Red organic dye identification is an important topic for conservation of Japanese ukiyo-e prints. Of particular interest are the works of Suzuki Harunobu, who was working at the inception of full-color printmaking. These prints were made on thin kōzo paper and woodblock printed with semi-transparent to opaque regions of dye(s) and/or pigment(s) mixed with binder. This study used imaging analysis, X-ray fluorescence (XRF), Raman, and surface-enhanced Raman spectroscopies (SERS) to identify the red dyes and pigments on Harunobu prints in the collection of the Portland Art Museum. Through image analysis (visible, UV, and IR illuminations), 23 prints were categorized by appearance. XRF results provided identification of vermilion and ochre pigments, and identified color fields that contained lead. Raman analysis allowed the identification of red lead, and SERS was used to identify both safflower and madder dyes. This work is expected to contribute to the body of knowledge regarding the red dye and pigment palette and mixtures in use in the mid- to late eighteenth century, in the critical early years of full-color printmaking. Graphical Abstract

We demonstrate a method for the preparation of fully solution processed inorganic solar cells from a spin and spray coating deposition of nanocrystal inks. For the photoactive absorber layer, colloidal CdTe and CdSe nanocrystals (3-5 nm) are synthesized using an inert hot injection technique and cleaned with precipitations to remove excess starting reagents. Similarly, gold nanocrystals (3-5 nm) are synthesized under ambient conditions and dissolved in organic solvents. In addition, precursor solutions for transparent conductive indium tin oxide (ITO) films are prepared from solutions of indium and tin salts paired with a reactive oxidizer. Layer-by-layer, these solutions are deposited onto a glass substrate following annealing (200-400 °C) to build the nanocrystal solar cell (glass/ITO/CdSe/CdTe/Au). Pre-annealing ligand exchange is required for CdSe and CdTe nanocrystals where films are dipped in NH4Cl:methanol to replace long-chain native ligands with small inorganic Cl(-) anions. NH4Cl(s) was found to act as a catalyst for the sintering reaction (as a non-toxic alternative to the conventional CdCl2(s) treatment) leading to grain growth (136±39 nm) during heating. The thickness and roughness of the prepared films are characterized with SEM and optical profilometry. FTIR is used to determine the degree of ligand exchange prior to sintering, and XRD is used to verify the crystallinity and phase of each material. UV/Vis spectra show high visible light transmission through the ITO layer and a red shift in the absorbance of the cadmium chalcogenide nanocrystals after thermal annealing. Current-voltage curves of completed devices are measured under simulated one sun illumination. Small differences in deposition techniques and reagents employed during ligand exchange have been shown to have a profound influence on the device properties. Here, we examine the effects of chemical (sintering and ligand exchange agents) and physical treatments (solution concentration, spray-pressure, annealing time and annealing temperature) on photovoltaic device performance.

Solution-processed transparent conductive oxides offer the advantages of low-cost, high-throughput fabrication of electronic devices compared to the specific requirements of vacuum deposition techniques. However, adapting the current state of the art to ink deposition calls for optimization of the precursor ink composition and the postdeposition process. Solution processing of indium tin oxide films can be accomplished at reduced temperatures (250–400 °C) by annealing soluble precursor metal salts together with a fuel/oxidizer, causing an exothermic reaction with elevated local temperatures. Following layer-by-layer cycles of deposition and annealing, a postprocessing step is required via heating (300 °C) under a 5% H2 reducing atmosphere. To address the discrepancy between the versatility of ink deposition and the limitations of controlled atmosphere postprocessing, here we investigate the effects of postprocess dipping in aqueous sodium borohydride at room temperature as an alternative, which allows for a completely solution-based process from ink to film. In addition to postprocessing, the solution composition was also optimized by removing the fuel additive and by adjusting the In/Sn content. Indium tin oxide (ITO) films were spin-coated and annealed in air at 250, 300, and 400 °C and characterized by UV/vis spectroscopy to obtain optical transmittance, atomic force microscopy to obtain film thickness and surface morphology, and a Hall effect system for electrical parameters. Additional data from X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) indicate that crystallinity is affected by the reducing environment. Results revealed an order-of-magnitude improvement of the Haacke figure of merit (FOM) from 4.3 × 10–4 Ω–1, 382 Ω/□ sheet resistance (R s), and 84% transmittance (%T) for the traditional 9:1 In/Sn precursor ink with fuel additive followed by 300 °C of 5% H2-furnace post-treatment compared to that of the optimized fully solution-processed 8.5:1.5 In/Sn ink without fuel followed by an ambient air at 25 °C dipping in aqueous sodium borohydride, leading to 3.0 × 10–3 Ω–1 FOM, 84.5 Ω/□ R s, and 87%T including the glass substrate.

We demonstrate a method for the preparation of fully solution processed inorganic solar cells from a spin and spray coating deposition of nanocrystal inks. For the photoactive absorber layer, colloidal CdTe and CdSe nanocrystals (3-5 nm) are synthesized using an inert hot injection technique and cleaned with precipitations to remove excess starting reagents. Similarly, gold nanocrystals (3-5 nm) are synthesized under ambient conditions and dissolved in organic solvents. In addition, precursor solutions for transparent conductive indium tin oxide (ITO) films are prepared from solutions of indium and tin salts paired with a reactive oxidizer. Layer-by-layer, these solutions are deposited onto a glass substrate following annealing (200-400 °C) to build the nanocrystal solar cell (glass/ITO/CdSe/CdTe/Au). Pre-annealing ligand exchange is required for CdSe and CdTe nanocrystals where films are dipped in NH 4 Cl:methanol to replace long-chain native ligands with small inorganic Cl anions. NH 4 Cl (s) was found to act as a catalyst for the sintering reaction (as a non-toxic alternative to the conventional CdCl 2(s) treatment) leading to grain growth (136±39 nm) during heating. The thickness and roughness of the prepared films are characterized with SEM and optical profilometry. FTIR is used to determine the degree of ligand exchange prior to sintering, and XRD is used to verify the crystallinity and phase of each material. UV/Vis spectra show high visible light transmission through the ITO layer and a red shift in the absorbance of the cadmium chalcogenide nanocrystals after thermal annealing. Current-voltage curves of completed devices are measured under simulated one sun illumination. Small differences in deposition techniques and reagents employed during ligand exchange have been shown to have a profound influence on the device properties. Here, we examine the effects of chemical (sintering and ligand exchange agents) and physical treatments (solution concentration, spray-pressure, annealing time and annealing temperature) on photovoltaic device performance.