Roman Y. Korotkov

Tuning the optical properties of mesoporous TiO2 films by nanoscale engineering.

The optical properties of spin-coated titanium dioxide films have been tuned by introducing mesoscale pores into the inorganic matrix. Differently sized pores were templated using Pluronic triblock copolymers as surfactants in the sol-gel precursor solutions and adjusted by varying the process parameters, such as the polymer concentration, annealing temperature, and time. The change in refractive index observed for different mesoporous anatase films annealed at 350, 400, or 450 °C directly correlates with changes in the pore size. Additionally, the index of refraction is influenced by the film thickness and the density of pores within the films. The band gap of these films is blue-shifted, presumably due to stress the introduction of pores exerts on the inorganic matrix. This study focused on elucidating the effect different templating materials (Pluronic F127 and P123) have on the pore size of the final mesoporous titania film and on understanding the relation of varying the polymer concentration (taking P123 as an example) in the sol-gel solution to the pore density and size in the resultant titania film. Titania thin film samples or corresponding titanium dioxide powders were characterized by X-ray diffraction, cross-section transmission electron microscopy, nitrogen adsorption, ellipsometery, UV/vis spectrometry, and other techniques to understand the interplay between mesoporosity and optical properties.

Aerosol-Assisted Chemical Vapor Deposition of Tungsten Oxide Films and Nanorods from Oxo Tungsten(VI) Fluoroalkoxide Precursors

Aerosol-assisted chemical vapor deposition (AACVD) of WOx was demonstrated using the oxo tungsten(VI) fluoroalkoxide single-source precursors, WO[OCCH3(CF3)2]4 and WO[OC(CH3)2CF3]4. Substoichiometric amorphous tungsten oxide thin films were grown on indium tin oxide (ITO) substrates in nitrogen at low deposition temperature (100-250 °C). At growth temperatures above 300 °C, the W18O49 monoclinic crystalline phase was observed. The surface morphology and roughness, visible light transmittance, electrical conductivity, and work function of the tungsten oxide materials are reported. The solvent and carrier gas minimally affected surface morphology and composition at low deposition temperature; however, material crystallinity varied with solvent choice at higher temperatures. The work function of the tungsten oxide thin films grown between 150 and 250 °C was determined to be in the range 5.0 to 5.7 eV, according to ultraviolet photoelectron spectroscopy (UPS).

Dioxo–Fluoroalkoxide Tungsten(VI) Complexes for Growth of WOx Thin Films by Aerosol-Assisted Chemical Vapor Deposition

The soluble bis(fluoroalkoxide) dioxo tungsten(VI) complexes WO2(OR)2(DME) [1, R = C(CF3)2CH3; 2, R = C(CF3)3] have been synthesized by alkoxide-chloride metathesis and evaluated as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WOx. The (1)H NMR and (19)F NMR spectra of 1 and 2 are consistent with an equilibrium between the dimethoxyethane (DME) complexes 1 and 2 and the solvato complexes WO2(OR)2(CD3CN)2 [1b, R = C(CF3)2CH3; 2b, R = C(CF3)3] in acetonitrile-d3 solution. Studies of the fragmentation of 1 and 2 by mass spectrometry and thermolysis resulted in observation of DME and the corresponding alcohols, with hexafluoroisobutylene also generated from 1. DFT calculations on possible decomposition mechanisms for 1 located pathways for hydrogen abstraction by a terminal oxo to form hexafluoroisobutylene, followed by dimerization of the resulting terminal hydroxide complex and dissociation of the alcohol. AACVD using 1 occurred between 100 and 550 °C and produced both substoichiometric amorphous WOx and a polycrystalline W18O49 monoclinic phase, which exhibits 1-D preferred growth in the [010] direction. The work function (4.9-5.6 eV), mean optical transmittance (39.1-91.1%), conductivity (0.4-2.3 S/cm), and surface roughness (3.4-7.9 nm) of the WOx films are suitable for charge injection layers in organic electronics.

Partially fluorinated oxo-alkoxide tungsten(VI) complexes as precursors for deposition of WOx nanomaterials

The partially fluorinated oxo-alkoxide tungsten(VI) complexes WO(OR)4 [4; R = C(CH3)2CF3, 5; R = C(CH3)(CF3)2] have been synthesized as precursors for chemical vapour deposition (CVD) of WOx nanocrystalline material. Complexes 4 and 5 were prepared by salt metathesis between sodium salts of the fluoroalkoxides and WOCl4. Crystallographic structure analysis allows comparison of the bonding in 4 and 5 as the fluorine content of the fluoroalkoxide ligands is varied. Screening of as a CVD precursor by mass spectrometry and thermogravimetric analysis was followed by deposition of WOx nanorods.

Properties of TCO anodes deposited by atmospheric pressure chemical vapor deposition and their application to OLED lighting

Doped ZnO is one of the materials currently being considered in commercial optoelectronic applications as a potential indium tin oxide (ITO) replacement for the transparent conducting oxide (TCO). The properties of doped ZnO anodes prepared at Arkema Inc. are analyzed using spectroscopic ellipsometer (230 to 1700 nm) and Hall-effect. The modeling of the refractive indexes is conducted using a double oscillator model. The model parameters are tested on a double layer: undoped and doped structure deposited by atmospheric pressure chemical vapor deposition (APCVD) on glass substrates. Excellent correlation between calculated and experimental parameters was obtained.

Properties of TCO anodes deposited by APCVD and their applications to OLEDs

Doped ZnO is one of the materials currently being considered in industrial applications as a possible replacement for ITO as a transparent conducting oxide. The properties of doped ZnO anodes prepared at Arkema Inc. are analyzed in 3D using high-throughput mapping tools. The 2D resistivities of the coatings measured by 4-point probe compare well with the resistivity values calculated from the spectroscopic ellipsometer measurements. It was found that the dependence of effective mass of doped ZnO on Hall-electron concentration influences optically-calculated mobilities and electron concentrations. To study the variation of the film properties along z-axis, the films are polished using mechanical planarization technique. The electrical and crystallographic depth profiles for these films are studied by differential Hall-effect and grazing-angle x-ray spectroscopy. The electron mobility increases continuously from the glass-film interface (12 cm2/Vs) to the ZnO film surface (19 cm2/Vs). The electron concentration depth profile has bell-like dependence with a maximum at 1.55 x 1021 cm-3. In addition to the increasing grain size, the texture coefficients for the (002) reflection decrease and (103) reflection increase towards the air-film interface. Examples of the applications of the doped ZnO anodes in the OLED structures suggest improvement of external quantum efficiency with introduction of an Al2O3 undercoat.