department of Chemistry and Pharmacy, IZNF, Friedrich-Alexander University of Erlangen-Nürnberg, Cauerstr. 3, 91058 Erlangen, Germany. 2. Institute of Particle Technology, Friedrich-Alexander University Erlangen-Nürnberg, Cauerstr. 3, 91058 Erlangen, Germany. 3. Institute of Chemistry Saint-Petersburg State University Universitetskii pr. 26, St. Petersburg 198504, Russia. 4. Institute for Crystallography and Structure Physics, Friedrich-Alexander University Erlangen-Nürnberg, Staudtstrasse 3, 91058 Erlangen, Germany.
Resume : The preparation of a highly ordered nanostructured transparent electrode based on a combination of nanosphere lithography and anodization is presented. The size of perfectly ordered pore domains is improved by an order of magnitude with respect to the state of the art. The concomitantly reduced density of defect pores increases the fraction of pores that are in good electrical contact with the underlying transparent conductive substrate. This improvement in structural quality translates directly and linearly into an improved performance of energy conversion devices built from such electrodes in a linear manner.
S11 : TBD
Authors : Ofer Burg, Rajashekharayya A. Sanguramath, Elisheva Michman, Noga Eren, Inna Popov, Roy Shenhar
Affiliations : Institute of Chemistry and the Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel
Resume : Patterned metallic nanostructures are useful for many applications such as photonics and catalysis. Alternating structures composed of two or more metals are particularly interesting, as they may give rise to novel surfaces with hybrid properties. However, creating such structures on the nanoscale requires the employment of sophisticated fabrication schemes, which usually involves a few steps and extensive use of lithography. In this work, we demonstrate a simple self-assembly approach for the creation of alternating wires of two metallic structures, which relies on block copolymers as templates. Our approach harnesses the chemical distinction between the domains to selectively adsorb the metal precursors, and employs different conditions to influence the penetration depth of the precursors in order to effect composition alternation between the final nanowires. Specifically, the P2VP cylinders exposed at the surface of a microphase separated PS-b-P2VP film were impregnated with one type of metal precursors, and the second metal precursor were introduced into the P2VP cylinders buried deeper into the film under acidic conditions. This process gave different spatial distributions of metal-impregnated P2VP domains within the film, which were converted into metallic nanostructures by subsequent reactive ion etching. Alternating nanowires with different compositions of palladium, platinum, and silver were thus obtained. This approach was also applied for selective deposition of gold nanoparticles on the block copolymer film prior to the process, which resulted in alternating bare and decorated nanowires.
Authors : Morgan Stefik
Affiliations : University of South Carolina
Resume : Few aspects are as prevalent and important to energy conversion and storage as the dimension control of porous nanomaterial architectures. The study of nanostructure-dependent electrochemical behavior, however, has been broadly limited by access to well-defined nanomaterials with independent control over the pore and wall dimensions. This historic limitation is partially due to reliance upon equilibrating self-assembly processes that obscure nanostructure cause-and-effect since the resulting sample series convolve multiple spatial variables. Persistent micelle templates (PMT) are a new nanofabrication approach based upon kinetic micelle control where the pore diameter and wall thickness are independently tunable.1-6 This approach enables investigations that vary one spatial variable at a time with seamless access from meso-to-macroporous materials and a remarkable ~2 Å precision of tuning. Recent energy device research enabled by PMT will be presented where tailored nanomaterials provide a unique perspective to unambiguously identify nanostructure-property-performance relationships.
Authors : Alberto Alvarez-Fernandez (1), Barry Reid (1), Maximiliano Jara Fornerod (1), Guillaume Fleury (2), Virginie Ponsinet (3) and Stefan Guldin (1)
Affiliations : (1) Department of Chemical Engineering, University College London, Torrington Place, London, UK (2) CNRS, Univ. Bordeaux, Bordeaux INP, LCPO, UMR 5629, Pessac, France (3) CNRS, Univ. Bordeaux, Centre de Recherche Paul Pascal, UMR 5031, 115 Avenue Schweitzer, 33600 Pessac, France
Resume : Metallic and dielectric nanoarchitectures are attracting increased attention for optical applications, due to their unique electromagnetic properties.(1) These nanocomposites are prominent in optical metamaterials, which are artiﬁcially structured materials engineered to gain optical properties not only from their composition, but from their design. Their geometry, size and arrangement can aﬀect the propagation of light in an unconventional manner, giving rise to properties which are not available in bulk materials. Metamaterials and nanophotonic devices are classically fabricated by lithography techniques, but alternative simpler techniques are needed to reach characteristic sizes on the tens of nanometers length scale. In this sense, block copolymer (BCP) self-assembly has emerged over the past decade as a practical approach, offering unrivalled opportunities to design nanometric features with controlled periodicity over extensive areas at low energy and technology cost. (2) In this work, we present the high versatility that BCP templating and co-assembly offers for optical metasurface and metamaterial fabrication. In a first step, different molecular weight PS-b-P4VP BCP self-assembled films were used as templates for the fabrication gold arrays, regularly organized in a hexagonal lattice.(3) BCP macromolecular engineering allowed complete tuning of the structural parameters of the created arrays. In a second example, perpendicular lamellar structures of PS-P2VP BCP were used as scaffold to create gold decorated surfaces. (4) In this case, the shape of the produced gold NPs was tuned by varying the metal content within the P2VP lamellae, using different impregnation conditions. This resulted in different gold nanofeature shapes from well-defined Au dots to rodlike particles of increasing aspect ratio. Interestingly, more complex structures were prepared using more elaborated fabrication approaches. In this sense, on-demand bimetallic Au@Al2O3 raspberry-like nanoclusters has been fabricated using BCP multi-layer self-assembly strategy.(5) Finally, BCP co-assembly approach, in combination with the so-called persistent micelle templating method, allows the fabrication of ordered inverse-opal mesoporous dielectric architecture. More specifically, we identify the chromatographic fractionation of a polydisperse amphiphilic PIB-b-PEO BCP as a straightforward method to create tailored inorganic mesoporous thin films. Crucially, we identify the role of molecular weight, composition and dispersity on the resulting pore size distribution.(6) The precise control on the shape, structure, size and materials obtained with the previously described fabrication processes, allows a complete modulation of the optical response of the fabricated materials. AFM, GISAXS, Ellipsometric porosimetry, SEM and X-ray Photoelectron Spectrometry, have been used to follow each step of the fabrication process. Besides, optical properties were studied by variable-angle spectroscopic ellipsometric. (1) D. R. Smith, et al, Phys. Rev. Lett. 2000, 84, 4184. (2) A. Alvarez-Fernandez, et al., Advanced Optical Meterials, 2021, https://doi.org/10.1002/adom.202100175 (3) A. Alvarez-Fernandez, et al, J. Vac. Sci. Tech.. B 2020, 38, 013601. (4) A. Alvarez-Fernandez, et al, Nanoscale Adv. 2019, 1, 849. (5) A. Alvarez-Fernandez, et al, RSC Adv. 2020, 10, 41088. (6) A. Alvarez-Fernandez, et al, Nanoscale 2020, 12 (35), 18455.
Authors : F. Ferrarese Lupi,1 I. Murataj,1-2 E. Cara,1 M. Channab,2 F. Pirri,2 L. Boarino,1 A. Angelini,1
Affiliations : 1Advanced Materials and Life Sciences, Istituto Nazionale di Ricerca Metrologica (INRiM), Strada delle Cacce 91, Turin 10135, Italy 2 Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, C.so Duca degli Abruzzi 24, Turin 10129, Italy
Resume : opportunities for confinement and propagation of light at the nanoscale. In-plane orientation of the optical axis, in the direction coinciding with the anisotropy of the HMMs, is desirable for a variety of novel applications in nanophotonics and imaging. To date, most of the HMMs presented in the literature are realized by metal/dielectric multilayers or by electrodeposition in nanoporous templates. Here we will present a novel method for creating localized HMMs with in-plane optical axis, based on the dewetting of block copolymer (BCP)-homopolymer ternary blends. On a flat unpatterned substrate, the thermally induced thin film instability give rise to the formation of micrometric droplets composed by a single and defectless grain, randomly distributed on the surface. On the other hand, when the dewetting of BCP is achieved over topographically defined substrates with micrometric periodicity, a hierarchical pattern composed of well-ordered lamellar or cylindrical nanostructures. The presented solution represent a valuable and cost-effective platform for the subsequent pattern transfer into a metal/dielectric HMM, exhibiting hyperbolic behavior in a broad wavelength range in the visible spectrum. A computed Purcell factor as high as 32 at 580 nm supports the strong reduction in the fluorescence lifetime of defects in nanodiamonds placed on top of the HMM. The realization of BCP-based hierarchical patterns paves the way for an easy fabrication of more complex photonic devices such as photonic hypercrystals  and hyperbolic waveguides  and provides an additional degree of freedom for the fabrication of graded index elements.  N. Meinzer, W. L. Barnes, I. R. Hooper, Nat. Photonics 2014, 8, 889 F. Ferrarese Lupi et al. ACS Nano 2018, 12, 7076  I. Murataj et al. Adv. Optical Mater. 2021, 2001933  E. E. Narimanov, Phys. Rev. X 2014, 4, 041014.  D. J. Roth et al. ACS Photonics 2017, 4, 2513 M. Naffouti et al. Sci. Adv. 2017, 3, eaao1472
Authors : Abeer FAHES, Aotmane EN NACIRI, Mohammad NAVVABPOUR, Safi JRADI, Suzanna AKIL
Affiliations : Laboratoire de Chimie-Physique Approche Multiéchelle des Milieux Complexes (LCP-A2MC), Université de Lorraine, 1 Boulevard Arago, 57070 Metz, France ; Laboratoire de Nanotechnologie et d’Instrumentation Optique (LNIO), Université de Technologie de Troyes, 12 rue Marie Curie, 10004 Troyes, France.
Resume : The incorporation of two metallic nanoparticles (MNPs) into one system has enormous benefits in achieving advanced multifunctional nanomaterials in diverse applications such as catalysis, Surface-enhanced Raman Scattering (SERS), localized surface plasmon resonance (LSPR) sensors, and photothermal conversion . Recently, an unprecedented approach known as Vapor Induced Phase Separation (VIPS) was developed for the fabrication of precisely shaped gold nanoparticles embedded in a poly (methyl-methacrylate) PMMA layer . The main principle of this technique relies on the self-assembly of PMMA thin layer into nanoholes, which are used as MNPs synthesis reactors. Among several synthetic procedures, VIPS is considered as a powerful and simple route because it provides excellent control of structural properties of NPs. It offers compelling evidence for producing efficient SERS platforms with controlled size, shape, and interparticle gap distances [3,4]. Inspired by this approach, we aim to fabricate multifunctional hybrid nanomaterials such as Ag-Au bimetallic nanoparticles (BNPs). This is a new insight in the synthesis of BNPs by a surface-based strategy. Precisely, we carried out a parametric study dealing with the influence of different experimental parameters on optical and structural properties of monometallic and BNPs. The optical properties of synthesized BNPs substrates were analyzed by micro-extinction and ellipsometric measurements. Ultimately, the significance of the present work lies in assuring the effectiveness of the substrates produced in SERS applications by inducing highly sensitive, stable, and reproducible SERS substrates over a large scale. . M. Chen, Y. He, & J. Zhu, International Journal of Heat and Mass Transfer. 114, 1098-1104 (2017). . R. Omar, A. E. Naciri, S. Jradi, et al., Journal of Materials Chemistry C. 5(41), 10813-10821 (2017). . R. Omar, A. E. Naciri, A. Fahes, et al., Soft Matter. 16(7), 1857-1865 (2020). . S. Akil-Jradi, S. Jradi, J. Plain, et al., RSC advances. 2(20), 7837-7842 (2012).
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