| 1. |
- Löhrer, F. C., et al.
(author)
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Following in Situ the Deposition of Gold Electrodes on Low Band Gap Polymer Films
- 2020
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In: ACS Applied Materials and Interfaces. - : American Chemical Society. - 1944-8244 .- 1944-8252. ; 12:1, s. 1132-1141
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Journal article (peer-reviewed)abstract
- Metal top electrodes such as gold are widely used in organic solar cells. The active layer can be optimized by modifications of the polymer band gap via side-chain engineering, and low band gap polymers based on benzodithiophene units such as PTB7 and PTB7-Th are successfully used. The growth of gold contacts on PTB7 and PTB7-Th films is investigated with in situ grazing incidence small-angle X-ray scattering (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS) during the sputter deposition of gold. From GIWAXS, the crystal structure of the gold film is determined. Independent of the type of side chain, gold crystals form in the very early stages and improve in quality during the sputter deposition until the late stages. From GISAXS, the nanoscale structure is determined. Differences in terms of gold cluster size and growth phase limits for the two polymers are caused by the side-chain modification and result in a different surface coverage in the early phases. The changes in the diffusion and coalescence behavior of the forming gold nanoparticles cause differences in the morphology of the gold contact in the fully percolated regime, which is attributed to the different amount of thiophene rings of the side chains acting as nucleation sites.
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| 2. |
- Schaper, S. J., et al.
(author)
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Revealing the growth of copper on polystyrene- : Block -poly(ethylene oxide) diblock copolymer thin films with in situ GISAXS
- 2021
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In: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 13:23, s. 10555-10565
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Journal article (peer-reviewed)abstract
- Copper (Cu) as an excellent electrical conductor and the amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-b-PEO) as a polymer electrolyte and ionic conductor can be combined with an active material in composite electrodes for polymer lithium-ion batteries (LIBs). As interfaces are a key issue in LIBs, sputter deposition of Cu contacts on PS-b-PEO thin films with high PEO fraction is investigated with in situ grazing-incidence small-angle X-ray scattering (GISAXS) to follow the formation of the Cu layer in real-time. We observe a hierarchical morphology of Cu clusters building larger Cu agglomerates. Two characteristic distances corresponding to the PS-b-PEO microphase separation and the Cu clusters are determined. A selective agglomeration of Cu clusters on the PS domains explains the origin of the persisting hierarchical morphology of the Cu layer even after a complete surface coverage is reached. The spheroidal shape of the Cu clusters growing within the first few nanometers of sputter deposition causes a highly porous Cu-polymer interface. Four growth stages are distinguished corresponding to different kinetics of the cluster growth of Cu on PS-b-PEO thin films: (I) nucleation, (II) diffusion-driven growth, (III) adsorption-driven growth, and (IV) grain growth of Cu clusters. Percolation is reached at an effective Cu layer thickness of 5.75 nm.
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| 3. |
- Schwartzkopf, M., et al.
(author)
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Role of Sputter Deposition Rate in Tailoring Nanogranular Gold Structures on Polymer Surfaces
- 2017
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In: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 9:6, s. 5629-5637
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Journal article (peer-reviewed)abstract
- The reproducible low-cost fabrication of functional polymer-metal interfaces via self-assembly is of crucial importance in organic electronics and organic photovoltaics. In particular, submonolayer and nanogranular systems expose highly interesting electrical, plasmonic, and catalytic properties. The exploitation of their great potential requires tailoring of the structure on the nanometer scale and below. To obtain full control over the complex nanostructural evolution at the polymer-metal interface, we monitor the evolution of the metallic layer morphology with in situ time-resolved grazing-incidence small-angle X-ray scattering during sputter deposition. We identify the impact of different deposition rates on the growth regimes: the deposition rate affects primarily the nucleation process and the adsorption-mediated growth, whereas rather small effects on diffusion-mediated growth processes are observed. Only at higher rates are initial particle densities higher due to an increasing influence of random nucleation, and an earlier onset of thin film percolation occurs. The obtained results are discussed to identify optimized morphological parameters of the gold cluster ensemble relevant for various applications as a function of the effective layer thickness and deposition rate. Our study opens up new opportunities to improve the fabrication of tailored metal-polymer nanostructures for plasmonic-enhanced applications such as organic photovoltaics and sensors.
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| 4. |
- Shelemin, A., et al.
(author)
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Nucleation and Growth of Magnetron-Sputtered Ag Nanoparticles as Witnessed by Time-Resolved Small Angle X-Ray Scattering
- 2019
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In: Particle and Particle Systems Characterization. - : John Wiley & Sons. - 0934-0866 .- 1521-4117.
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Journal article (peer-reviewed)abstract
- Kinetic aspects of the synthesis of Ag nanoparticles (NPs) by magnetron sputtering are studied by in situ and time‐resolved small angle X‐ray scattering (SAXS). Part of the NPs are found to become confined within a capture zone at 1–10 mm from the surface of the target and circumscribed by the plasma ring. Three regimes of the NP growth are identified: 1) early growth at which the average NP diameter rapidly increases to 90 nm; 2) cycling instabilities at which the SAXS signal periodically fluctuates either due to expelling of large NPs from the capture zone or due to the axial rotation of the NP cloud; and 3) steady‐state synthesis at which stable synthesis of the NPs is achieved. The NP confinement within the capture zone is driven by the balance of forces, the electrostatic force being dominant. On reaching the critical size, large NPs acquire an excessive charge and become expelled from the capture zone via the electrostatic interactions. As a result, significant NP deposits are formed on the inner walls of the aggregation chamber as well as in the central area of the target.
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