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Investigating Gold Deposition with High-Power Impulse Magnetron Sputtering and Direct-Current Magnetron Sputtering on Polystyrene, Poly-4-vinylpyridine, and Polystyrene Sulfonic Acid
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  • Yusuf Bulut
    Yusuf Bulut
    Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
    Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany
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    Orcidhttps://orcid.org/0000-0003-0090-3990
  • Benedikt Sochor
    Benedikt Sochor
    Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
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  • Kristian A. Reck
    Kristian A. Reck
    Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany
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    Orcidhttps://orcid.org/0000-0002-0823-6216
  • Bernhard Schummer
    Bernhard Schummer
    Fraunhofer Institute for Integrated Circuits IIS, Development Center for X-ray Technology EZRT, Flugplatzstr. 75, Fürth 90768, Germany
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  • Alexander Meinhardt
    Alexander Meinhardt
    Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
    Department of Physics, University of Hamburg, Notkestr. 9-11, Hamburg 22607, Germany
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    Orcidhttps://orcid.org/0000-0003-0552-3188
  • Jonas Drewes
    Jonas Drewes
    Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany
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    Orcidhttps://orcid.org/0000-0002-8539-1543
  • Suzhe Liang
    Suzhe Liang
    Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany
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    Orcidhttps://orcid.org/0000-0001-8773-897X
  • Tianfu Guan
    Tianfu Guan
    Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany
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    Orcidhttps://orcid.org/0000-0002-9887-9265
  • Arno Jeromin
    Arno Jeromin
    Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
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  • Andreas Stierle
    Andreas Stierle
    Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
    Department of Physics, University of Hamburg, Notkestr. 9-11, Hamburg 22607, Germany
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    Orcidhttps://orcid.org/0000-0002-0303-6282
  • Thomas F. Keller
    Thomas F. Keller
    Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
    Department of Physics, University of Hamburg, Notkestr. 9-11, Hamburg 22607, Germany
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    Orcidhttps://orcid.org/0000-0002-3770-6344
  • Thomas Strunskus
    Thomas Strunskus
    Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany
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    Orcidhttps://orcid.org/0000-0003-3931-5635
  • Franz Faupel
    Franz Faupel
    Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany
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    Orcidhttps://orcid.org/0000-0003-3367-1655
  • Peter Müller-Buschbaum
    Peter Müller-Buschbaum
    Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany
    Heinz Maier-Leibnitz Zentrum (MLZ), Technical University of Munich, Lichtenbergstraße 1, Garching 85748, Germany
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    Orcidhttps://orcid.org/0000-0002-9566-6088
  • Stephan V. Roth*
    Stephan V. Roth
    Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
    KTH Royal Institute of Technology, Teknikringen 56-58, Stockholm 100 44, Sweden
    *E-mail: [email protected], [email protected]
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    Orcidhttps://orcid.org/0000-0002-6940-6012
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Langmuir

Cite this: Langmuir 2024, 40, 43, 22591–22601
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https://doi.org/10.1021/acs.langmuir.4c02344
Published October 14, 2024

Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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Fabricating thin metal layers and particularly observing their formation process in situ is of fundamental interest to tailor the quality of such a layer on polymers for organic electronics. In particular, the process of high power impulse magnetron sputtering (HiPIMS) for establishing thin metal layers has sparsely been explored in situ. Hence, in this study, we investigate the growth of thin gold (Au) layers with HiPIMS and compare their growth with thin Au layers prepared by conventional direct current magnetron sputtering (dcMS). Au was chosen because it is an inert noble metal and has a high scattering length density. This allows us to track the growing nanostructures via grazing incidence scattering. In particular, Au deposition on the polymer polystyrene (PS) with the respective structural analogues poly-4-vinlypyridine (P4VP) and polystyrene sulfonic acid (PSS) is studied. Additionally, the nanostructured layers on these different polymer films are further probed by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray reflectometry (XRR), and four-point probe measurements. We report that HiPIMS leads to smaller island-to-island distances throughout the whole sputter process. Moreover, an increased cluster density and an earlier percolation threshold are achieved compared to dcMS. Additionally, in the early stage, we observe a significant increase in coverage by HiPIMS, which is favorable for the improvement of the polymer–metal interface.

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Introduction

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Functional materials are of vital interest for various applications including sensors, batteries, and wearables. (1−3) The class of polymer-based applications increased in recent decades; especially, the usage of polymer–metal hybrid materials gained attention. (4−7) Gold is favorable and is used as a material for photoluminescence, (8) plasmonics, (9−12) mirrors, (13−15) catalysis, (16−19) sensors, (20−22) solar cells, (23−26) and electrodes. (27−30) Direct current magnetron sputtering (dcMS) is a well-established and well-understood technique that is being used for fabricating thin metal layers in the aforementioned applications. However, the favorable physical properties of the metal layer are still not obtained in a single step since a preprocessing step like a plasma pretreatment is required to increase the adhesion in dcMS. (31,32) This is undesirable if metal–polymer hybrid structures are fabricated using substrates being sensitive toward these preprocessing treatments. One emerging physical vapor deposition technique to overcome these pretreatments is high-power impulse magnetron sputtering (HiPIMS). (31,32) This technique increases the adhesion of metal–polymer composites while being benign for heat sensitive substrates. Grazing incidence small angle X-ray scattering (GISAXS) and grazing incidence wide angle X-ray scattering (GIWAXS) studies were conducted to understand the formation behavior of dcMS-deposited metals films, but sparse studies were undertaken to understand the in situ film formation of HiPIMS deposited metals. (28,33) Under dcMS and HiPIMS conditions, ionized and nonionized metal species are formed simultaneously during ablation at the sputter target. Depending on the target material, dcMS achieves a degree of ionization of up to 10%, and in the case of HiPIMS, the fraction of the ionized species condensing on the substrate can make up between 50 and 90%. (31,34) Thus, it is important to obtain similar sputter conditions of both dcMS and HiPIMS, e.g., sample-to-target distance sputter target, substrate, pressure, and sputter rate, in order to understand the differences in the underlying physical film formation. (35) Particularly, changing the sputter rate has an influence on the percolation threshold, which was made sure to be similar in this study. (36−38) This focuses on the quantification of the differences in depositing Au with dcMS and HiPIMS on three different polymers, namely, polystyrene (PS), poly-4-vinylpyridine (P4VP), and polystyrene sulfonic acid (PSS). These polymers differ in their structure and have different functional groups apparent. PS is a one-dimensional polymer chain consisting of a substituted polyethylene structure with pendant aromatic rings being phenyl groups as functional groups. PS is a well-known polymer and was previously used in former studies as a standard reference substrate to compare the growth of metals with other polymers. (38,39) P4VP is like PS, a one-dimensional polymer chain consisting of a substituted polyethylene structure with pendant aromatic rings consisting of pyridine as a functional group. Furthermore, PSS is a one-dimensional polymer chain consisting of a substituted polyethylene structure with pendant aromatic rings consisting of a sulfonic acid functional group on the phenyl group located on the para position. Due to different functional groups being apparent in the polymeric structure, it is expected that the different chemical structures change the surface energy of the polymers and thus particularly influence the growth of gold during deposition. The skeletal structure of the polymer can be found in Figure S1. The morphology of Au deposition via dcMS and HiPIMS on PS, P4VP, and PSS is investigated by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), grazing incidence small-angle X-ray scattering (GISAXS), grazing incidence wide-angle X-ray scattering (GIWAXS), X-ray reflectometry (XRR), and four-point-probe measurements. We observe in situ the structural evolution of the Au cluster during dcMS and HiPIMS deposition on the polymers PS, P4VP, and PSS. We show that an increase of Au coverage can be achieved with HiPIMS.

Experimental Section

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Materials

Silicon wafers (Si-Mat Silicon Materials, Germany) were cut into 12 mm × 15 mm-sized pieces. They were cleaned in acidic bath containing a ratio of hydrogen peroxide (30%, Carl Roth) to sulfuric acid (96%, Carl Roth) of 1:2.2 at 70 °C for 15 min. After the cleaning procedure, the silicon wafer was rinsed with ultrapure water and stored in an ultrapure water bath. Polystyrene (PS, Mn = 62.0 kg/mol, PDI = 1.04), poly-4-vinylpyridine (P4VP, Mn = 77.5 kg/mol, PDI = 1.05), and polystyrene sulfonic acid (PSS, Mn = 62.0 kg/mol, PDI = 1.02) were supplied by Polymer Source (Canada). PS was dissolved in toluene with a concentration of cPS = 9 mg/mL, poly-4-vinylpyridine was dissolved in dimethylformamide with a concentration of cP4VP = 26 mg/mL, and polystyrene sulfonic acid was dissolved in ultrapure water with a concentration of cPSS = 25 mg/mL. PS and P4VP solutions were heat treated for 2 h at 70 °C, and PSS solution was heat treated at 90 °C for 15 min and stirred afterward for 2 h at RT.

Polymer Film Preparation

The precleaned silicon wafer pieces were removed from the storage bath and rinsed with ultrapure water, which was followed by blowing them dry with a nitrogen steam. These silicon pieces were loaded into a spin coater (6-RC, SÜSS MicroTec Lithography, Germany). For PS and P4VP, 3600 rpm was used with the ramp-up setting of 9 for 30 s. For PSS, 6000 rpm was chosen with a ramp up setting of 9 for 30 s to obtain smooth thins films. The ramp-up setting of 9 corresponds to the highest acceleration rate allowed by the spin coater reaching the targeted rotation speed. The spin-coated polymer films were further used as spun in the following procedures. The thickness of the polymer films was determined by X-ray reflectometry (XRR) (Figure S2) with the corresponding SLD profiles shown in Figure S3 as δPS = 39 ± 1 nm for PS, δP4VP = 40 ± 1 nm for P4VP, and δPSS = 28 ± 1 nm for PSS. The fits are displayed in Figure S2 and the SLD curves are displayed in Figure S3. The film thicknesses are large enough to neglect potential influences of the substrate (Si/SiO2). (40)

Physical Vapor Deposition

The self-built sputter deposition chamber was described in a previous article. (38) For all experiments, a 2 in. size Au (Kurt J. Lesker, purity 99.999%) target was used. The dynamic working pressure was pAr = 0.36 Pa with an argon flow adjusted to 10 sccm. The average power for dcMS was PdcMS = 27 W. For HiPIMS, deposition was performed at PHiPIMS = 40 W with the pulse length being 50 μs and the frequency being 1 kHz. The chosen dcMS and HiPIMS conditions were stable throughout the experiment. In case of dcMS, the average kinetic energy of the sputtered atoms is 3.9 ± 0.1 eV. The average kinetic energy of the sputtered atoms for HiPIMS is 9.7 ± 0.1 eV having a non-Gaussian distribution. The average kinetic energy of the sputtered atoms for both sputtering modes were measured with a Quantum Probe (Impedans, Ireland). The distance between the target and sample was 13 cm. The deposition rates were determined by a quartz crystal microbalance (QCM) being 0.294 ± 0.006 nm/s for HiPIMS and dcMS. The QCM deposition rates were verified by measuring final thicknesses of deposited gold films on silicon with a profilometer (Dektak XT, Bruker). In addition, the last detector frames of the in situ sequence were used by extracting the distance of adjacent vertical peaks in the qz direction with the relation δ = 2π/Δqz to determine the final deposited thickness for all in situ thicknesses. (41) The last detector frames of the in situ sequences are displayed in Figure S4. Additionally, XRR was performed before and after the in situ deposition on the polymers PS, P4VP, and PSS, which are shown in Figure S2 for the pristine polymers and in Figure S5 for the after in situ deposition.

Characterization

Field Emission Scanning Electron Microscopy

High-resolution field emission scanning electron microscopy (FESEM) images were taken with a Nova Nano SEM 450 (FEI Thermofisher) at DESY NanoLab. (42) For the visualization of the images, the software ImageJ was used. (43) The nanoparticle size was determined with ImageJ by counting only individual clusters that were not connected and measured manually. FESEM images of the pristine thin films are displayed in Figure S6. No difference in surface morphology is observed for the pristine polymer films. In a 100 nm × 100 nm frame, the size of clusters is summarized in Table S1.

X-ray Scattering

The grazing-incidence small-angle X-ray scattering (GISAXS), grazing-incidence wide-angle X-ray scattering, and X-ray reflectometry experiments were conducted at DESY (P03/PETRA III, Hamburg, Germany) with a mobile sputter deposition chamber, which was previously reported. (38) A wavelength of λ = 0.105 nm was chosen. For the measurements, the X-ray beam had a point shape with a size of 30 μm × 25 μm with an incident angle αI = 0.4°. For GISAXS, a Pilatus 2 M (pixel size 172 μm, Dectris Ltd., Switzerland) was placed at a distance to the sample of SDDGISAXS of 3230 ± 2 mm. The data acquisition rate was set for HiPIMS to 20 Hz and that for dcMS to 10 Hz. Raw GISAXS images are displayed in the Supporting Information for Au:PSdcMS (Figure S7), Au:PSHiPIMS (Figure S8), Au:P4VPdcMS (Figure S9), Au:P4VPHiPIMS (Figure S10), Au:PSSdcMS (Figure S11), and Au:PSSHiPIMS (Figure S12). For GIWAXS, a Lambda 9 M (X-Spectrum, Germany) was used with the distance to the sample being SDDGIWAXS = 193 ± 2 mm. For HiPIMS deposition, the data acquisition rate was set to 2 Hz, and for dcMS, it was set to 1 Hz. The pixel size of one pixel of the Lambda 9 M is 55 μm × 55 μm. Raw GIWAXS images are displayed in the Supporting Information for Au:PSdcMS (Figure S13), Au:PSHiPIMS (Figure S14), Au:P4VPdcMS (Figure S15), Au:P4VPHiPIMS (Figure S16), Au:PSSdcMS (Figure S17), and Au:PSSHiPIMS (Figure S18). The software DPDAK was used for analyzing the measured GISAXS and GIWAXS data. (44) X-ray reflectometry (XRR) measurements were performed with the aforementioned energy and were analyzed with MOTOFIT 0.1.20. (45)

Atomic Force Microscopy

The atomic force microscopy (AFM) measurements were taken with a Bruker (Dimension Icon equipped with a NanoScope V controller) at DESY NanoLab. (42) RTESPA-150 (Bruker) cantilevers were used having a nominal tip radius of 8 nm. The software NanoScope Analysis was used for data visualization, and with ImageJ, the scale bar was included.

Four-Point Probe Measurements

Four-point probe measurements (Ossila, UK) were conducted with a probe spacing of 1.27 mm. The measurement range is between 100 mΩ/square and 10 MΩ/square. After 578 days, the samples were measured again and summarized in Table S2.

Results and Discussion

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Au was deposited by direct current magnetron sputtering (dcMS) and by high power impulse magnetron sputtering (HiPIMS) on three different polymer films (PS, P4VP, and PSS). The morphologies of the Au layer at selected thicknesses (δAu = 2 and 4 nm) for both dcMS and HiPIMS are shown in the FESEM images in Figure 1 for PS, P4VP, and PSS.

Figure 1

Figure 1. FESEM images of Au-coated (a, d, g, j) Au:PS, (b ,e, h, k) Au:P4VP, and (c, f, i, l) Au:PSS. Panels a–c were coated with δAu,dcMS = 2 nm, panels d–f were coated with δAu,HiPIMS = 2 nm, panels g–i were coated with δAu,dcMS = 4 nm, and panels j–l were coated with δAu,HiPIMS = 4 nm.

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From Figure 1a–f at δAu = 2 nm, it is clear that in both cases, HiPIMS (PSHiPIMS, P4VPHiPIMS, PSSHiPIMS) or dcMS (PSdcMS, P4VPdcMS, and PSSdcMS), Au islands coalesced, forming a branched network, which is visible. The average size of the isolated Au islands is dAu,cluster = 4 ± 2 nm. Distinct changes between HIPIMS and dcMS are visible with more Au deposition in the FESEM images, for example, in Figure 1g,j in the case of Au:PS. At δAu = 4 nm, the surface coverage (Figure S19) of Au:PSHiPIMS-deposited Au is 93 ± 1%, which is higher than with Au:PSdcMS deposition being 76 ± 1%. This trend can be further explored with P4VP. Au:P4VPHiPIMS has a coverage of 93 ± 1%, which is higher than that with Au:P4VPdcMS deposition being 77 ± 1%. PSS shows the highest surface coverage after deposition for Au:PSSHiPIMS, 96 ± 1%, again being higher than the coverage of Au on the polymer thin films Au:PS and Au:P4VP. Au:PSSdcMS deposition has an intermediate coverage of 84 ± 1%. At δAu = 8 nm, all polymer films are completely covered with a thin granular gold film (Figure S20). Furthermore, AFM topography images are acquired at δAu = 3 nm for dcMS- and HiPIMS-deposited Au on Au:PS, Au:P4VP, and Au:PSS, see Figure 2.

Figure 2

Figure 2. AFM images of (a, c, e) dcMS- and (b, d, f) HiPIMS-deposited gold δAu = 3 nm on (a, b) Au:PS, (c, d) Au:P4VP, and (e, f) Au:PSS are shown. The red box highlights the magnification of the region of interest. The red circle in the magnified box highlights the isolated Au islands.

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In Figure 2a, in the case of dcMS-deposited Au:PS, a network of percolated Au islands is clearly visible, which is not dominantly apparent at δAu = 2 nm, see Figure 1a. This gives an indication that Au islands start to be in contact with the neighboring Au islands at a thickness of δAu,dcMS,PS = 3 nm. A similar behavior is also observed for Au:PSHiPIMS (Figure 2b) at a thickness of δAu,HiPIMS,PS = 3 nm, showing sparsely singular nonpercolated islands, but the majority of the Au islands already percolated into a network. In the case of dcMS and HiPIMS deposition of Au at a thickness of δAu = 3 nm for Au:P4VP and Au:PSS, similar behavior is observed, as described in the case of PS. The majority of the Au islands are percolated, and small amounts of isolated Au islands are still observable. This trend is observed throughout all of the AFM images in Figure 2. In-situ dcMS and HiPIMS deposition experiments are performed utilizing the GISAXS geometry to exploit its statistical relevance and track the real time evolution of the Au nanostructure up to a thickness of δAu = 8 nm since an already closed Au layer is observed at that thickness. The aim is to elucidate the mechanism behind the increased coverage comparing HiPIMS and dcMS, similar to the FESEM and AFM measurement; see Figure 1 and Figure 2.
In Figure 3, the in situ evolution of distance and cluster density of Au deposited on PS, P4VP, and PSS upon dcMS and HiPIMS deposition is presented. The correlation distance (D) is extracted from the peak position (qi), see Figure S24:
D≈2πqi
(1)

Figure 3

Figure 3. In-situ evolution of the distance of Au islands forming on (a) Au:PS, (b) Au:P4VP, and (c) Au:PSS. In situ evolution of the cluster density of Au islands on (d) Au:PS, (e) Au:P4VP, and (f) Au:PSS.

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In all cases, for 0 nm < δAu ≤ 0.35 nm, no structure peak is apparent in the in situ GISAXS data, as the very first Au atoms are arriving on the sample surface. First, impinging Au atoms are adsorbed on the polymer surface and Au atoms are diffusing along the substrate surface; stable nuclei are formed when two or more adatoms are being united. (46,47) Upon continuous deposition, these nuclei grow in the manner of the Volmer–Weber growth, thus growing in height resulting in a low surface coverage, and the probability to form nuclei is reduced, as the new incoming Au atoms grow alongside the preexisting nuclei. (46,47) The nucleation stage (I) is followed by the lateral growth stage. After a critical cluster density is reached, the apparently formed nuclei and clusters grow in size with new impinging Au atoms during the process. (41,46) Additionally, the apparent nuclei and clusters are able to diffuse along the surface, resulting in a diffusion-mediated coalescence of clusters into larger structures (stage II). (48) Both processes result in the increase of the surface coverage of the polymer surface. (46) The third stage is the coarsening stage in which diffusion of the clusters is greatly reduced; thus, diffusion-mediated coalescence is not the dominant factor anymore. Instead, it will be accommodated by adatoms adsorbing on these clusters supporting the growth in the lateral direction (stage III). (41,46) This can be observed at δAu = 2 nm in the FESEM images in Figure 1 showing sparsely isolated Au islands and branched Au islands. During this process, more Au islands branch into a network that can be observed at δAu = 3 nm in the AFM images in Figure 2. Even upon further deposition, the surface coverage increases due to lateral growth, which can be seen by the FESEM images in Figure 1 at δAu = 4 nm. The fourth stage is reached when the surface is fully covered. This stage is called vertical growth or grain growth stage, where the film growth occurs only vertically, since the surface is fully covered. (41,46) Upon continuation of deposition, a polycrystalline grainy structure is obtained, which can be seen in the FESEM images in Figure S23. (46) In detail, the different stages occur for PSdcMS and PSHiPIMS in the range 0 nm ≤ δAu ≲ 0.4 nm/0.4 nm (stage I), 0.4 nm/0.4 nm ≤ δAu ≲ 1.6 nm/1.8 nm (stage II), 1.6 nm/1.8 nm nm ≤ δAu ≲ 3.7 nm/3.9 nm (stage III), and 3.7 nm/3.9 nm nm ≤ δAu until the end of the deposition being stage IV. For P4VPdcMS and P4VPHiPIMS, the ranges were 0 nm ≤ δAu ≲ 0.4 nm/0.4 nm (stage I), and 0.4 nm/0.4 nm ≤ δAu ≲ 1.8 nm/1.8 nm (stage II), 1.8 nm/1.8 nm ≤ δAu ≲ 3.7 nm/3.9 nm (stage III), and 3.9 nm/4.2 nm ≤ δAu until the end of the deposition being stage IV. Finally, for PSSdcMS and PSSHiPIMS, the ranges were 0 nm ≤ δAu ≲ 0.4 nm/0.4 nm (stage I), 0.4 nm/0.4 nm ≤ δAu ≲ 1.6 nm/1.7 nm (stage II), 1.6 nm/1.7 nm ≤ δAu ≲ 3.7 nm/3.9 nm (stage III), and 3.7 nm/4.0 nm ≤ δAu until the end of the deposition being stage IV. Clearly, strong deviations in cluster sizes and distance start to occur in stage II for dcMS and HiPIMS. This is attributed to the increased initial cluster density, see Figure 3, due to the difference in the kinetic energy distribution of the ionized fraction of the impinging atoms. The same fundamental behavior is expected on PS, P4VP, and PSS due to the similarity in the polymer structure. Here, it is important to note the difference during Au deposition between dcMS and HiPIMS on PS, P4VP, and PSS. In Figure 3a, the in situ structure evolution of Au:PSdcMS and Au:PSHiPIMS is shown, being similar in the range δAu = 0.35 nm up to δAu = 1.8 nm. Beyond δAu = 1.8 nm, it is obvious that Au:PSdcMS has a larger average distance during the in situ evolution compared to Au:PSHiPIMS. This trend continues until the end of the in situ sequence probed in the present study. In Figure 3b, the in situ structure evolution of Au:P4VPdcMS and Au:P4VPHiPIMS is shown, and within errors from δAu = 0.35 nm up to δAu = 2.4 nm, the average distances are similar. Au:P4VPdcMS again has a larger average correlation distance compared to Au:P4VPHiPIMS toward the end of the in situ sequence. In Figure 3c, the in situ sequences of Au:PSSdcMS and Au:PSSHiPIMS are displayed. Here, from δAu = 0.35 nm up to δAu = 2.4 nm, Au:PSSdcMS and Au:PSSHiPIMS islands have a similar distance. Upon δAu = 2.4 nm, Au:PSSdcMS has an average higher distance than Au:PSSHiPIMS similar to our findings for Au:PS and Au:P4VP. Additionally, after δAu = 8 nm for PSHiPIMS, P4VPdcMS, P4VPHiPIMS, and PSSdcMS, no structure peak of Au is being observed anymore in this particular GISAXS geometry. For PSdcMS and PSSHiPIMS, no clear structure peak is observed already at δAu = 7.9 nm and δAu = 7.6 nm, respectively. Hence, the abscissa in the corresponding figures ends at δAu = 8 nm and not at the final deposited thickness. With no structure peak being present, it is not possible to track the Au growth between δAu = 8 nm and the final targeted deposited thickness around 12 nm for each sample (see Figure S4) in this GISAXS geometry. The reason is that either the average correlated distance sizes are too large to be resolved at this particular chosen distance for the GISAXS measurement or no average structure is present on the sample surface after this deposited thickness. In case larger distances are present on the sample surface after δAu = 8 nm, a larger sample-to-detector distance in the GISAXS geometry is required to resolve these larger structures. In order to further quantify the Au islands’ layer morphology, it is derived using the following relation: (38)
ρ=23·D2
(2)
It is clearly seen that the number of islands for PSdcMS and PSHiPIMS (Figure 3d) decreases during the deposition. This behavior is due to the coalescence of Au islands. Yet, it is worth noting that the number of Au islands is higher for PSHiPIMS than for PSdcMS until the end of the deposition process. This observation explains the increased coverage of PSHiPIMS compared to PSdcMS seen in Figure 1g,j) since a larger number of islands is apparent during the structure evolution. In the case of P4VP (Figure 3e), the same trend is observable. For δAu ≥ 2 nm, Au:P4VPHiPIMS shows a larger number of islands during deposition compared to Au:P4VPdcMS, which again explains the increase in coverage for HiPIMS in Figure 1h,k. The same trend is observable for PSS (Figure 3f). It is clearly seen that Au:PSSHiPIMS has an increased number of islands compared to Au:PSSdcMS during the deposition, which supports the observation of the increase in coverage in Figure 1 i,l. From these results, it is possible to deduce that under HiPIMS conditions, an increased amount of nucleation sites are formed due to defect formation induced by an increase of the average kinetic energy of the ionized Au fraction of HiPIMS 9.7 ± 0.1 eV compared to dcMS 3.9 ± 0.1 eV. (49) Reck et al. shows by studying the effect of dcMS and HiPIMS on silicon substrate and polystyrene substrate with Ag deposition that the probability of creating surface defects with fast metal ions is enhanced. (50) The increased average kinetic energy results in an increased number of Au islands with a smaller size and correspondingly in a smaller correlation distance during sputter deposition. This finding is supported by the FESEM images in Figure 1g–l, showing that the coverage by HiPIMS deposition is increased due to the appearance of an increased number of smaller islands (compared to dcMS). This in turn manifests itself in the higher cluster density for HiPIMS. In previous investigations, the Au deposition on PS was investigated. (38) In order to extract information on the radius of the Au islands, the cluster shape was approximated as being hemispherical. (38) By taking the ratio of the cluster diameter to the average distance, we obtained information on the percolation threshold. The percolation threshold defines the nominal layer thickness, the moment in which islands are in direct contact with the neighboring islands, resulting in conductive metallic behavior of the nanogranular film. This geometric hemispherical model considers the structure peak position qi, the amount of Au in one cluster, and the cluster shape (hemisphere). Thus, the radius is thus related to the deposited material and the cluster distance via: (38)
R=31.5π·δAuqi23
(3)
It is noteworthy to mention that the derived radius is model- and shape-dependent, as outlined below, see eq 5 and ref (52).
In Figure 4, the in situ evolution of the cluster sizes and the ratio 2R/D of PS, P4VP, and PSS is depicted as extracted from the geometrical model. The evolution of radii R of Au islands on Au:PSdcMS and Au:PSHiPIMS during deposition shows that the Au islands on Au:PSHiPIMS have a smaller radius than the Au islands on Au:PSdcMS (Figure 4a) above δAu ≥ 1.8 nm. This trend holds during full in situ evolution. Moreover, in Figure 4b, in case of Au:P4VP, it is observable only after δAu = 2.4 nm that Au:P4VPHiPIMS islands have a smaller radius during the subsequent evolution than Au:P4VPdcMS. This behavior continued until the end of the deposition process. Furthermore, in Figure 4c, the radius evolution during in situ deposition of Au:PSSHiPIMS and Au:PSSdcMS is shown. Au:PSSHiPIMS has on average a smaller radius than Au:PSSdcMS. Thus, Au cluster sizes in all polymers show the same trend during deposition, which is the result of the average increased kinetic energy of the ionized fraction, as mentioned above. Additionally, using the geometrical model, it is possible to calculate the ratio of the diameter (2R) and the distance between the islands. When this ratio 2R/D is equal to 1, this implies that on average throughout the sample, every cluster is touching its neighbor and a conductive path is formed. In Figure 4d, 2R/D for Au:PSdcMS has a percolation threshold of δAu,Percolation = 3.9 ± 0.5 nm, while Au:PSHiPIMS has a percolation threshold of δAu,Percolation = 3.0 ± 0.7 nm, which is in agreement with our previous investigation. (38) In Figure 4e, it is visible that Au:P4VPdcMS percolates at δAu,percolation = 4.0 ± 0.5 nm, and in the case of Au:P4VPHiPIMS, it percolates at δAu,percolation = 2.4 ± 0.3 nm. Moreover, Figure 4f shows that Au:PSSdcMS has a percolation threshold of δAu,percolation = 7.0 ± 1.0 nm, and in the case of HiPIMS deposition, Au:PSSHiPIMS has a percolation threshold of δAu,percolation = 4.7 ± 0.6 nm.

Figure 4

Figure 4. In-situ evolution of the radius R derived from the hemispherical geometrical model for (a) Au:PS, (b) Au:P4VP, and (c) Au:PSS. In-situ evolution of the ratio two times the radius (2R = cluster diameter) and the correlation distance D to determine the percolation threshold for (d) Au:PS, (e) Au:P4VP, and (f) Au:PSS. The pink line at 2R/D = 1.0 in (d–f) denotes the percolation threshold.

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In Figure 5, four-point-probe measurements of ex-situ deposited PS, P4VP, and PSS are shown with the corresponding sigmoidal Boltzmann fit for the determination of the percolation threshold. (51) At δAu = 1 nm and 2 nm, no conductivity was measured and the sheet resistance was set to 10 MΩ due to the upper limit of the 4-point probe to measure resistance. Figure 5a,d shows the resistivity measurements for Au:PSdcMS and Au:PSHiPIMS with the corresponding fits. The percolation thresholds are δAu,percolation = 2.6 ± 0.1 nm for Au:PSdcMS and δAu,percolation = 2.6 ± 0.1 nm for Au:PSHiPIMS. The percolation threshold for Au:P4VPdcMS and Au:P4VPHiPIMS (Figure 5b) is δAu,percolation = 2.8 ± 0.2 nm for Au:P4VPdcMS for P4VPHiPIMS is δAu,percolation = 2.7 ± 0.1 nm, which is earlier than Au:PV4PdcMS. A similar behavior is observed in Figure 5c for PSS (Au:PSSdcMS δAu,percolation = 2.9 ± 0.1 nm vs Au:PSSHiPIMS δAu,percolation = 2.6 ± 0.1 nm). In Table 1, the results regarding the percolation threshold extracted by GISAXS utilizing the hemispherical model and the 4-point-probe measurements are summed up. The comparison shows that the agreement of Au:PSHiPIMS and Au:P4VPHiPIMS fits well with four-point-probe measurements and the hemispherical model. In the case of Au:PSdcMS and Au:P4VPdcMS, there is a slight discrepancy apparently of roughly ∼1 nm matching the percolation threshold. This discrepancy occurs due to the simplicity of the hemispherical model only considering the monodisperse size of Au islands during the growth on a triangular arrangement. Particularly, for Au:PSSdcMS and Au:PSSHiPIMS, the discrepancy is enhanced. One reason is, as described, that the hemispherical model considers only monodisperse Au islands. On the other hand, it can be seen in the FESEM images in Figure 1 that the surface coverage of Au on PSS is larger under dcMS and HiPIMS conditions compared to PS and P4VP. As it is extracted from the GISAXS data, Au growing on PSS either in dcMS or HiPIMS conditions leads to larger structures than PS and P4VP, which can be seen in Figure S23. Particularly, the cluster density is lower for Au growing on PSS compared with PS and P4VP, which can be seen in Figure S24. We expect that the higher surface energy for PSS leads to an improved wetting behavior and that faster larger structures are grown. Due to the faster growth, the structures are more oblate compared to the simple hemispherical model. In a previous in situ investigation of Cu growth on PS-b-PEO, it could be seen that the Cu islands deviate strongly from the hemispherical shape. They grow more elongated in the height being described by the hemispherical elongation factor with H being the height and R being the radius of the Cu islands: (52)
f=HR
(4)
R=3·D2δAu4πf3
(5)

Figure 5

Figure 5. 4-point-probe measurements with the corresponding sigmoidal Boltzmann fit for (a) Au:PSHiPIMS, (b) Au:P4VPHiPIMS, (c) Au:PSSHiPIMS, (d) Au:PSdcMS, (e) Au:P4VPdcMS, and (f) Au:PSSdcMS with a deposited thickness being δAu = 1, 2, 3, 4, 6, and 8 nm.

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Table 1. Summary of the Percolation Threshold Extracted by 4-Point-Probe Measurements and GISAXS Data Utilizing the Hemispherical Model
MaterialPercolation threshold 4-point-probe (nm)Percolation threshold hemispherical model (nm)
PS dcMS2.6 ± 0.13.9 ± 0.5
PS HiPIMS2.6 ± 0.13.0 ± 0.7
P4VP dcMS2.8 ± 0.14.0 ± 0.5
P4VP HiPIMS2.7 ± 0.12.4 ± 0.3
PSS dcMS2.9 ± 0.17.0 ± 1.0
PSS HiPIMS2.6 ± 0.14.7 ± 0.6
Schaper et al. observed in this case that the Cu islands had a hemispherical elongation factor f = 2.75 due to the strong Cu–Cu interaction and surface containing oxygen due to the diblock copolymer PS-b-PEO. (52) In the case of the hemispherical model, the elongation factor is f = 1. We expect for PSS that the hemispherical elongation factor f is lower than 1 due to the increased surface coverage being observed in Figure 1 for PSS at δAu = 4 nm. Using the hemispherical elongation factor of f = 0.9 for PSSdcMS and PSSHiPIMS, results are matching with the percolation threshold for PSSHiPIMS being at δAu = 2.6 ± 0.6 nm. In the case of PSSdcMS, the percolation threshold would result in δAu = 3.9 ± 1.0 nm. Thus, the introduction of a microscopy-based elongation factor reduces the difference between the 4-point-probe and model-based extraction of percolation threshold in Table 1 for PSS.
For completeness, the in situ GIWAXS evolution during deposition is displayed in Figure 6. GIWAXS is used in situ during the sputter deposition to detect the crystallite size evolution. The in situ crystallite size evolution for Au on PS, P4VP, and PSS deposited with dcMS and HiPIMS condition is displayed in Figure 6. Due to experimental restrictions of the in situ GIWAXS geometry for the simultaneous combination with in-situ GISAXS and sputter deposition, only a fraction of the necessary angular range is measured for strain analysis. Thus, a complete strain analysis representing the sample is hence omitted. (53,54) It has to be noted that the strain analysis can influence the crystallite size by the Scherrer analysis. The crystallite size was extracted following Figure S22 using the Scherrer equation with K = 0.9 and coressponds to the <111> reflex of Au. (55,56) In the case of Au:PSdcMS, the first noticeable Au crystallites can be detected at around δAu,dcMS = 1.8 nm with the size being 3.7 ± 0.8 nm (Figure 6a). Upon further deposition, the crystallite size increases to 9.2 ± 0.2 nm at the final deposited thickness δAu,dcMS = 8 nm. In the case of Au:PSHiPIMS, the same trend can be observed. First noticeable crystallites start to appear at around δAu = 1.7 nm, with their size being 3.8 ± 1.0 nm. With the continuation of the deposition process, the crystallite size increases up to 8.9 ± 0.3 nm at a final deposited thickness of δAu = 8 nm. In the case of Au:P4VPdcMS and Au:P4VPHiPIMS, the same trend is observed when Au was deposited on P4VPdcMS. First noticeable crystallites start to form at δAu,dcMS = 1.8 nm with the average crystallite size being 4.4 ± 0.6 nm, and at δAu,dcMS = 8 nm, the crystallite size has increased to 9.9 ± 0.2 nm. This behavior is in a similar range as Au:P4VPHiPIMS, which shows first noticeable crystallites in the size of 3.7 ± 1.1 nm at δAu,HiPIMS = 1.4 nm and a final crystallite size of 9.5 ± 0.3 nm at the final deposited thickness δAu,HiPIMS = 8 nm. In the case of Au:PSSdcMS in Figure 6c, the first noticeable crystallites occur at δAu,dcMS = 1.8 nm with a size of 4.1 ± 0.7 nm, which increases during deposition to 9.7 ± 0.2 nm. For Au:PSSHiPIMS noticeable crystallites start to form at δAu,HiPIMS = 1.6 nm with the average crystallite size being 3.7 ± 1.1 nm and increase to 9.5 ± 0.3 nm at δAu,HiPIMS = 8 nm. This observation shows that by keeping the dcMS and HiPIMS conditions similar, the crystallite size is the same during deposition. Moreover, in all cases, the crystallite size increased upon continuous Au deposition. Additionally, independent from the polymer, it can be clearly seen that there is no difference in the crystallite size for the polymers PS, P4VP, and PSS for both dcMS and HiPIMS conditions. Only their radius, distance, and cluster density differ. Particularly, differences during the in situ deposition are observed within the polymers in terms of distance (Figure S23), cluster density (Figure S24), and the radius (Figure S25). In Table 2 at various Au thicknesses, the distance, radius, crystallite size, and sheet resistance are summarized. In the case of the dcMS deposition (Figures S23 and S25) environment, PS has, with its phenyl functional groups, bigger distances and radius than P4VP, with its pyridine functional group, up to δAu,dcMS = 4.1 nm. After that threshold value, the distance and radius are similar. Additionally, until δAu,dcMS = 4.1 nm, P4VP has a higher cluster density than PS, which after that is similar. In contrast, PSS has throughout the in situ deposition a bigger distance and radius than PS and P4VP, which is induced due to the sulfonic acid functional group and has the smallest amount of cluster density during deposition. In case of HiPIMS deposition, environment PSS has still the biggest radius and distance throughout the deposition and the lowest cluster density. In case of PS and P4VP, both have the same radius and distance size, which originates due to the increased kinetic energy distribution of the ionized fraction during deposition, showing a reduced influence of the pyridine functional group of P4VP toward the phenyl functional group of PS. Löhrer et al. showed in a previous study already that the growth of Au is influenced by an addition of a benzodithiophene functional group resulting in a change of distance and radius during deposition. (28)

Figure 6

Figure 6. In-situ GIWAXS evolution of the crystallite size of (a) Au:PS, (b) Au:P4VP, and (c) Au:PSS.

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Table 2. Summary of Distance, Radius, Crystallite Size, and Sheet Resistance of Au Under dcMS and HiPIMS Conditions for PS, P4VP, and PSSa
  Distance [nm]Radius [nm]Crystallite size [nm]Sheet resistance [Ω/□]
MaterialThickness (δAu) [nm]dcMSHiPIMSdcMSHiPIMSdcMSHiPIMSdcMSHiPIMS
PS15.2 ± 0.14.8 ± 0.12.2 ± 0.12.1 ± 0.1---*-*
 28.2 ± 0.17.1 ± 0.13.9 ± 0.13.5 ± 0.14.1 ± 0.74.3 ± 0.9-*-*
 311.7 ± 0.19.9 ± 0.15.5 ± 0.15.0 ± 0.15.2 ± 0.55.4 ± 0.793.8 ± 0.153.3 ± 0.1
 413.8 ± 0.212.4 ± 0.16.8 ± 0.16.3 ± 0.16.2 ± 0.36.2 ± 0.531.5 ± 0.125.5± 0.1
 616.3 ± 0.314.4 ± 0.18.7 ± 0.18.1 ± 0.17.6 ± 0.37.4 ± 0.416.2 ± 0.114.0 ± 0.1
 8-15.8 ± 0.3-9.4 ± 0.19.2 ± 0.28.9 ± 0.39.9 ± 0.19.3 ± 0.1
P4VP14.5 ± 0.14.5 ± 0.12.0 ± 0.12.0 ± 0.1---*-*
 27.3 ± 0.16.9 ± 0.13.5 ± 0.13.4 ± 0.14.8 ± 0.54.5 ± 0.7-*-*
 310.6 ± 0.19.9 ± 0.15.2 ± 0.14.9 ± 0.15.8 ± 0.45.5 ± 0.5126.5 ± 0.155.6 ± 0.1
 413.2 ± 0.211.5 ± 0.16.6 ± 0.16.0 ± 0.16.6 ± 0.36.4 ± 0.437.6 ± 0.124.1 ± 0.1
 616.0 ± 0.313.7 ± 0.28.6 ± 0.17.7 ± 0.18.4 ± 0.28.0 ± 0.316.1 ± 0.112.8 ± 0.1
 817.2 ± 0.315.8 ± 0.310.0 ± 0.19.4 ± 0.19.9 ± 0.29.5 ± 0.310.9 ± 0.18.7 ± 0.1
PSS15.2 ± 0.14.9 ± 0.12.3 ± 0.12.1 ± 0.1---*-*
 28.2 ± 0.14.8 ± 0.14.1 ± 0.13.7 ± 0.14.6 ± 0.64.0 ± 0.9-*-*
 311.7 ± 0.17.1 ± 0.15.9 ± 0.15.4 ± 0.15.5 ± 0.45.2 ± 0.6120.4 ± 0.172.6 ± 0.1
 413.8 ± 0.29.9 ± 0.17.5 ± 0.16.9 ± 0.16.6 ± 0.36.3 ± 0.549.2 ± 0.128.1 ± 0.1
 616.3 ± 0.312.4 ± 0.110.5 ± 0.29.4 ± 0.18.3 ± 0.37.9 ± 0.416.1 ± 0.112.4 ± 0.1
 8-14.4 ± 0.112.9 ± 0.2-9.7 ± 0.29.5 ± 0.311.5 ± 0.18.6 ± 0.1
a

*: no conductivity was measured and the sheet resistance was set to 10 MΩ, which is the upper limit of the 4-point-probe range to measure the sheet resistance.

Conclusion

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Using a broad portfolio of real space and reciprocal space imaging methods, we present the nanoscale understanding of the influence of the atom kinetic energies and ionized fraction on the polymer–metal interface induced by two very important physical vapor deposition methods. This study about the dcMS and HiPIMS deposition of Au on thin PS, P4VP, and PSS films shows for early stages at δAu = 2 nm that only well separated Au islands are apparent. At δAu = 4 nm, HiPIMS deposition greatly increases the coverage compared to the dcMS. GISAXS reveals that an increase of the cluster density is responsible for an increase of coverage, which occurs due to an increase of nucleation points during the deposition. Furthermore, four-point-probe measurements reveal that HiPIMS-deposited Au has an earlier percolation threshold only for PSS. In-situ GISAXS investigation using the hemispherical model reveals that under the HiPIMS condition, the percolation threshold is earlier than dcMS for all polymeric templates. Additionally, it can be extracted that HiPIMS-deposited Au islands have a smaller average radius compared to dcMS-deposited Au islands. Furthermore, GIWAXS measurements reveal that with the chosen dcMS and HiPIMS parameters, the crystallite sizes remain similar throughout the entire deposition being independent from the chosen polymeric templates. These results provide a profound understanding of the formation of thin gold electrodes on polymers. It can be summed up that these results show that with HiPIMS deposition an increased coverage is achieved which is important for applications in the field of organic electronics. Future work fill focus on the effect of pulse duration and frequency on the growth behavior and microstructure.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.4c02344.

  • Skeletal structure of the polymers; XRR measurements; SLD profiles; FESEM measurements; GISAXS and GIWAXS detector images; surface coverage analysis with FESEM; GISAXS and GIWAXS scattering profiles with the corresponding fit; comparison of in situ analysis; comparison of FESEM- and GISAXS-derived cluster density; sheet resistance measurement (PDF)

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Author Information

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  • Corresponding Author
  • Authors
    • Yusuf Bulut - Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany;  Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany;  Orcidhttps://orcid.org/0000-0003-0090-3990
    • Benedikt Sochor - Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
    • Kristian A. Reck - Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany;  Orcidhttps://orcid.org/0000-0002-0823-6216
    • Bernhard Schummer - Fraunhofer Institute for Integrated Circuits IIS, Development Center for X-ray Technology EZRT, Flugplatzstr. 75, Fürth 90768, Germany
    • Alexander Meinhardt - Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany;  Department of Physics, University of Hamburg, Notkestr. 9-11, Hamburg 22607, Germany;  Orcidhttps://orcid.org/0000-0003-0552-3188
    • Jonas Drewes - Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany;  Orcidhttps://orcid.org/0000-0002-8539-1543
    • Suzhe Liang - Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany;  Orcidhttps://orcid.org/0000-0001-8773-897X
    • Tianfu Guan - Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany;  Orcidhttps://orcid.org/0000-0002-9887-9265
    • Arno Jeromin - Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany
    • Andreas Stierle - Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany;  Department of Physics, University of Hamburg, Notkestr. 9-11, Hamburg 22607, Germany;  Orcidhttps://orcid.org/0000-0002-0303-6282
    • Thomas F. Keller - Centre for X-ray and Nano Science CXNS, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, Hamburg 22607, Germany;  Department of Physics, University of Hamburg, Notkestr. 9-11, Hamburg 22607, Germany;  Orcidhttps://orcid.org/0000-0002-3770-6344
    • Thomas Strunskus - Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany;  Orcidhttps://orcid.org/0000-0003-3931-5635
    • Franz Faupel - Chair for Multicomponent Materials, Department for Materials Science, Faculty of Engineering, Kiel University, Kaiserstr. 2, Kiel 24143, Germany;  Orcidhttps://orcid.org/0000-0003-3367-1655
    • Peter Müller-Buschbaum - Department of Physics, Chair for Functional Materials, Technical University of Munich, TUM School of Natural Sciences, James-Franck-Str. 1, Garching 85748, Germany;  Heinz Maier-Leibnitz Zentrum (MLZ), Technical University of Munich, Lichtenbergstraße 1, Garching 85748, Germany;  Orcidhttps://orcid.org/0000-0002-9566-6088
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – project 459798762 (RO 4638/3-1, FA 234/36-1, and MU 1487/39-1). S.L. and T.G. acknowledge the financial support from the China Scholarship Council (CSC). We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III and at the DESY NanoLab, and we would like to thank Jan Rubeck and Matthias Schwartzkopf for assistance in using P03. Beamtime was allocated for proposal I-20210291.

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    Cobalt (Co) sputter deposition onto a colloidal polymer template is studied using grazing incidence small-angle x-ray scattering (GISAXS), SEM, and at. force microscopy (AFM). SEM and AFM data picture the sample topog., GISAXS the surface and near-surface film structure. A two-phase model is proposed to describe the time evolution of the Co growth. The presence of the colloidal template results in the correlated deposition of an ultrathin Co film on the sample surface and thus in the creation of Co capped polystyrene (PS) colloids. Well below the percolation threshold, the radial growth is restricted and only height growth is obsd.
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  8. 8
    Ziefuss, A. R.; Steenbock, T.; Benner, D.; Plech, A.; Göttlicher, J.; Teubner, M.; Grimm-Lebsanft, B.; Rehbock, C.; Comby-Zerbino, C.; Antoine, R. Photoluminescence of Fully Inorganic Colloidal Gold Nanocluster and Their Manipulation Using Surface Charge Effects. Adv. Mater. 2021, 33 (31), 2101549,  DOI: 10.1002/adma.202101549
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    Wang, Y.; Chen, J.; Zhong, Y.; Jeong, S.; Li, R.; Ye, X. Structural Diversity in Dimension-Controlled Assemblies of Tetrahedral Gold Nanocrystals. J. Am. Chem. Soc. 2022, 144 (30), 13538– 13546,  DOI: 10.1021/jacs.2c03196
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    9
    Structural Diversity in Dimension-Controlled Assemblies of Tetrahedral Gold Nanocrystals
    Wang, Yi; Chen, Jun; Zhong, Yaxu; Jeong, Soojin; Li, Ruipeng; Ye, Xingchen
    Journal of the American Chemical Society (2022), 144 (30), 13538-13546CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Polyhedron packings have fascinated humans for centuries and continue to inspire scientists of modern disciplines. Despite extensive computer simulations and a handful of exptl. investigations, understanding of the phase behaviors of synthetic tetrahedra has remained fragmentary largely due to the lack of tetrahedral building blocks with tunable size and versatile surface chem. Here, we report the remarkable richness of and complexity in dimension-controlled assemblies of gold nanotetrahedra. By tailoring nanocrystal interactions from long-range repulsive to hard-particle-like or to systems with short-ranged directional attractions through control of surface ligands and assembly conditions, nearly a dozen of two-dimensional and three-dimensional superstructures including the cubic diamond and hexagonal diamond polymorphs are selectively assembled. We further demonstrate multiply twinned icosahedral supracrystals by drying aq. gold nanotetrahedra on a hydrophobic substrate. This study expands the toolbox of the superstructure by design using tetrahedral building blocks and could spur future computational and exptl. work on self-assembly and phase behavior of anisotropic colloidal particles with tunable interactions.
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  10. 10
    Sousa, G. P.; de Barros, A.; Shimizu, F. M.; Sigoli, F. A.; Mazali, I. O. Plasmonic Photocatalysis Driven by Indirect Gold Excitation Via Upconversion Nanoparticle Emission Monitored In Situ by Surface-Enhanced Raman Spectroscopy. ACS Appl. Nano Mater. 2023, 6, 9206,  DOI: 10.1021/acsanm.3c00704
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    Amarandei, G.; O’Dwyer, C.; Arshak, A.; Corcoran, D. Fractal Patterning of Nanoparticles on Polymer Films and Their SERS Capabilities. ACS Appl. Mater. Interfaces 2013, 5 (17), 8655– 8662,  DOI: 10.1021/am402285e
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    Metwalli, E.; Couet, S.; Schlage, K.; Röhlsberger, R.; Körstgens, V.; Ruderer, M.; Wang, W.; Kaune, G.; Roth, S. V.; Müller-Buschbaum, P. In Situ GISAXS Investigation of Gold Sputtering onto a Polymer Template. Langmuir 2008, 24 (8), 4265– 4272,  DOI: 10.1021/la7038587
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    In situ GISAXS investigation of gold sputtering onto a polymer template
    Metwalli, E.; Couet, S.; Schlage, K.; Roehlsberger, R.; Koerstgens, V.; Ruderer, M.; Wang, W.; Kaune, G.; Roth, S. V.; Mueller-Buschbaum, P.
    Langmuir (2008), 24 (8), 4265-4272CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    Microphase-sepn. structures in mixed diblock-triblock copolymer thin films are used for the incorporation of gold atoms inside the polymer matrix via sputtering of gold. Polystyrene (PS) spheres are arranged in a liquidlike type with a well defined nearest neighbor distance inside a polyisoprene matrix acting as a template for directing the gold atoms. Sputtering conditions are selected with a very low sputtering rate to avoid clustering in the atm. so that gold reaches the polymer surface in its at. state. Due to the mobility of the gold atoms and the selective interaction with the PS parts of the microphase sepn. structure, gold is accumulated inside the polymer film in the PS spheres, as probed in situ with grazing incidence small-angle x-ray scattering (GISAXS). Nominally 4.3 Å of gold is deposited, which by diffusion is spread out vertically over a thickness of 280 nm. UV-vis spectroscopy reveals a small blue shift for the gold sputtered polymer film. At. force microscopy proves the absence of gold clusters on the film surface. For low sputtering rate, GISAXS proves good sensitivity for gold migration inside the polymer film and opens new possibilities for studying polymer-metal interaction.
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  13. 13
    Soria, E.; Gomez-Rodriguez, P.; Tromas, C.; Camelio, S.; Babonneau, D.; Serna, R.; Gonzalo, J.; Toudert, J. Self-Assembled, 10 Nm-Tailored, Near Infrared Plasmonic Metasurface Acting as Broadband Omnidirectional Polarizing Mirror. Adv. Opt. Mater 2020, 8 (21), 2000321,  DOI: 10.1002/adom.202000321
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    Zheng, T.; Kwon, H.; Faraon, A. Nanoelectromechanical Tuning of High- Q Slot Metasurfaces. Nano Lett. 2023, 23 (12), 5588– 5594,  DOI: 10.1021/acs.nanolett.3c00999
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    Walter, H.; Leitner, A. Role of Granular Structure in Metal Layers on the Optical Properties of Absorbing Mirrors. Opt. Eng. 2006, 45 (10), 103801,  DOI: 10.1117/1.2363167
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    Frank, M.; Bulut, Y.; Czympiel, L.; Weißing, R.; Nahrstedt, V.; Wilhelm, M.; Grosch, M.; Raauf, A.; Verma, A.; Fischer, T. Piezo-Enhanced Activation of Dinitrogen for Room Temperature Production of Ammonia. Nanotechnology 2021, 32 (46), 465601,  DOI: 10.1088/1361-6528/ac1a96
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    Cai, X.; Li, G.; Hu, W.; Zhu, Y. Catalytic Conversion of CO2over Atomically Precise Gold-Based Cluster Catalysts. ACS Catal. 2022, 12 (17), 10638– 10653,  DOI: 10.1021/acscatal.2c02595
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    Sankar, M.; He, Q.; Engel, R. V.; Sainna, M. A.; Logsdail, A. J.; Roldan, A.; Willock, D. J.; Agarwal, N.; Kiely, C. J.; Hutchings, G. J. Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts. Chem. Rev. 2020, 120 (8), 3890– 3938,  DOI: 10.1021/acs.chemrev.9b00662
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    Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts
    Sankar, Meenakshisundaram; He, Qian; Engel, Rebecca V.; Sainna, Mala A.; Logsdail, Andrew J.; Roldan, Alberto; Willock, David J.; Agarwal, Nishtha; Kiely, Christopher J.; Hutchings, Graham J.
    Chemical Reviews (Washington, DC, United States) (2020), 120 (8), 3890-3938CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. In this review, we discuss selected examples from recent literature on the role of the support on directing the nanostructures of Au-based monometallic and bimetallic nanoparticles. The role of support is then discussed in relation to the catalytic properties of Au-based monometallic and bimetallic nanoparticles using different gas phase and liq. phase reactions. The reactions discussed include CO oxidn., aerobic oxidn. of monohydric and polyhydric alcs., selective hydrogenation of alkynes, hydrogenation of nitroaroms., CO2 hydrogenation, C-C coupling, and methane oxidn. Only studies where the role of support has been explicitly studied in detail have been selected for discussion. However, the role of support is also examd. using examples of reactions involving unsupported metal nanoparticles (i.e., colloidal nanoparticles). It is clear that the support functionality can play a crucial role in tuning the catalytic activity that is obsd. and that advanced theory and characterization add greatly to our understanding of these fascinating catalysts.
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    Langer, N.; LeGrand, M.; Kedem, O. Cationic Polymer Coating Increases the Catalytic Activity of Gold Nanoparticles toward Anionic Substrates. ACS Appl. Mater. Interfaces 2023, 15 (24), 29160– 29169,  DOI: 10.1021/acsami.3c04087
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    19
    Cationic Polymer Coating Increases the Catalytic Activity of Gold Nanoparticles toward Anionic Substrates
    Langer, Nicholas; LeGrand, Mason; Kedem, Ofer
    ACS Applied Materials & Interfaces (2023), 15 (24), 29160-29169CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Org. coatings on catalytic metal nanoparticles (NPs) typically hinder their activity due to the blocking of active sites. Therefore, considerable effort is made to remove org. ligands when prepg. supported NP catalytic materials. Here, cationic polyelectrolyte coatings are shown to increase the catalytic activity of partially embedded gold nanoislands (Au NIs) toward transfer hydrogenation and oxidn. reactions with anionic substrates compared to the activity of identical but uncoated Au NIs. Any potential steric hindrance caused by the coating is countered by a decrease in the activation energy of the reaction by half, resulting in overall enhancement. The direct comparison to identical but uncoated NPs isolates the role of the coating and provides conclusive evidence of enhancement. Our findings show that engineering the microenvironment of heterogeneous catalysts, creating hybrid materials that cooperatively interact with the reactants involved, is a viable and exciting path to improving their performance.
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  20. 20
    Kang, T.; Zhu, J.; Luo, X.; Jia, W.; Wu, P.; Cai, C. Controlled Self-Assembly of a Close-Packed Gold Octahedra Array for SERS Sensing Exosomal MicroRNAs. Anal. Chem. 2021, 93 (4), 2519– 2526,  DOI: 10.1021/acs.analchem.0c04561
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    20
    Controlled self-assembly of a close-packed gold octahedra array for SERS sensing exosomal microRNAs
    Kang, Tuli; Zhu, Jingtian; Luo, Xiaojun; Jia, Wenyu; Wu, Ping; Cai, Chenxin
    Analytical Chemistry (Washington, DC, United States) (2021), 93 (4), 2519-2526CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
    MicroRNAs (miRNAs) in exosomes can be transferred from parental cells to recipient cells by trafficking exosomes, and they are effective in regulating the gene expression of the recipient cells. Therefore, exosomal miRNAs play a vital role in cancer biol. and could be potential biomarkers for cancer diagnosis and therapeutic responses. However, accurate detection of exosomal miRNAs is still challenging due to the low abundance of any given miRNA in exosomes. Herein, a surface-enhanced Raman scattering (SERS)-based sensor was developed for the quant. detn. of let-7a miRNAs in MCF-7 cell-derived exosomes (MCF-7 exosomes) using a close-packed and ordered Au octahedral array as a sensing platform. Au octahedra in the array uniformly stand on their triangular face. This kind of orientation produces "hot surfaces" rather than "hot spots" and greatly improves the detection sensitivity and uniformity. Let-7a detection with single-base specificity was thus achieved from the SERS intensity change induced by the structural switch of the probing DNA from a hairpin to a duplex in the presence of the target. The sensor showed a broad linear range (10 aM to 10 nM) and a low detection limit (5.3 aM) without using any signal amplification strategy. Moreover, this sensor could accurately detect target let-7a in MCF-7 exosomes and further value the impact of drug treatment on exosomal let-7a expression, indicating promising applications of the developed sensor for cancer diagnostics and therapy.
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  21. 21
    Meyer, S. M.; Murphy, C. J. Anisotropic Silica Coating on Gold Nanorods Boosts Their Potential as SERS Sensors. Nanoscale 2022, 14 (13), 5214– 5226,  DOI: 10.1039/D1NR07918B
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    Anisotropic silica coating on gold nanorods boosts their potential as SERS sensors
    Meyer, Sean M.; Murphy, Catherine J.
    Nanoscale (2022), 14 (13), 5214-5226CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
    Gold nanorods are well-known surface-enhanced Raman scattering substrates. Under longitudinal plasmonic excitation, the ends of the nanorods experience larger local elec. fields compared to the sides of the rods, suggesting that Raman-active mols. would be best detected if the mols. could preferentially bind to the ends of the nanorods. Coating the tips of gold nanorods with anionic mesoporous silica caps enabled surface-enhanced Raman scattering (SERS) detection of the cationic dye methylene blue at lower concns. than obsd. for the corresponding silica coating of the entire rod. By analyzing the intensity ratio of two Raman active modes of methylene blue and the surface plasmon resonance peak shift of the gold nanorod composites, it can be inferred that at a low concn. of methylene blue, mols. adsorb to the tips of the tip coated silica gold nanorods. Functionalization of the anionic silica endcaps with cationic groups eliminates the SERS enhancement for the cationic methylene blue, demonstrating the electrostatic nature of the adsorption process in this case. These results show that anisotropic silica coatings can conc. analytes at the tips of gold nanorods for improvements in chem. sensing and diagnostics.
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  22. 22
    Grys, D.-B.; Niihori, M.; Arul, R.; Sibug-Torres, S. M.; Wyatt, E. W.; de Nijs, B.; Baumberg, J. J. Controlling Atomic-Scale Restructuring and Cleaning of Gold Nanogap Multilayers for Surface-Enhanced Raman Scattering Sensing. ACS Sens. 2023, 8 (7), 2879– 2888,  DOI: 10.1021/acssensors.3c00967
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    Guo, P.; Zhu, H.; Zhao, W.; Liu, C.; Zhu, L.; Ye, Q.; Jia, N.; Wang, H.; Zhang, X.; Huang, W.; Vinokurov, V. A.; Ivanov, E.; Shchukin, D.; Harvey, D.; Ulloa, J. M.; Hierro, A.; Wang, H. Interfacial Embedding of Laser-Manufactured Fluorinated Gold Clusters Enabling Stable Perovskite Solar Cells with Efficiency Over 24%. Adv. Mater. 2021, 33 (36), 1– 11,  DOI: 10.1002/adma.202101590
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    Notarianni, M.; Vernon, K.; Chou, A.; Aljada, M.; Liu, J.; Motta, N. Plasmonic Effect of Gold Nanoparticles in Organic Solar Cells. Sol. Energy 2014, 106, 23– 37,  DOI: 10.1016/j.solener.2013.09.026
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    Plasmonic effect of gold nanoparticles in organic solar cells
    Notarianni, Marco; Vernon, Kristy; Chou, Alison; Aljada, Muhsen; Liu, Jinzhang; Motta, Nunzio
    Solar Energy (2014), 106 (), 23-37CODEN: SRENA4; ISSN:0038-092X. (Elsevier Ltd.)
    A review. Light trapping, due to the embedding of metallic nanoparticles, has been shown to be beneficial for a better photoabsorption in org. solar cells. Researchers in plasmonics and in the org. photovoltaics fields are working together to improve the absorption of sunlight and the photon-electron coupling to boost the performance of the devices.Recent advances in the field of plasmonics for org. solar cells focus on the incorporation of gold nanoparticles. This article reviews the different methods to produce and embed gold nanoparticles into org. solar cells. In particular, concn., size and geometry of gold nanoparticles are key factors that directly influence the light absorption in the devices. It is shown that a careful choice of size, concn. and location of gold nanoparticles in the device result in an enhancement of the power conversion efficiencies when compared to std. org. solar cell devices.Our latest results on gold nanoparticles embedded in on org. solar cell devices are included. We demonstrate that embedded gold nanoparticles, created by depositing and annealing a gold film on transparent electrode, generate a plasmonic effect which can be exploited to increase the power conversion efficiency of a bulk heterojunction solar cell up to 10%.
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    Domanski, K.; Correa-Baena, J. P.; Mine, N.; Nazeeruddin, M. K.; Abate, A.; Saliba, M.; Tress, W.; Hagfeldt, A.; Grätzel, M. Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells. ACS Nano 2016, 10 (6), 6306– 6314,  DOI: 10.1021/acsnano.6b02613
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    Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells
    Domanski, Konrad; Correa-Baena, Juan-Pablo; Mine, Nicolas; Nazeeruddin, Mohammad Khaja; Abate, Antonio; Saliba, Michael; Tress, Wolfgang; Hagfeldt, Anders; Gratzel, Michael
    ACS Nano (2016), 10 (6), 6306-6314CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    Perovskite solar cells (PSCs) have now achieved efficiencies in excess of 22%, but very little is known about their long-term stability under thermal stress. So far, stability reports have hinted at the importance of substituting the org. components, but little attention has been given to the metal contact. We investigated the stability of state-of-the-art PSCs with efficiencies exceeding 20%. Remarkably, we found that exposing PSCs to a temp. of 70 °C is enough to induce gold migration through the hole-transporting layer (HTL), spiro-MeOTAD, and into the perovskite material, which in turn severely affects the device performance metrics under working conditions. Importantly, we found that the main cause of irreversible degrdn. is not due to decompn. of the org. and hybrid perovskite layers. By introducing a Cr metal interlayer between the HTL and gold electrode, high-temp.-induced irreversible long-term losses are avoided. This key finding is essential in the quest for achieving high efficiency, long-term stable PSCs which, in order to be com. viable, need to withstand hard thermal stress tests.
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  26. 26
    Cao, S.; Yu, D.; Lin, Y.; Zhang, C.; Lu, L.; Yin, M.; Zhu, X.; Chen, X.; Li, D. Light Propagation in Flexible Thin-Film Amorphous Silicon Solar Cells with Nanotextured Metal Back Reflectors. ACS Appl. Mater. Interfaces 2020, 12 (23), 26184– 26192,  DOI: 10.1021/acsami.0c05330
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    Goyal, A.; Koper, M. T. M. The Interrelated Effect of Cations and Electrolyte PH on the Hydrogen Evolution Reaction on Gold Electrodes in Alkaline Media. Angew. Chem., Int. Ed. 2021, 60 (24), 13452– 13462,  DOI: 10.1002/anie.202102803
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    The Interrelated Effect of Cations and Electrolyte pH on the Hydrogen Evolution Reaction on Gold Electrodes in Alkaline Media
    Goyal, Akansha; Koper, Marc T. M.
    Angewandte Chemie, International Edition (2021), 60 (24), 13452-13462CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    In this work we study the role of alkali metal cation concn. and electrolyte pH in altering the kinetics of the hydrogen evolution reaction (HER) at gold (Au) electrodes. We show that at moderately alk. pH (pH 11), increasing the cation concn. significantly enhances the HER activity on Au electrodes (with a reaction order ≈0.5). Based on these results we suggest that cations play a central role in stabilizing the transition state of the rate-detg. Volmer step by favorably interacting with the dissocg. water mol. (*H-OHδ--cat+). Moreover, we show that increasing electrolyte pH (pH 10 to pH 13) tunes the local field strength, which in turn indirectly enhances the activity of HER by tuning the near-surface cation concn. Interestingly, a too high near-surface cation concn. (at high pH and high cation concn.) leads to a lowering of the HER activity, which we ascribe to a blockage of the surface by near-surface cations.
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  28. 28
    Löhrer, F. C.; Körstgens, V.; Semino, G.; Schwartzkopf, M.; Hinz, A.; Polonskyi, O.; Strunskus, T.; Faupel, F.; Roth, S. V.; Müller-Buschbaum, P. Following in Situ the Deposition of Gold Electrodes on Low Band Gap Polymer Films. ACS Appl. Mater. Interfaces 2020, 12 (1), 1132– 1141,  DOI: 10.1021/acsami.9b17590
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    Kas, R.; Yang, K.; Bohra, D.; Kortlever, R.; Burdyny, T.; Smith, W. A. Electrochemical Co2 Reduction on Nanostructured Metal Electrodes: Fact or Defect?. Chem. Sci. 2020, 11 (7), 1738– 1749,  DOI: 10.1039/C9SC05375A
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    29
    Electrochemical CO2 reduction on nanostructured metal electrodes: fact or defect?
    Kas, Recep; Yang, Kailun; Bohra, Divya; Kortlever, Ruud; Burdyny, Thomas; Smith, Wilson A.
    Chemical Science (2020), 11 (7), 1738-1749CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    A review. Electrochem. CO2 redn. has received an increased amt. of interest in the last decade as a promising avenue for storing renewable electricity in chem. bonds. Despite considerable progress on catalyst performance using nanostructured electrodes, the sensitivity of the reaction to process conditions has led to debate on the origin of the activity and high selectivity. Addnl., this raises questions on the transferability of the performance and knowledge to other electrochem. systems. At its core, the discrepancy is primarily a result of the highly porous nature of nanostructured electrodes, which are vulnerable to both mass transport effects and structural changes during the electrolysis. Both effects are not straightforward to identify and difficult to decouple. Despite the susceptibility of nanostructured electrodes to mass transfer limitations, we highlight that nanostructured silver electrodes exhibit considerably higher activity when normalized to the electrochem. active surface in contrast to gold and copper electrodes. Alongside, we provide a discussion on how active surface area and thickness of the catalytic layer itself can influence the onset potential, selectivity, stability, activity and mass transfer inside and outside of the three dimensional catalyst layer. Key parameters and potential solns. are highlighted to decouple mass transfer effects from the measured activity in electrochem. cells utilizing CO2 satd. aq. solns.
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    Marcandalli, G.; Goyal, A.; Koper, M. T. M. Electrolyte Effects on the Faradaic Efficiency of CO2Reduction to CO on a Gold Electrode. ACS Catal. 2021, 11 (9), 4936– 4945,  DOI: 10.1021/acscatal.1c00272
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    Bandorf, R.; Waschke, S.; Carreri, F. C.; Vergöhl, M.; Grundmeier, G.; Bräuer, G. Direct Metallization of PMMA with Aluminum Films Using HIPIMS. Surf. Coat. Technol. 2016, 290, 77– 81,  DOI: 10.1016/j.surfcoat.2015.10.070
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    Bandorf, R.; Waschke, S.; Vergöhl, M.; Grundmeier, G.; Bräuer, G. Direct Metallization of Plastics by High Power Impulse Magnetron Sputtering. Vak. Forsch. Prax. 2015, 27 (4), 18– 23,  DOI: 10.1002/vipr.201500587
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    Bulut, Y.; Sochor, B.; Harder, C.; Reck, K.; Drewes, J.; Xu, Z.; Jiang, X.; Meinhardt, A.; Jeromin, A.; Kohantorabi, M.; Noei, H.; Keller, T. F.; Strunskus, T.; Faupel, F.; Müller-Buschbaum, P.; Roth, S. V. Diblock Copolymer Pattern Protection by Silver Cluster Reinforcement. Nanoscale 2023, 15 (38), 15768– 15774,  DOI: 10.1039/D3NR03215A
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    Christou, C.; Barber, Z. H. Ionization of Sputtered Material in a Planar Magnetron Discharge. J. Vac. Sci. Technol. A 2000, 18 (6), 2897– 2907,  DOI: 10.1116/1.1312370
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    Lundin, D.; Larsson, P.; Wallin, E.; Lattemann, M.; Brenning, N.; Helmersson, U. Cross-Field Ion Transport during High Power Impulse Magnetron Sputtering. Plasma Sources Sci. Technol 2008, 17 (3), 035021,  DOI: 10.1088/0963-0252/17/3/035021
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    Lü, B.; Münger, E. P.; Sarakinos, K. Coalescence-Controlled and Coalescence-Free Growth Regimes during Deposition of Pulsed Metal Vapor Fluxes on Insulating Surfaces. J. Appl. Phys. 2015, 117 (13), 134304,  DOI: 10.1063/1.4916983
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    36
    Coalescence-controlled and coalescence-free growth regimes during deposition of pulsed metal vapor fluxes on insulating surfaces
    Lu, B.; Munger, E. P.; Sarakinos, K.
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    The morphol. and phys. properties of thin films deposited by vapor condensation on solid surfaces are predominantly set by the processes of island nucleation, growth and coalescence. When deposition is performed using pulsed vapor fluxes, three distinct nucleation regimes are known to exist depending on the temporal profile of the flux. These regimes can be accessed by tuning deposition conditions; however, their effect on film microstructure becomes marginal when coalescence sets in and erases morphol. features obtained during nucleation. By preventing coalescence from being completed, these nucleation regimes can be used to control microstructure evolution and thus access a larger palette of film morphol. features. Recently, the authors derived the quant. criterion to stop coalescence during continuous metal vapor flux deposition on insulating surfaces-which typically yields 3-dimensional growth-by describing anal. the competition between island growth by at. incorporation and the coalescence rate of islands [Lu et al., (2014)]. Here, the authors develop the anal. framework for entering a coalescence-free growth regime for metal vapor deposition on insulating substrates using pulsed vapor fluxes, showing that there exist three distinct criteria for suppressing coalescence that correspond to the three nucleation regimes of pulsed vapor flux deposition. The theor. framework developed herein is substantiated by kinetic Monte Carlo growth simulations. The findings highlight the possibility of using atomistic nucleation theory for pulsed vapor deposition to control morphol. of thin films beyond the point of island d. satn. (c) 2015 American Institute of Physics.
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    Role of Sputter Deposition Rate in Tailoring Nanogranular Gold Structures on Polymer Surfaces
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    To obtain full control over the complex nanostructural evolution at the polymer-metal interface, the authors monitor the evolution of the metallic layer morphol. with in situ time-resolved grazing-incidence small-angle X-ray scattering during sputter deposition. The authors 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 obsd. 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 morphol. parameters of the gold cluster ensemble relevant for various applications as a function of the effective layer thickness and deposition rate.
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  • Abstract

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    Figure 1

    Figure 1. FESEM images of Au-coated (a, d, g, j) Au:PS, (b ,e, h, k) Au:P4VP, and (c, f, i, l) Au:PSS. Panels a–c were coated with δAu,dcMS = 2 nm, panels d–f were coated with δAu,HiPIMS = 2 nm, panels g–i were coated with δAu,dcMS = 4 nm, and panels j–l were coated with δAu,HiPIMS = 4 nm.

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    Figure 2

    Figure 2. AFM images of (a, c, e) dcMS- and (b, d, f) HiPIMS-deposited gold δAu = 3 nm on (a, b) Au:PS, (c, d) Au:P4VP, and (e, f) Au:PSS are shown. The red box highlights the magnification of the region of interest. The red circle in the magnified box highlights the isolated Au islands.

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    Figure 3

    Figure 3. In-situ evolution of the distance of Au islands forming on (a) Au:PS, (b) Au:P4VP, and (c) Au:PSS. In situ evolution of the cluster density of Au islands on (d) Au:PS, (e) Au:P4VP, and (f) Au:PSS.

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    Figure 4

    Figure 4. In-situ evolution of the radius R derived from the hemispherical geometrical model for (a) Au:PS, (b) Au:P4VP, and (c) Au:PSS. In-situ evolution of the ratio two times the radius (2R = cluster diameter) and the correlation distance D to determine the percolation threshold for (d) Au:PS, (e) Au:P4VP, and (f) Au:PSS. The pink line at 2R/D = 1.0 in (d–f) denotes the percolation threshold.

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    Figure 5

    Figure 5. 4-point-probe measurements with the corresponding sigmoidal Boltzmann fit for (a) Au:PSHiPIMS, (b) Au:P4VPHiPIMS, (c) Au:PSSHiPIMS, (d) Au:PSdcMS, (e) Au:P4VPdcMS, and (f) Au:PSSdcMS with a deposited thickness being δAu = 1, 2, 3, 4, 6, and 8 nm.

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    Figure 6

    Figure 6. In-situ GIWAXS evolution of the crystallite size of (a) Au:PS, (b) Au:P4VP, and (c) Au:PSS.

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      There is no corresponding record for this reference.
    4. 4
      Ren, H.-T.; Cai, C.-C.; Cao, W.-B.; Li, D.-S.; Li, T.-T.; Lou, C.-W.; Lin, J.-H. Superhydrophobic TiN-Coated Cotton Fabrics with Nanoscale Roughness and Photothermal Self-Healing Properties for Effective Oil–Water Separation. ACS Appl. Nano Mater. 2023, 6 (13), 11925– 11933,  DOI: 10.1021/acsanm.3c01763
      There is no corresponding record for this reference.
    5. 5
      Morisue, M.; Hoshino, Y.; Shimizu, M.; Tomita, S.; Sasaki, S.; Sakurai, S.; Hikima, T.; Kawamura, A.; Kohri, M.; Matsui, J.; Yamao, T. A Metal-Lustrous Porphyrin Foil. Chem. Commun. 2017, 53 (77), 10703– 10706,  DOI: 10.1039/C7CC06159E
      There is no corresponding record for this reference.
    6. 6
      Chen, A. X.; Lau, H. Y.; Teo, J. Y.; Wang, Y.; Choong, D. Z. Y.; Wang, Y.; Luo, H.-K.; Yang, Y. Y.; Li, N. Water-Mediated In Situ Fabrication of CuI Nanoparticles on Flexible Cotton Fabrics as a Sustainable and Skin-Compatible Coating with Broad-Spectrum Antimicrobial Efficacy. ACS Appl. Nano Mater. 2023, 6 (14), 13238– 13249,  DOI: 10.1021/acsanm.3c01961
      There is no corresponding record for this reference.
    7. 7
      Buffet, A.; Abul Kashem, M. M.; Schlage, K.; Couet, S.; Röhlsberger, R.; Rothkirch, A.; Herzog, G.; Metwalli, E.; Meier, R.; Kaune, G.; Rawolle, M.; Müller-Buschbaum, P.; Gehrke, R.; Roth, S. V. Time-Resolved Ultrathin Cobalt Film Growth on a Colloidal Polymer Template. Langmuir 2011, 27 (1), 343– 346,  DOI: 10.1021/la102900v
      7
      Time-Resolved Ultrathin Cobalt Film Growth on a Colloidal Polymer Template
      Buffet, Adeline; Abul Kashem, Mottakin M.; Schlage, Kai; Couet, Sebastien; Rohlsberger, Ralph; Rothkirch, Andre; Herzog, Gerd; Metwalli, Ezzeldin; Meier, Robert; Kaune, Gunar; Rawolle, Monica; Muller-Buschbaum, Peter; Gehrke, Rainer; Roth, Stephan V.
      Langmuir (2011), 27 (1), 343-346CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      Cobalt (Co) sputter deposition onto a colloidal polymer template is studied using grazing incidence small-angle x-ray scattering (GISAXS), SEM, and at. force microscopy (AFM). SEM and AFM data picture the sample topog., GISAXS the surface and near-surface film structure. A two-phase model is proposed to describe the time evolution of the Co growth. The presence of the colloidal template results in the correlated deposition of an ultrathin Co film on the sample surface and thus in the creation of Co capped polystyrene (PS) colloids. Well below the percolation threshold, the radial growth is restricted and only height growth is obsd.
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    8. 8
      Ziefuss, A. R.; Steenbock, T.; Benner, D.; Plech, A.; Göttlicher, J.; Teubner, M.; Grimm-Lebsanft, B.; Rehbock, C.; Comby-Zerbino, C.; Antoine, R. Photoluminescence of Fully Inorganic Colloidal Gold Nanocluster and Their Manipulation Using Surface Charge Effects. Adv. Mater. 2021, 33 (31), 2101549,  DOI: 10.1002/adma.202101549
      There is no corresponding record for this reference.
    9. 9
      Wang, Y.; Chen, J.; Zhong, Y.; Jeong, S.; Li, R.; Ye, X. Structural Diversity in Dimension-Controlled Assemblies of Tetrahedral Gold Nanocrystals. J. Am. Chem. Soc. 2022, 144 (30), 13538– 13546,  DOI: 10.1021/jacs.2c03196
      9
      Structural Diversity in Dimension-Controlled Assemblies of Tetrahedral Gold Nanocrystals
      Wang, Yi; Chen, Jun; Zhong, Yaxu; Jeong, Soojin; Li, Ruipeng; Ye, Xingchen
      Journal of the American Chemical Society (2022), 144 (30), 13538-13546CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Polyhedron packings have fascinated humans for centuries and continue to inspire scientists of modern disciplines. Despite extensive computer simulations and a handful of exptl. investigations, understanding of the phase behaviors of synthetic tetrahedra has remained fragmentary largely due to the lack of tetrahedral building blocks with tunable size and versatile surface chem. Here, we report the remarkable richness of and complexity in dimension-controlled assemblies of gold nanotetrahedra. By tailoring nanocrystal interactions from long-range repulsive to hard-particle-like or to systems with short-ranged directional attractions through control of surface ligands and assembly conditions, nearly a dozen of two-dimensional and three-dimensional superstructures including the cubic diamond and hexagonal diamond polymorphs are selectively assembled. We further demonstrate multiply twinned icosahedral supracrystals by drying aq. gold nanotetrahedra on a hydrophobic substrate. This study expands the toolbox of the superstructure by design using tetrahedral building blocks and could spur future computational and exptl. work on self-assembly and phase behavior of anisotropic colloidal particles with tunable interactions.
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    10. 10
      Sousa, G. P.; de Barros, A.; Shimizu, F. M.; Sigoli, F. A.; Mazali, I. O. Plasmonic Photocatalysis Driven by Indirect Gold Excitation Via Upconversion Nanoparticle Emission Monitored In Situ by Surface-Enhanced Raman Spectroscopy. ACS Appl. Nano Mater. 2023, 6, 9206,  DOI: 10.1021/acsanm.3c00704
      There is no corresponding record for this reference.
    11. 11
      Amarandei, G.; O’Dwyer, C.; Arshak, A.; Corcoran, D. Fractal Patterning of Nanoparticles on Polymer Films and Their SERS Capabilities. ACS Appl. Mater. Interfaces 2013, 5 (17), 8655– 8662,  DOI: 10.1021/am402285e
      There is no corresponding record for this reference.
    12. 12
      Metwalli, E.; Couet, S.; Schlage, K.; Röhlsberger, R.; Körstgens, V.; Ruderer, M.; Wang, W.; Kaune, G.; Roth, S. V.; Müller-Buschbaum, P. In Situ GISAXS Investigation of Gold Sputtering onto a Polymer Template. Langmuir 2008, 24 (8), 4265– 4272,  DOI: 10.1021/la7038587
      12
      In situ GISAXS investigation of gold sputtering onto a polymer template
      Metwalli, E.; Couet, S.; Schlage, K.; Roehlsberger, R.; Koerstgens, V.; Ruderer, M.; Wang, W.; Kaune, G.; Roth, S. V.; Mueller-Buschbaum, P.
      Langmuir (2008), 24 (8), 4265-4272CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      Microphase-sepn. structures in mixed diblock-triblock copolymer thin films are used for the incorporation of gold atoms inside the polymer matrix via sputtering of gold. Polystyrene (PS) spheres are arranged in a liquidlike type with a well defined nearest neighbor distance inside a polyisoprene matrix acting as a template for directing the gold atoms. Sputtering conditions are selected with a very low sputtering rate to avoid clustering in the atm. so that gold reaches the polymer surface in its at. state. Due to the mobility of the gold atoms and the selective interaction with the PS parts of the microphase sepn. structure, gold is accumulated inside the polymer film in the PS spheres, as probed in situ with grazing incidence small-angle x-ray scattering (GISAXS). Nominally 4.3 Å of gold is deposited, which by diffusion is spread out vertically over a thickness of 280 nm. UV-vis spectroscopy reveals a small blue shift for the gold sputtered polymer film. At. force microscopy proves the absence of gold clusters on the film surface. For low sputtering rate, GISAXS proves good sensitivity for gold migration inside the polymer film and opens new possibilities for studying polymer-metal interaction.
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    13. 13
      Soria, E.; Gomez-Rodriguez, P.; Tromas, C.; Camelio, S.; Babonneau, D.; Serna, R.; Gonzalo, J.; Toudert, J. Self-Assembled, 10 Nm-Tailored, Near Infrared Plasmonic Metasurface Acting as Broadband Omnidirectional Polarizing Mirror. Adv. Opt. Mater 2020, 8 (21), 2000321,  DOI: 10.1002/adom.202000321
      There is no corresponding record for this reference.
    14. 14
      Zheng, T.; Kwon, H.; Faraon, A. Nanoelectromechanical Tuning of High- Q Slot Metasurfaces. Nano Lett. 2023, 23 (12), 5588– 5594,  DOI: 10.1021/acs.nanolett.3c00999
      There is no corresponding record for this reference.
    15. 15
      Walter, H.; Leitner, A. Role of Granular Structure in Metal Layers on the Optical Properties of Absorbing Mirrors. Opt. Eng. 2006, 45 (10), 103801,  DOI: 10.1117/1.2363167
      There is no corresponding record for this reference.
    16. 16
      Frank, M.; Bulut, Y.; Czympiel, L.; Weißing, R.; Nahrstedt, V.; Wilhelm, M.; Grosch, M.; Raauf, A.; Verma, A.; Fischer, T. Piezo-Enhanced Activation of Dinitrogen for Room Temperature Production of Ammonia. Nanotechnology 2021, 32 (46), 465601,  DOI: 10.1088/1361-6528/ac1a96
      There is no corresponding record for this reference.
    17. 17
      Cai, X.; Li, G.; Hu, W.; Zhu, Y. Catalytic Conversion of CO2over Atomically Precise Gold-Based Cluster Catalysts. ACS Catal. 2022, 12 (17), 10638– 10653,  DOI: 10.1021/acscatal.2c02595
      There is no corresponding record for this reference.
    18. 18
      Sankar, M.; He, Q.; Engel, R. V.; Sainna, M. A.; Logsdail, A. J.; Roldan, A.; Willock, D. J.; Agarwal, N.; Kiely, C. J.; Hutchings, G. J. Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts. Chem. Rev. 2020, 120 (8), 3890– 3938,  DOI: 10.1021/acs.chemrev.9b00662
      18
      Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts
      Sankar, Meenakshisundaram; He, Qian; Engel, Rebecca V.; Sainna, Mala A.; Logsdail, Andrew J.; Roldan, Alberto; Willock, David J.; Agarwal, Nishtha; Kiely, Christopher J.; Hutchings, Graham J.
      Chemical Reviews (Washington, DC, United States) (2020), 120 (8), 3890-3938CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. In this review, we discuss selected examples from recent literature on the role of the support on directing the nanostructures of Au-based monometallic and bimetallic nanoparticles. The role of support is then discussed in relation to the catalytic properties of Au-based monometallic and bimetallic nanoparticles using different gas phase and liq. phase reactions. The reactions discussed include CO oxidn., aerobic oxidn. of monohydric and polyhydric alcs., selective hydrogenation of alkynes, hydrogenation of nitroaroms., CO2 hydrogenation, C-C coupling, and methane oxidn. Only studies where the role of support has been explicitly studied in detail have been selected for discussion. However, the role of support is also examd. using examples of reactions involving unsupported metal nanoparticles (i.e., colloidal nanoparticles). It is clear that the support functionality can play a crucial role in tuning the catalytic activity that is obsd. and that advanced theory and characterization add greatly to our understanding of these fascinating catalysts.
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    19. 19
      Langer, N.; LeGrand, M.; Kedem, O. Cationic Polymer Coating Increases the Catalytic Activity of Gold Nanoparticles toward Anionic Substrates. ACS Appl. Mater. Interfaces 2023, 15 (24), 29160– 29169,  DOI: 10.1021/acsami.3c04087
      19
      Cationic Polymer Coating Increases the Catalytic Activity of Gold Nanoparticles toward Anionic Substrates
      Langer, Nicholas; LeGrand, Mason; Kedem, Ofer
      ACS Applied Materials & Interfaces (2023), 15 (24), 29160-29169CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Org. coatings on catalytic metal nanoparticles (NPs) typically hinder their activity due to the blocking of active sites. Therefore, considerable effort is made to remove org. ligands when prepg. supported NP catalytic materials. Here, cationic polyelectrolyte coatings are shown to increase the catalytic activity of partially embedded gold nanoislands (Au NIs) toward transfer hydrogenation and oxidn. reactions with anionic substrates compared to the activity of identical but uncoated Au NIs. Any potential steric hindrance caused by the coating is countered by a decrease in the activation energy of the reaction by half, resulting in overall enhancement. The direct comparison to identical but uncoated NPs isolates the role of the coating and provides conclusive evidence of enhancement. Our findings show that engineering the microenvironment of heterogeneous catalysts, creating hybrid materials that cooperatively interact with the reactants involved, is a viable and exciting path to improving their performance.
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    20. 20
      Kang, T.; Zhu, J.; Luo, X.; Jia, W.; Wu, P.; Cai, C. Controlled Self-Assembly of a Close-Packed Gold Octahedra Array for SERS Sensing Exosomal MicroRNAs. Anal. Chem. 2021, 93 (4), 2519– 2526,  DOI: 10.1021/acs.analchem.0c04561
      20
      Controlled self-assembly of a close-packed gold octahedra array for SERS sensing exosomal microRNAs
      Kang, Tuli; Zhu, Jingtian; Luo, Xiaojun; Jia, Wenyu; Wu, Ping; Cai, Chenxin
      Analytical Chemistry (Washington, DC, United States) (2021), 93 (4), 2519-2526CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
      MicroRNAs (miRNAs) in exosomes can be transferred from parental cells to recipient cells by trafficking exosomes, and they are effective in regulating the gene expression of the recipient cells. Therefore, exosomal miRNAs play a vital role in cancer biol. and could be potential biomarkers for cancer diagnosis and therapeutic responses. However, accurate detection of exosomal miRNAs is still challenging due to the low abundance of any given miRNA in exosomes. Herein, a surface-enhanced Raman scattering (SERS)-based sensor was developed for the quant. detn. of let-7a miRNAs in MCF-7 cell-derived exosomes (MCF-7 exosomes) using a close-packed and ordered Au octahedral array as a sensing platform. Au octahedra in the array uniformly stand on their triangular face. This kind of orientation produces "hot surfaces" rather than "hot spots" and greatly improves the detection sensitivity and uniformity. Let-7a detection with single-base specificity was thus achieved from the SERS intensity change induced by the structural switch of the probing DNA from a hairpin to a duplex in the presence of the target. The sensor showed a broad linear range (10 aM to 10 nM) and a low detection limit (5.3 aM) without using any signal amplification strategy. Moreover, this sensor could accurately detect target let-7a in MCF-7 exosomes and further value the impact of drug treatment on exosomal let-7a expression, indicating promising applications of the developed sensor for cancer diagnostics and therapy.
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    21. 21
      Meyer, S. M.; Murphy, C. J. Anisotropic Silica Coating on Gold Nanorods Boosts Their Potential as SERS Sensors. Nanoscale 2022, 14 (13), 5214– 5226,  DOI: 10.1039/D1NR07918B
      21
      Anisotropic silica coating on gold nanorods boosts their potential as SERS sensors
      Meyer, Sean M.; Murphy, Catherine J.
      Nanoscale (2022), 14 (13), 5214-5226CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
      Gold nanorods are well-known surface-enhanced Raman scattering substrates. Under longitudinal plasmonic excitation, the ends of the nanorods experience larger local elec. fields compared to the sides of the rods, suggesting that Raman-active mols. would be best detected if the mols. could preferentially bind to the ends of the nanorods. Coating the tips of gold nanorods with anionic mesoporous silica caps enabled surface-enhanced Raman scattering (SERS) detection of the cationic dye methylene blue at lower concns. than obsd. for the corresponding silica coating of the entire rod. By analyzing the intensity ratio of two Raman active modes of methylene blue and the surface plasmon resonance peak shift of the gold nanorod composites, it can be inferred that at a low concn. of methylene blue, mols. adsorb to the tips of the tip coated silica gold nanorods. Functionalization of the anionic silica endcaps with cationic groups eliminates the SERS enhancement for the cationic methylene blue, demonstrating the electrostatic nature of the adsorption process in this case. These results show that anisotropic silica coatings can conc. analytes at the tips of gold nanorods for improvements in chem. sensing and diagnostics.
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    22. 22
      Grys, D.-B.; Niihori, M.; Arul, R.; Sibug-Torres, S. M.; Wyatt, E. W.; de Nijs, B.; Baumberg, J. J. Controlling Atomic-Scale Restructuring and Cleaning of Gold Nanogap Multilayers for Surface-Enhanced Raman Scattering Sensing. ACS Sens. 2023, 8 (7), 2879– 2888,  DOI: 10.1021/acssensors.3c00967
      There is no corresponding record for this reference.
    23. 23
      Guo, P.; Zhu, H.; Zhao, W.; Liu, C.; Zhu, L.; Ye, Q.; Jia, N.; Wang, H.; Zhang, X.; Huang, W.; Vinokurov, V. A.; Ivanov, E.; Shchukin, D.; Harvey, D.; Ulloa, J. M.; Hierro, A.; Wang, H. Interfacial Embedding of Laser-Manufactured Fluorinated Gold Clusters Enabling Stable Perovskite Solar Cells with Efficiency Over 24%. Adv. Mater. 2021, 33 (36), 1– 11,  DOI: 10.1002/adma.202101590
      There is no corresponding record for this reference.
    24. 24
      Notarianni, M.; Vernon, K.; Chou, A.; Aljada, M.; Liu, J.; Motta, N. Plasmonic Effect of Gold Nanoparticles in Organic Solar Cells. Sol. Energy 2014, 106, 23– 37,  DOI: 10.1016/j.solener.2013.09.026
      24
      Plasmonic effect of gold nanoparticles in organic solar cells
      Notarianni, Marco; Vernon, Kristy; Chou, Alison; Aljada, Muhsen; Liu, Jinzhang; Motta, Nunzio
      Solar Energy (2014), 106 (), 23-37CODEN: SRENA4; ISSN:0038-092X. (Elsevier Ltd.)
      A review. Light trapping, due to the embedding of metallic nanoparticles, has been shown to be beneficial for a better photoabsorption in org. solar cells. Researchers in plasmonics and in the org. photovoltaics fields are working together to improve the absorption of sunlight and the photon-electron coupling to boost the performance of the devices.Recent advances in the field of plasmonics for org. solar cells focus on the incorporation of gold nanoparticles. This article reviews the different methods to produce and embed gold nanoparticles into org. solar cells. In particular, concn., size and geometry of gold nanoparticles are key factors that directly influence the light absorption in the devices. It is shown that a careful choice of size, concn. and location of gold nanoparticles in the device result in an enhancement of the power conversion efficiencies when compared to std. org. solar cell devices.Our latest results on gold nanoparticles embedded in on org. solar cell devices are included. We demonstrate that embedded gold nanoparticles, created by depositing and annealing a gold film on transparent electrode, generate a plasmonic effect which can be exploited to increase the power conversion efficiency of a bulk heterojunction solar cell up to 10%.
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    25. 25
      Domanski, K.; Correa-Baena, J. P.; Mine, N.; Nazeeruddin, M. K.; Abate, A.; Saliba, M.; Tress, W.; Hagfeldt, A.; Grätzel, M. Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells. ACS Nano 2016, 10 (6), 6306– 6314,  DOI: 10.1021/acsnano.6b02613
      25
      Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells
      Domanski, Konrad; Correa-Baena, Juan-Pablo; Mine, Nicolas; Nazeeruddin, Mohammad Khaja; Abate, Antonio; Saliba, Michael; Tress, Wolfgang; Hagfeldt, Anders; Gratzel, Michael
      ACS Nano (2016), 10 (6), 6306-6314CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      Perovskite solar cells (PSCs) have now achieved efficiencies in excess of 22%, but very little is known about their long-term stability under thermal stress. So far, stability reports have hinted at the importance of substituting the org. components, but little attention has been given to the metal contact. We investigated the stability of state-of-the-art PSCs with efficiencies exceeding 20%. Remarkably, we found that exposing PSCs to a temp. of 70 °C is enough to induce gold migration through the hole-transporting layer (HTL), spiro-MeOTAD, and into the perovskite material, which in turn severely affects the device performance metrics under working conditions. Importantly, we found that the main cause of irreversible degrdn. is not due to decompn. of the org. and hybrid perovskite layers. By introducing a Cr metal interlayer between the HTL and gold electrode, high-temp.-induced irreversible long-term losses are avoided. This key finding is essential in the quest for achieving high efficiency, long-term stable PSCs which, in order to be com. viable, need to withstand hard thermal stress tests.
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    26. 26
      Cao, S.; Yu, D.; Lin, Y.; Zhang, C.; Lu, L.; Yin, M.; Zhu, X.; Chen, X.; Li, D. Light Propagation in Flexible Thin-Film Amorphous Silicon Solar Cells with Nanotextured Metal Back Reflectors. ACS Appl. Mater. Interfaces 2020, 12 (23), 26184– 26192,  DOI: 10.1021/acsami.0c05330
      There is no corresponding record for this reference.
    27. 27
      Goyal, A.; Koper, M. T. M. The Interrelated Effect of Cations and Electrolyte PH on the Hydrogen Evolution Reaction on Gold Electrodes in Alkaline Media. Angew. Chem., Int. Ed. 2021, 60 (24), 13452– 13462,  DOI: 10.1002/anie.202102803
      27
      The Interrelated Effect of Cations and Electrolyte pH on the Hydrogen Evolution Reaction on Gold Electrodes in Alkaline Media
      Goyal, Akansha; Koper, Marc T. M.
      Angewandte Chemie, International Edition (2021), 60 (24), 13452-13462CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      In this work we study the role of alkali metal cation concn. and electrolyte pH in altering the kinetics of the hydrogen evolution reaction (HER) at gold (Au) electrodes. We show that at moderately alk. pH (pH 11), increasing the cation concn. significantly enhances the HER activity on Au electrodes (with a reaction order ≈0.5). Based on these results we suggest that cations play a central role in stabilizing the transition state of the rate-detg. Volmer step by favorably interacting with the dissocg. water mol. (*H-OHδ--cat+). Moreover, we show that increasing electrolyte pH (pH 10 to pH 13) tunes the local field strength, which in turn indirectly enhances the activity of HER by tuning the near-surface cation concn. Interestingly, a too high near-surface cation concn. (at high pH and high cation concn.) leads to a lowering of the HER activity, which we ascribe to a blockage of the surface by near-surface cations.
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    28. 28
      Löhrer, F. C.; Körstgens, V.; Semino, G.; Schwartzkopf, M.; Hinz, A.; Polonskyi, O.; Strunskus, T.; Faupel, F.; Roth, S. V.; Müller-Buschbaum, P. Following in Situ the Deposition of Gold Electrodes on Low Band Gap Polymer Films. ACS Appl. Mater. Interfaces 2020, 12 (1), 1132– 1141,  DOI: 10.1021/acsami.9b17590
      There is no corresponding record for this reference.
    29. 29
      Kas, R.; Yang, K.; Bohra, D.; Kortlever, R.; Burdyny, T.; Smith, W. A. Electrochemical Co2 Reduction on Nanostructured Metal Electrodes: Fact or Defect?. Chem. Sci. 2020, 11 (7), 1738– 1749,  DOI: 10.1039/C9SC05375A
      29
      Electrochemical CO2 reduction on nanostructured metal electrodes: fact or defect?
      Kas, Recep; Yang, Kailun; Bohra, Divya; Kortlever, Ruud; Burdyny, Thomas; Smith, Wilson A.
      Chemical Science (2020), 11 (7), 1738-1749CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      A review. Electrochem. CO2 redn. has received an increased amt. of interest in the last decade as a promising avenue for storing renewable electricity in chem. bonds. Despite considerable progress on catalyst performance using nanostructured electrodes, the sensitivity of the reaction to process conditions has led to debate on the origin of the activity and high selectivity. Addnl., this raises questions on the transferability of the performance and knowledge to other electrochem. systems. At its core, the discrepancy is primarily a result of the highly porous nature of nanostructured electrodes, which are vulnerable to both mass transport effects and structural changes during the electrolysis. Both effects are not straightforward to identify and difficult to decouple. Despite the susceptibility of nanostructured electrodes to mass transfer limitations, we highlight that nanostructured silver electrodes exhibit considerably higher activity when normalized to the electrochem. active surface in contrast to gold and copper electrodes. Alongside, we provide a discussion on how active surface area and thickness of the catalytic layer itself can influence the onset potential, selectivity, stability, activity and mass transfer inside and outside of the three dimensional catalyst layer. Key parameters and potential solns. are highlighted to decouple mass transfer effects from the measured activity in electrochem. cells utilizing CO2 satd. aq. solns.
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    30. 30
      Marcandalli, G.; Goyal, A.; Koper, M. T. M. Electrolyte Effects on the Faradaic Efficiency of CO2Reduction to CO on a Gold Electrode. ACS Catal. 2021, 11 (9), 4936– 4945,  DOI: 10.1021/acscatal.1c00272
      There is no corresponding record for this reference.
    31. 31
      Bandorf, R.; Waschke, S.; Carreri, F. C.; Vergöhl, M.; Grundmeier, G.; Bräuer, G. Direct Metallization of PMMA with Aluminum Films Using HIPIMS. Surf. Coat. Technol. 2016, 290, 77– 81,  DOI: 10.1016/j.surfcoat.2015.10.070
      There is no corresponding record for this reference.
    32. 32
      Bandorf, R.; Waschke, S.; Vergöhl, M.; Grundmeier, G.; Bräuer, G. Direct Metallization of Plastics by High Power Impulse Magnetron Sputtering. Vak. Forsch. Prax. 2015, 27 (4), 18– 23,  DOI: 10.1002/vipr.201500587
      There is no corresponding record for this reference.
    33. 33
      Bulut, Y.; Sochor, B.; Harder, C.; Reck, K.; Drewes, J.; Xu, Z.; Jiang, X.; Meinhardt, A.; Jeromin, A.; Kohantorabi, M.; Noei, H.; Keller, T. F.; Strunskus, T.; Faupel, F.; Müller-Buschbaum, P.; Roth, S. V. Diblock Copolymer Pattern Protection by Silver Cluster Reinforcement. Nanoscale 2023, 15 (38), 15768– 15774,  DOI: 10.1039/D3NR03215A
      There is no corresponding record for this reference.
    34. 34
      Christou, C.; Barber, Z. H. Ionization of Sputtered Material in a Planar Magnetron Discharge. J. Vac. Sci. Technol. A 2000, 18 (6), 2897– 2907,  DOI: 10.1116/1.1312370
      There is no corresponding record for this reference.
    35. 35
      Lundin, D.; Larsson, P.; Wallin, E.; Lattemann, M.; Brenning, N.; Helmersson, U. Cross-Field Ion Transport during High Power Impulse Magnetron Sputtering. Plasma Sources Sci. Technol 2008, 17 (3), 035021,  DOI: 10.1088/0963-0252/17/3/035021
      There is no corresponding record for this reference.
    36. 36
      Lü, B.; Münger, E. P.; Sarakinos, K. Coalescence-Controlled and Coalescence-Free Growth Regimes during Deposition of Pulsed Metal Vapor Fluxes on Insulating Surfaces. J. Appl. Phys. 2015, 117 (13), 134304,  DOI: 10.1063/1.4916983
      36
      Coalescence-controlled and coalescence-free growth regimes during deposition of pulsed metal vapor fluxes on insulating surfaces
      Lu, B.; Munger, E. P.; Sarakinos, K.
      Journal of Applied Physics (Melville, NY, United States) (2015), 117 (13), 134304/1-134304/9CODEN: JAPIAU; ISSN:0021-8979. (American Institute of Physics)
      The morphol. and phys. properties of thin films deposited by vapor condensation on solid surfaces are predominantly set by the processes of island nucleation, growth and coalescence. When deposition is performed using pulsed vapor fluxes, three distinct nucleation regimes are known to exist depending on the temporal profile of the flux. These regimes can be accessed by tuning deposition conditions; however, their effect on film microstructure becomes marginal when coalescence sets in and erases morphol. features obtained during nucleation. By preventing coalescence from being completed, these nucleation regimes can be used to control microstructure evolution and thus access a larger palette of film morphol. features. Recently, the authors derived the quant. criterion to stop coalescence during continuous metal vapor flux deposition on insulating surfaces-which typically yields 3-dimensional growth-by describing anal. the competition between island growth by at. incorporation and the coalescence rate of islands [Lu et al., (2014)]. Here, the authors develop the anal. framework for entering a coalescence-free growth regime for metal vapor deposition on insulating substrates using pulsed vapor fluxes, showing that there exist three distinct criteria for suppressing coalescence that correspond to the three nucleation regimes of pulsed vapor flux deposition. The theor. framework developed herein is substantiated by kinetic Monte Carlo growth simulations. The findings highlight the possibility of using atomistic nucleation theory for pulsed vapor deposition to control morphol. of thin films beyond the point of island d. satn. (c) 2015 American Institute of Physics.
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    37. 37
      Magnfält, D.; Elofsson, V.; Abadias, G.; Helmersson, U.; Sarakinos, K. Time-Domain and Energetic Bombardment Effects on the Nucleation and Coalescence of Thin Metal Films on Amorphous Substrates. J. Phys. D: Appl. Phys. 2013, 46 (21), 215303,  DOI: 10.1088/0022-3727/46/21/215303
      There is no corresponding record for this reference.
    38. 38
      Schwartzkopf, M.; Hinz, A.; Polonskyi, O.; Strunskus, T.; Löhrer, F. C.; Körstgens, V.; Müller-Buschbaum, P.; Faupel, F.; Roth, S. V. Role of Sputter Deposition Rate in Tailoring Nanogranular Gold Structures on Polymer Surfaces. ACS Appl. Mater. Interfaces 2017, 9 (6), 5629– 5637,  DOI: 10.1021/acsami.6b15172
      38
      Role of Sputter Deposition Rate in Tailoring Nanogranular Gold Structures on Polymer Surfaces
      Schwartzkopf, Matthias; Hinz, Alexander; Polonskyi, Oleksandr; Strunskus, Thomas; Loehrer, Franziska C.; Koerstgens, Volker; Mueller-Buschbaum, Peter; Faupel, Franz; Roth, Stephan V.
      ACS Applied Materials & Interfaces (2017), 9 (6), 5629-5637CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      To obtain full control over the complex nanostructural evolution at the polymer-metal interface, the authors monitor the evolution of the metallic layer morphol. with in situ time-resolved grazing-incidence small-angle X-ray scattering during sputter deposition. The authors 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 obsd. 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 morphol. parameters of the gold cluster ensemble relevant for various applications as a function of the effective layer thickness and deposition rate.
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    39. 39
      Schwartzkopf, M.; Santoro, G.; Brett, C. J.; Rothkirch, A.; Polonskyi, O.; Hinz, A.; Metwalli, E.; Yao, Y.; Strunskus, T.; Faupel, F.; Müller-Buschbaum, P.; Roth, S. V. Real-Time Monitoring of Morphology and Optical Properties during Sputter Deposition for Tailoring Metal–Polymer Interfaces. ACS Appl. Mater. Interfaces 2015, 7 (24), 13547– 13556,  DOI: 10.1021/acsami.5b02901
      39
      Real-Time Monitoring of Morphology and Optical Properties during Sputter Deposition for Tailoring Metal-Polymer Interfaces
      Schwartzkopf, Matthias; Santoro, Gonzalo; Brett, Calvin J.; Rothkirch, Andre; Polonskyi, Oleksandr; Hinz, Alexander; Metwalli, Ezzeldin; Yao, Yuan; Strunskus, Thomas; Faupel, Franz; Mueller-Buschbaum, Peter; Roth, Stephan V.
      ACS Applied Materials & Interfaces (2015), 7 (24), 13547-13556CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      The reproducible low-cost fabrication of functional metal-polymer nanocomposites with tailored optoelectronic properties for advanced applications remains a major challenge in applied nanotechnol. To obtain full control over the nanostructural evolution at the metal-polymer interface and its impact on optoelectronic properties, we employed combined in situ time-resolved microfocus grazing incidence small angle X-ray scattering (μGISAXS) with in situ UV/vis specular reflectance spectroscopy (SRS) during sputter deposition of gold on thin polystyrene films. On the basis of the temporal evolution of the key scattering features in the real-time μGISAXS expt., we directly obsd. four different growth regimes: nucleation, isolated island growth, growth of larger aggregates via partial coalescence, and continuous layer growth. Moreover, their individual thresholds were identified with subnanometer resoln. and correlated to the changes in optical properties. During sputter deposition, a change in optical reflectivity of the pristine gray-blue PS film was obsd. ranging from dark blue color due to the presence of isolated nanoclusters at the interface to bright red color from larger Au aggregates. We used simplified geometrical assumptions to model the evolution of av. real space parameters (distance, size, d., contact angle) in excellent agreement with the qual. observation of key scattering features. A decrease of contact angles was obsd. during the island-to-percolation transition and confirmed by simulations. Furthermore, a surface diffusion coeff. according to the kinetic freezing model and interfacial energy of Au on PS at room temp. were calcd. based on a real-time expt. The morphol. characterization is complemented by X-ray reflectivity, optical, and electron microscopy. Our study permits a better understanding of the growth kinetics of gonnld clusters and their self-organization into complex nanostructures on polymer substrates. It opens up the opportunity to improve nanofabrication and tailoring of metal-polymer nanostructures for optoelectronic applications, org. photovoltaics, and plasmonic-enhanced technologies.
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    40. 40
      Amarandei, G.; O’Dwyer, C.; Arshak, A.; Corcoran, D. The Stability of Thin Polymer Films as Controlled by Changes in Uniformly Sputtered Gold. Soft Matter 2013, 9 (9), 2695– 2702,  DOI: 10.1039/c3sm27130g
      There is no corresponding record for this reference.
    41. 41
      Schwartzkopf, M.; Buffet, A.; Körstgens, V.; Metwalli, E.; Schlage, K.; Benecke, G.; Perlich, J.; Rawolle, M.; Rothkirch, A.; Heidmann, B.; Herzog, G.; Müller-Buschbaum, P.; Röhlsberger, R.; Gehrke, R.; Stribeck, N.; Roth, S. V. From Atoms to Layers: In Situ Gold Cluster Growth Kinetics during Sputter Deposition. Nanoscale 2013, 5 (11), 5053– 5062,  DOI: 10.1039/c3nr34216f
      41
      From atoms to layers: in situ gold cluster growth kinetics during sputter deposition
      Schwartzkopf, Matthias; Buffet, Adeline; Koerstgens, Volker; Metwalli, Ezzeldin; Schlage, Kai; Benecke, Gunthard; Perlich, Jan; Rawolle, Monika; Rothkirch, Andre; Heidmann, Berit; Herzog, Gerd; Mueller-Buschbaum, Peter; Roehlsberger, Ralf; Gehrke, Rainer; Stribeck, Norbert; Roth, Stephan V.
      Nanoscale (2013), 5 (11), 5053-5062CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
      The adjustment of size-dependent catalytic, elec. and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnol. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resoln. by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resoln. and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extn. of morphol. real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphol. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufg. parameters, saving energy and resources.
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    42. 42
      Stierle, A.; Keller, T. F.; Noei, H.; Vonk, V.; Roehlsberger, R. DESY NanoLab. J. Large-Scale Res. Facil. 2016, 2 (A76), A76,  DOI: 10.17815/jlsrf-2-140
      There is no corresponding record for this reference.
    43. 43
      Schneider, C. A.; Rasband, W. S.; Eliceiri, K. W. NIH Image to ImageJ: 25 Years of Image Analysis. Nat. Methods 2012, 9 (7), 671– 675,  DOI: 10.1038/nmeth.2089
      43
      NIH Image to ImageJ: 25 years of image analysis
      Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W.
      Nature Methods (2012), 9 (7_part1), 671-675CODEN: NMAEA3; ISSN:1548-7091. (Nature Publishing Group)
      For the past 25 years NIH Image and ImageJ software have been pioneers as open tools for the anal. of scientific images. We discuss the origins, challenges and solns. of these two programs, and how their history can serve to advise and inform other software projects.
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    44. 44
      Benecke, G.; Wagermaier, W.; Li, C.; Schwartzkopf, M.; Flucke, G.; Hoerth, R.; Zizak, I.; Burghammer, M.; Metwalli, E.; Müller-Buschbaum, P.; Trebbin, M.; Förster, S.; Paris, O.; Roth, S. V.; Fratzl, P. A Customizable Software for Fast Reduction and Analysis of Large X-Ray Scattering Data Sets: Applications of the New DPDAK Package to Small-Angle X-Ray Scattering and Grazing-Incidence Small-Angle X-Ray Scattering. J. Appl. Crystallogr. 2014, 47 (5), 1797– 1803,  DOI: 10.1107/S1600576714019773
      44
      A customizable software for fast reduction and analysis of large X-ray scattering data sets: applications of the new DPDAK package to small-angle X-ray scattering and grazing-incidence small-angle X-ray scattering
      Benecke, Gunthard; Wagermaier, Wolfgang; Li, Chenghao; Schwartzkopf, Matthias; Flucke, Gero; Hoerth, Rebecca; Zizak, Ivo; Burghammer, Manfred; Metwalli, Ezzeldin; Mueller-Buschbaum, Peter; Trebbin, Martin; Foerster, Stephan; Paris, Oskar; Roth, Stephan V.; Fratzl, Peter
      Journal of Applied Crystallography (2014), 47 (5), 1797-1803CODEN: JACGAR; ISSN:1600-5767. (International Union of Crystallography)
      X-ray scattering expts. at synchrotron sources are characterized by large and constantly increasing amts. of data. The great no. of files generated during a synchrotron expt. is often a limiting factor in the anal. of the data, since appropriate software is rarely available to perform fast and tailored data processing. Furthermore, it is often necessary to perform online data redn. and anal. during the expt. in order to interactively optimize exptl. design. This article presents an open-source software package developed to process large amts. of data from synchrotron scattering expts. These data redn. processes involve calibration and correction of raw data, one- or two-dimensional integration, as well as fitting and further anal. of the data, including the extn. of certain parameters. The software, DPDAK (directly programmable data anal. kit), is based on a plug-in structure and allows individual extension in accordance with the requirements of the user. The article demonstrates the use of DPDAK for on- and offline anal. of scanning small-angle X-ray scattering (SAXS) data on biol. samples and microfluidic systems, as well as for a comprehensive anal. of grazing-incidence SAXS data. In addn. to a comparison with existing software packages, the structure of DPDAK and the possibilities and limitations are discussed.
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    45. 45
      Nelson, A. R. J.; Prescott, S. W. Refnx: Neutron and X-Ray Reflectometry Analysis in Python. J. Appl. Crystallogr. 2019, 52, 193– 200,  DOI: 10.1107/S1600576718017296
      45
      refnx: neutron and X-ray reflectometry analysis in Python
      Nelson, Andrew R. J.; Prescott, Stuart W.
      Journal of Applied Crystallography (2019), 52 (1), 193-200CODEN: JACGAR; ISSN:1600-5767. (International Union of Crystallography)
      Refnx is a model-based neutron and X-ray reflectometry data anal. package written in Python. It is cross platform and has been tested on Linux, macOS and Windows. Its graphical user interface is browser based, through a Jupyter notebook. Model construction is modular, being composed from a series of components that each describe a subset of the interface, parameterized in terms of phys. relevant parameters (vol. fraction of a polymer, lipid area per mol. etc.). The model and data are used to create an objective, which is used to calc. the residuals, log-likelihood and log-prior probabilities of the system. Objectives are combined to perform co-refinement of multiple data sets and mixed-area models. The software offers a choice of fitting approaches, including least-squares (global and gradient-based optimizers) and a Bayesian approach using a Markov-chain Monte Carlo algorithm to investigate the posterior distribution of the model parameters. The Bayesian approach is useful for examg. parameter covariances, model selection and variability in the resulting scattering length d. profiles. The package is designed to facilitate reproducible research; its use in Jupyter notebooks, and subsequent distribution of those notebooks as supporting information, permits straightforward reprodn. of analyses.
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    46. 46
      Kaune, G.; Ruderer, M. A.; Metwalli, E.; Wang, W.; Couet, S.; Schlage, K.; Röhlsberger, R.; Roth, S. V.; Müller-Buschbaum, P. Situ GISAXS Study of Gold Film Growth on Conducting Polymer Films. ACS Appl. Mater. Interfaces 2009, 1 (2), 353– 360,  DOI: 10.1021/am8000727
      There is no corresponding record for this reference.
    47. 47
      Venables, J. A.; Spiller, G. D. T.; Hanbucken, M. Nucleation and Growth of Thin Films. Rep. Prog. Phys. 1984, 47 (4), 399– 459,  DOI: 10.1088/0034-4885/47/4/002
      47
      Nucleation and growth of thin films
      Venables, J. A.; Spiller, G. D. T.; Hanbuecken, M.
      Reports on Progress in Physics (1984), 47 (4), 399-459CODEN: RPPHAG; ISSN:0034-4885.
      A review with many refs.
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    48. 48
      Ehrlich, G. Direct Observations of the Surface Diffusion of Atoms and Clusters. Surf. Sci 1991, 246 (1–3), 1– 12,  DOI: 10.1016/0039-6028(91)90385-6
      48
      Direct observations of the surface diffusion of atoms and clusters
      Ehrlich, Gert
      Surface Science (1991), 246 (1-3), 1-12CODEN: SUSCAS; ISSN:0039-6028.
      A review. Diffusion of metal atoms on highly perfect planes was one of the first surface phenomena to be examd. on the at. level through the unique capability of the field ion microscope to reveal routinely individual adatoms. Despite subsequent advances in observational techniques, such as the development of high-resoln. electron microscopes and the scanning tunneling microscope, current understanding of the diffusion behavior of metal atoms is still based primarily upon field ion microscopic studies. Of the factors important in crystal growth (structural specificities in diffusion, mobility during deposition, the mechanisms of at. jumps, and the motion of clusters), it now appears that surface diffusion is a more complicated and interesting process than anticipated. 66 Refs.
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    49. 49
      Faupel, F.; Zaporojtchenko, V.; Strunskus, T.; Elbahri, M. Metal-Polymer Nanocomposites for Functional Applications. Adv. Eng. Mater. 2010, 12 (12), 1177– 1190,  DOI: 10.1002/adem.201000231
      There is no corresponding record for this reference.
    50. 50
      Reck, K. A.; Bulut, Y.; Xu, Z.; Liang, S.; Strunskus, T.; Sochor, B.; Gerdes, H.; Bandorf, R.; Müller-Buschbaum, P.; Roth, S. V.; Vahl, A.; Faupel, F. Early-Stage Silver Growth during Sputter Deposition on SiO2 and Polystyrene – Comparison of Biased DC Magnetron Sputtering, High-Power Impulse Magnetron Sputtering (HiPIMS) and Bipolar HiPIMS. Appl. Surf. Sci. 2024, 666 (May), 160392,  DOI: 10.1016/j.apsusc.2024.160392
      There is no corresponding record for this reference.
    51. 51
      Gensch, M.; Schwartzkopf, M.; Brett, C. J.; Schaper, S. J.; Kreuzer, L. P.; Li, N.; Chen, W.; Liang, S.; Drewes, J.; Polonskyi, O.; Strunskus, T.; Faupel, F.; Müller-Buschbaum, P.; Roth, S. V. Selective Silver Nanocluster Metallization on Conjugated Diblock Copolymer Templates for Sensing and Photovoltaic Applications. ACS Appl. Nano Mater. 2021, 4 (4), 4245– 4255,  DOI: 10.1021/acsanm.1c00829
      There is no corresponding record for this reference.
    52. 52
      Schaper, S. J.; Löhrer, F. C.; Xia, S.; Geiger, C.; Schwartzkopf, M.; Pandit, P.; Rubeck, J.; Fricke, B.; Frenzke, S.; Hinz, A. M.; Carstens, N.; Polonskyi, O.; Strunskus, T.; Faupel, F.; Roth, S. V.; Müller-Buschbaum, P. Revealing the Growth of Copper on Polystyrene- Block -Poly(Ethylene Oxide) Diblock Copolymer Thin Films with in Situ GISAXS. Nanoscale 2021, 13 (23), 10555– 10565,  DOI: 10.1039/D1NR01480C
      There is no corresponding record for this reference.
    53. 53
      Williamson, G. K.; Hall, W. H. X-Ray Line Broadening from Filed Aluminium and Wolfram. Acta Metall. 1953, 1 (1), 22– 31,  DOI: 10.1016/0001-6160(53)90006-6
      53
      X-ray line broadening from filed aluminum and tungsten
      Williamson, G. K.; Hall, W. H.
      Acta Metallurgica (1953), 1 (No. 1), 22-31CODEN: AMETAR; ISSN:0001-6160.
      Methods of analysis previously used in the interpretation of line broadening are discussed and are shown to be inadequate; more reliable methods being outlined. An analysis of published results by one of these methods suggests that the observed effects can be attributed to simultaneous small particle size and strain broadening. Measurements of the changes in intensity distribution have been made, with a Geiger counter spectrometer, in the spectra of cold-worked Al and W. The line breadths may be attributed to simultaneous small particle size and strain broadening, the latter predominating, particularly at the higher Bragg angles, and it is shown that the observed effects are produced by dislocations or some similar structural fault. The observed rise in the breadths of the high angle lines from annealed materials suggests that some dislocations remain after annealing. Fourier analysis of the line shapes in general merely confirm the results of the analysis of the line breadths, but in the case of the recovered specimens it suggests that the dislocations form into walls ("polygonization").
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    54. 54
      Zou, Y.; Eichhorn, J.; Zhang, J.; Apfelbeck, F. A. C.; Yin, S.; Wolz, L.; Chen, C. C.; Sharp, I. D.; Müller-Buschbaum, P. Microstrain and Crystal Orientation Variation within Naked Triple-Cation Mixed Halide Perovskites under Heat, UV, and Visible Light Exposure. ACS Energy Lett. 2024, 9 (2), 388– 399,  DOI: 10.1021/acsenergylett.3c02617
      There is no corresponding record for this reference.
    55. 55
      Milligan, W. O.; Morriss, R. H. Morphology of Colloidal Gold--A Comparative Study. J. Am. Chem. Soc. 1964, 86 (17), 3461– 3467,  DOI: 10.1021/ja01071a012
      There is no corresponding record for this reference.
    56. 56
      Davey, W. P. Precision Measurements of the Lattice Constants of Twelve Common Metals. Phys. Rev. 1925, 25 (6), 753– 761,  DOI: 10.1103/PhysRev.25.753
      56
      Precision measurements of the lattice constants of twelve common metals
      Davey, W. P.
      Physical Review (1925), 25 (), 753-61CODEN: PHRVAO; ISSN:0031-899X.
      The lattice const. a is detd. to 0.1% for Al, Fe, Ni, Cu, Mo, Pd, Ag, W, Pt, Au, Pb and Bi and the results are summarized in a table.
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  • Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.4c02344.

    • Skeletal structure of the polymers; XRR measurements; SLD profiles; FESEM measurements; GISAXS and GIWAXS detector images; surface coverage analysis with FESEM; GISAXS and GIWAXS scattering profiles with the corresponding fit; comparison of in situ analysis; comparison of FESEM- and GISAXS-derived cluster density; sheet resistance measurement (PDF)


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