In-situ Untersuchungen zu Kondensation, Nukleation und Wachstum von Metallfilmen und Nanostrukturen auf organischen Oberflächen während Sputterbeschichtung
Zusammenfassung der Projektergebnisse
In this project we observed in real-time the metal layer growth during sputter deposition of metals and alloys on complex, nanostructured templates using GISAXS, GIWAXS and synchrotron radiation. We corroborated our results by AFM, XPS, SEM, and TEM. As a big step forward, we successfully correlated the nanoscale changes during growth with the optoelectronic properties of the nanogranular metal layers. In detail, we were able to predict electronic properties from the GISAXS investigations, such as the percolation threshold, which marks the onset of electrical conductivity. We successfully quantified the growth mechanism of conductive metals (Ag, Cu, Al, Au) on a variety of organic templates, ranging from model systems to P3HT-based polymers applied in organic electronics and photovoltaics. Combined with XPS and AFM, we were able to understand the differences in selectivity. We even proved that novel low-band gap polymers, where the band gap is tailored via side chain engineering and which are used in champion devices, influence differently the growth of the metal electrode – surprisingly even beyond the percolation threshold. Using the sputter rate as a parameter, we directly correlated the nanoscale morphology induced by the sputter parameters with the organic surfaces’ defect density with the changes in percolation threshold. In terms of photovoltaics, where the interface between gold electrode and active polymer layer plays a crucial role, we were able to see the nascence and establishing of this enrichment layer in-situ and to quantify the gold content and the thickness of this layer as a function of time. For the first time, we quantify earliest non-equilibrium cluster geometries and near-surface embedding at industrial-relevant deposition rates. The observed near-surface gold-polymer enrichment layer promotes metal layer adhesion of gold on polymers fabricated by sputter deposition. The analysis here heavily relied on model-based simulations of the GISAXS data, which allowed us furthermore to quantify the templating effect of nanostructured templates. Furthermore, we extended our investigations to photocatalysis, materials for lithium based thin film batteries as well as quantum dot systems. As for alloys, miscible and immiscible systems were investigated. For the first time, combined in-situ GISAXS and GIWAXS observations of phase separation on growing nanostructures on organic thin films during sputter deposition was performed. In addition to the question at which length scale phase separation sets in, the resulting morphology and real-time monitoring of phase separation between different morphologies was investigated. We are able to compare our results to molecular dynamics simulations with the help of the interested partner (Bonitz group, CAU), corroborating the main results, yet being able to quantify transition thresholds for the demixing of immiscible alloys. Furthermore, we were able to correlate the influence of surface plasma treatment on metal growth on such surfaces with the processing (plasma treatment) parameters. We investigated a broad range of different polymers, which are applied in sensors and photovoltaics. By combining the results, we are able to yield of comprehensive understanding of the selectivity and nanogranular morphology of metals including alloys on a variety of complex, organic substrates. We thus reached our objective to elucidate the nanostructure function relationship. Our results show the big potential of in-situ GISAXS for elucidating the metal-polymer interface during nanostructure during growth and to correlate this with chemical interactions and optoelectronic properties. We want to stress that each deposition was performed in insitu campaigns, yielding 1,000 of GISAXS and GIWAXS pattern for each deposition. The huge amount of data still remaining is currently analyzed using our software (dpdak.desy.de), which was upgraded in the course of this project including new detectors being incorporated in the synchrotron campaigns in the course of this project. Based on our results, we were granted a novel DFG project entitled “Real-time monitoring of low temperature nucleation and growth processes during high power impulse magnetron sputtering”. Furthermore, the huge amount of data stimulated the use of machine learning, where we are currently applying for national and European funding.
Projektbezogene Publikationen (Auswahl)
- Role of Sputter Deposition Rate in Tailoring Nanogranular Gold Structures on Polymer Surfaces, ACS Appl. Mater. Interfaces 9, 5629 (2017)
M. Schwartzkopf, A. Hinz, O. Polonskyi, T. Strunskus, F. C. Löhrer, V. Körstgens, P. Müller-Buschbaum, F. Faupel, and S. V. Roth
(Siehe online unter https://doi.org/10.1021/acsami.6b15172) - Correlating Nanostructure, Optical and Electronic Properties of Nanogranular Silver Layers during Polymer-Template-Assisted Sputter Deposition, ACS Appl. Mater. Interfaces 11, 29416 (2019)
M. Gensch, M. Schwartzkopf, W. Ohm, C. J. Brett, P. Pandit, S. K. Vayalil, L. Bießmann, L. P. Kreuzer, J. Drewes, O. Polonskyi, T. Strunskus, F. Faupel, A. Stierle, P. Müller-Buschbaum, and S. V. Roth
(Siehe online unter https://doi.org/10.1021/acsami.9b08594) - Following in Situ the Deposition of Gold Electrodes on Low Band Gap Polymer Films, ACS Appl. Mater. Interfaces 12, 1132 (2020)
F. C. Löhrer, V. Körstgens, G. Semino, M. Schwartzkopf, A. Hinz, O. Polonskyi, T. Strunskus, F. Faupel, S. V. Roth, and P. Müller-Buschbaum
(Siehe online unter https://doi.org/10.1021/acsami.9b17590) - In Situ Grazing-Incidence Small-Angle X-Ray Scattering Observation of Gold Sputter Deposition on a PbS Quantum Dot Solid, ACS Appl. Mater. Interfaces 12, 46942 (2020)
W. Chen, S. Liang, F. C. Löhrer, S. J. Schaper, N. Li, W. Cao, L. P. Kreuzer, H. Liu, H. Tang, V. Körstgens, M. Schwartzkopf, K. Wang, X. W. Sun, S. V. Roth, and P. Müller-Buschbaum
(Siehe online unter https://doi.org/10.1021/acsami.0c12732) - In Situ Study of Sputtering Nanometer-Thick Gold Films onto 100-Nm-Thick Spiro-OMeTAD Films: Implications for Perovskite Solar Cells, ACS Appl. Nano Mater. 3, 5987 (2020)
L. Song, M. A. Niedermeier, V. Körstgens, F. C. Löhrer, Y. Chen, S. V. Roth, and P. Müller-Buschbaum
(Siehe online unter https://doi.org/10.1021/acsanm.0c01147) - Real-Time Insight into Nanostructure Evolution during the Rapid Formation of Ultra-Thin Gold Layers on Polymers, Nanoscale Horizons 6, 132 (2021)
M. Schwartzkopf, S.-J. Wöhnert, V. Waclawek, N. Carstens, A. Rothkirch, J. Rubeck, M. Gensch, J. Drewes, O. Polonskyi, T. Strunskus, A. M. Hinz, S. J. Schaper, V. Körstgens, P. Müller-Buschbaum, F. Faupel, and S. V. Roth
(Siehe online unter https://doi.org/10.1039/D0NH00538J) - Revealing the Growth of Copper on Polystyrene- Block - Poly(Ethylene Oxide) Diblock Copolymer Thin Films with in Situ GISAXS, Nanoscale 13, 10555 (2021)
S. J. Schaper, F. C. Löhrer, S. Xia, C. Geiger, M. Schwartzkopf, P. Pandit, J. Rubeck, B. Fricke, S. Frenzke, A. M. Hinz, N. Carstens, O. Polonskyi, T. Strunskus, F. Faupel, S. V. Roth, and P. Müller-Buschbaum
(Siehe online unter https://doi.org/10.1039/d1nr01480c) - Selective Silver Nanocluster Metallization on Conjugated Diblock Copolymer Templates for Sensing and Photovoltaic Applications, ACS Appl. Nano Mater. 4, 4245 (2021)
M. Gensch, M. Schwartzkopf, C. J. Brett, S. J. Schaper, L. P. Kreuzer, N. Li, W. Chen, S. Liang, J. Drewes, O. Polonskyi, T. Strunskus, F. Faupel, P. Müller-Buschbaum, and S. V. Roth
(Siehe online unter https://doi.org/10.1021/acsanm.1c00829) - Tailoring the Optical Properties of Sputter-Deposited Gold Nanostructures on Nanostructured Titanium Dioxide Templates Based on In Situ Grazing-Incidence Small-Angle X-Ray Scattering Determined Growth Laws, ACS Appl. Mater. Interfaces 13, 14728 (2021)
S. Liang, W. Chen, S. Yin, S. J. Schaper, R. Guo, J. Drewes, N. Carstens, T. Strunskus, M. Gensch, M. Schwartzkopf, F. Faupel, S. V. Roth, Y.-J. Cheng, and P. Müller-Buschbaum
(Siehe online unter https://doi.org/10.1021/acsami.1c00972)
