| 1. |
- Gensch, Marc, et al.
(författare)
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Correlating Nanostructure, Optical and Electronic Properties of Nanogranular Silver Layers during Polymer-Template-Assisted Sputter Deposition
- 2019
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Ingår i: ACS Applied Materials and Interfaces. - : AMER CHEMICAL SOC. - 1944-8244 .- 1944-8252. ; 11:32, s. 29416-29426
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Tidskriftsartikel (refereegranskat)abstract
- Tailoring the optical and electronic properties of nanostructured polymer-metal composites demonstrates great potential for efficient fabrication of modern organic optical and electronic devices such as flexible sensors, transistors, diodes, or photovoltaics. Self-assembled polymer metal nanocomposites offer an excellent perspective for creating hierarchical nanostructures on macroscopic scales by simple bottom-up processes. We investigate the growth processes of nanogranular silver (Ag) layers on diblock copolymer thin film templates during sputter deposition. The Ag growth is strongly driven by self-assembly and selective wetting on the lamella structure of polystyrene-block-poly (methyl methacrylate). We correlate the emerging nanoscale morphologies with collective optical and electronic properties and quantify the difference in Ag growth on the corresponding homopolymer thin films. Thus, we are able to determine the influence of the respective polymer template and observe substrate effects on the Ag cluster percolation threshold, which affects the insulator-to-metal transition (IMT). Optical spectroscopy in the UV-vis regime reveals localized surface plasmon resonance for the metal polymer composite. Their maximum absorption is observed around the IMT due to the subsequent long-range electron conduction in percolated nanogranular Ag layers. Using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, we identify the oxidation of Ag at the acrylate side chains as an essential influencing factor driving the selective wetting behavior in the early growth stages. The results of polymer-templated cluster growth are corroborated by atomic force microscopy and field emission scanning electron microscopy.
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| 2. |
- Hohn, Nuri, et al.
(författare)
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Amphiphilic diblock copolymer-mediated structure control in nanoporous germanium-based thin films
- 2019
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Ingår i: Nanoscale. - : ROYAL SOC CHEMISTRY. - 2040-3364 .- 2040-3372. ; 11:4, s. 2048-2055
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Tidskriftsartikel (refereegranskat)abstract
- Fabrication of porous, foam-like germanium-based (Ge-based) nanostructures is achieved with the use of the amphiphilic diblock copolymer polystyrene-b-polyethylene oxide as structure directing agent. Basic concepts of block copolymer assisted sol-gel synthesis are successfully realized based on the [Ge-9](4-) Zintl clusters as a precursor for Ge-based thin films. Material/elemental composition and crystalline Ge-based phases are investigated via X-ray photoelectron spectroscopy and X-ray diffraction measurements, respectively. Poor-good solvent pair induced phase separation leads to pore sizes in the Ge-based films up to 40 nm, which can be tuned through a change of the molar mixing ratio between polymer template and precursor as proven by grazing incidence small angle X-ray scattering and scanning electron microscopy.
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| 3. |
- Hohn, Nuri, et al.
(författare)
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Impact of Catalytic Additive on Spray Deposited and Nanoporous Titania in Films Observed via in Situ X-ray Scattering : Implications for hanced Photovoltaics
- 2018
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Ingår i: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 1:8, s. 4227-4235
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Tidskriftsartikel (refereegranskat)abstract
- With the aim of obtaining nanostructured titania thin films for the tential use in hybrid or dye sensitized solar cells, the amphiphilic block copolymer polystyrene-b-poly(ethylene oxide) is employed as a ructure directing template in combination with solgel chemistry. For sy upscaling, spraying is used as a deposition technique. In situ azing incidence small-angle X-ray scattering (GISAXS) measurements are rformed during spraying and show that most titania structures are ready formed within the solution prior to deposition. However, ructural rearrangement is enabled during the deposition period when all amounts of hydrochloric acid (HCl) are used as a catalytic ditive to the spray solution. This behavior is ascribed to an altering the reaction dynamics and phase separation in the presence of HCl, ich significantly improves the templating effect of the employed block copolymer. With HCl as an additive the final nanoscale rphologies exhibit smaller pore sizes and strongly enhanced order as mpared to thin films sprayed from solutions that do not contain HCl as antified with atomic force microscopy, scanning electron microscopy, d GISAXS.
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| 4. |
- Li, Nian, et al.
(författare)
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Morphology Phase Diagram of Slot-Die Printed TiO2 Films Based on Sol-Gel Synthesis
- 2019
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Ingår i: Advanced Materials Interfaces. - : WILEY. - 2196-7350. ; 6:12
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Tidskriftsartikel (refereegranskat)abstract
- Mesoporous titania films with tailored nanostructures are fabricated via slot-die printing, which is a simple and cost-effective thin-film deposition technique with the possibility of a large-scale manufacturing. Based on this technique, which is favorable in industry, TiO2 films possess the similar advantage with polymer semiconducting devices like ease of large-scale production. The titania morphologies, including foam-like nanostructures, nanowire aggregates, collapsed vesicles and nanogranules, are achieved via a so-called block-copolymer-assisted sol-gel synthesis. By adjusting the weight fraction of reactants, the ternary morphology phase diagram of the printed titania films is probed after template removal. The surface and inner morphology evolutions are explored with scanning electron microscopy and grazing incidence small-angle X-ray scattering, respectively. Special focus is set on foam-like titania nanostructures as they are of especial interest for, e.g., solar cell applications. At a low weight fraction of the titania precursor titanium(IV)isopropoxide (TTIP), foam-like titania films are achieved, which exhibit a high uniformity and possess large pore sizes. The anatase phase of the highly crystalline titania films is verified with X-ray diffraction and transmission electron microscopy.
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| 5. |
- Schwartzkopf, Matthias, et al.
(författare)
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In Situ Monitoring of Scale Effects on Phase Selection and Plasmonic Shifts during the Growth of AgCu Alloy Nanostructures for Anticounterfeiting Applications
- 2022
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Ingår i: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 5:3, s. 3832-3842
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Tidskriftsartikel (refereegranskat)abstract
- Tailoring of plasmon resonances is essential for applications in anticounterfeiting. This is readily achieved by tuning the composition of alloyed metal clusters; in the simplest case, binary alloys are used. Yet, one challenge is the correlation of cluster morphology and composition with the changing optoelectronic properties. Hitherto, the early stages of metal alloy nanocluster formation in immiscible binary systems such as silver and copper have been accessible by molecular dynamics (MD) simulations and transmission electron microscopy (TEM). Here, we investigate in real time the formation of supported silver, copper, and silver-copper-alloy nanoclusters during sputter deposition on poly(methyl methacrylate) by combining in situ surface-sensitive X-ray scattering with optical spectroscopy. While following the transient growth morphologies, we quantify the early stages of phase separation at the nanoscale, follow the shifts of surface plasmon resonances, and quantify the growth kinetics of the nanogranular layers at different thresholds. We are able to extract the influence of scaling effects on the nucleation and phase selection. The internal structure of the alloy cluster shows a copper-rich core/silver-rich shell structure because the copper core yields a lower mobility and higher crystallization tendency than the silver fraction. We compare our results to MD simulation and TEM data. This demonstrates a route to tailor accurately the plasmon resonances of nanosized, polymer-supported clusters which is a crucial prerequisite for anticounterfeiting.
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| 6. |
- Wang, Kun, et al.
(författare)
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Tuning of the Morphology and Optoelectronic Properties of ZnO/P3HT/P3HT-b-PEO Hybrid Films via Spray Deposition Method
- 2018
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Ingår i: ACS Applied Materials and Interfaces. - : AMER CHEMICAL SOC. - 1944-8244 .- 1944-8252. ; 10:24, s. 20569-20577
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Tidskriftsartikel (refereegranskat)abstract
- The self-assembly of amphiphilic diblock copolymers yields the possibility of using them as a template for tailoring the film morphologies of solgel chemistry-derived inorganic electron transport materials, such as mesoporous ZnO and TiO2. However, additional steps including etching and backfilling are required for the common bulk heterojunction fabrication process when using insulating diblock copolymers. Here, we use the conducting diblock copolymer poly(3-hexylthiophene)-block-poly(ethylene oxide) (P3HT-b-PEO) in which P3HT acts as charge carrier transport material and light absorber, whereas PEO serves as a template for ZnO synthesis. The initial solution is subsequently spray-coated to obtain the hybrid film. Scanning electron microscopy and grazing-incidence small-angle X-ray scattering measurements reveal a significant change in the morphology of the hybrid films during deposition. Optoelectronic properties illustrate the improved charge separation and charge transfer process. Both the amount of the diblock copolymer and the annealing temperature play an important role in tuning the morphology and the optoelectronic properties. Hybrid films being sprayed from a solution with the ratio of omega(ZnO), omega(P3HT), and omega(P3HT-b-PEO) of 2:1:1 and subsequent annealing at 80 degrees C show the most promising morphology combined with an optimal photoluminescence quenching. Thus, the presented simple, reagent- and energy-saving fabrication method provides a promising approach for a large-scale preparation of bulk heterojunction P3HT/ZnO films on flexible substrates.
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| 7. |
- Zhong, Qi, et al.
(författare)
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Effect of chain architecture on the swelling and thermal response of star-shaped thermo-responsive (poly(methoxy diethylene glycol acrylate)-block-polystyrene)(3) block copolymer films
- 2018
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Ingår i: Soft Matter. - : Royal Society of Chemistry. - 1744-683X .- 1744-6848. ; 14:31, s. 6582-6594
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Tidskriftsartikel (refereegranskat)abstract
- The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)(3)) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)(3) films show a transition temperature (TT) at 33 degrees C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)(3) films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)(3). However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)(3) films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)(3) films depends on the final temperature. It decreases from (9.7 +/- 0.3)% to (7.0 +/- 0.3)% or (6.0 +/- 0.3)% when the final temperatures are set to 35 degrees C, 45 degrees C and 50 degrees C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.
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