@techreport {58561, title = {Optical and Electrochromic Properties of Sol-Gel Deposited Doped Tungsten Oxide Films}, year = {1996}, month = {01/1996}, address = {Berkeley}, abstract = {

The goal of this study is to investigate the effects of doping of tungsten oxide on its electrochromic properties. The work is directed toward the development of neutral coloring tungsten oxide materials with properties superior to undoped tungsten oxide. Two basic types of sol-gel formulations were used for experimentation. Type 1 used a WOCl4 precursor. Type 2 used a proprietary (Donnelly) tungsten complex precursor. The Type 2 precursor was used only for comparison to Type 1. Doping experiments were performed using the Type 1 chemistry. The dopants studied were Co, Cr, Nb, Ti, V and Y. The range of dopant was 1-12 mole \%. Improved electrochromic behavior was observed for tungsten oxide films doped with V and Ti.

Analysis of the films included x-ray diffraction, ellipsometry, cyclic voltammetry and spectrophotometry. X-ray diffraction showed that all films heat treated at temperatures below 300{\textdegree}C were amorphous in structure. The refractive indices for undoped films were measured. We found the n, k values of the Type 1 films to be lower than the Type 2 films. The n and k values were n=1.79 and k=2.8x10-3, and n=2.08 and k=3.6x10-3 at 550 nm, for Type 1 and Type 2 films respectively. Both types of tungsten oxide films showed low absorption and high transparency in the visible range. As expected, we found that the film density, and hence the refractive index and extinction coefficient, depended on coating solution chemistry, hydration, and densification procedures. Undoped Type 1 films showed slightly higher lithium diffusion coefficients (DLi), compared to undoped Type 2 films,\ DLi=1.36x 10-9 cm2 s-1 and 1.31 x 10-9 cm2 s-1, respectively.

We also noted that the properties of the films could be reproduced for any coating chemistry and densification scheme. The electrochemical and optical behavior were determined by using an in-situ cuvette cell with a 1M LiCl04 / propylene carbonate electrolyte. Cyclic voltammetric measurements showed that doped Type 1 films exhibited electrochemical reversibility beyond 1200 cycles without change in charge capacity. A slight lowering of charge capacity was noted for the undoped films after cycling. The charge capacity for the V doped film was 16.9 mC/cm2 compared to undoped film, 9.6 mC/cm2. Spectrophotometry showed that doped films tended to exhibit a higher absorbance in their colored state compared to undoped films. Considerable improvement in the lithium diffusivity was noted for all the doped films. The greatest change was a factor of 20x for vanadium doping. Doping appeared to increase the cyclic durability of all the tungsten films out to 1200 cycles. Color changes by doping were noted for several dopants. The doped films with the best overall properties were about 8\% vanadium and titanium tungsten oxide. The optimum concentration lies in the range of 7 to 12 mol\%. The electrochromic color was a neutral brownish-blue for vanadium and grayish-blue for titanium doped tungsten oxide.

}, author = {Nilg{\"u}n {\"O}zer and Carl M Lampert and Michael D. Rubin} } @article {12147, title = {Optical Indices of Lithiated Electrochromic Oxides}, journal = {Solar Energy Materials and Solar Cells}, volume = {54}, number = {4-Jan}, year = {1996}, month = {07/1998}, pages = {49-57}, chapter = {49}, abstract = {

Optical indices have been determined for thin films of several electrochromic oxide materials. One of the most important materials in electrochromic devices, WO3, was thoroughly characterized for a range of electrochromic states by sequential injection of Li ions. Another promising material, Li0.5Ni0.5O, was also studied in detail. Less detailed results are presented for three other common lithium-intercalating electrochromic electrode materials: V2O5, LiCoO2, and CeO2-TiO2. The films were grown by sputtering, pulsed laser deposition (PLD) and sol-gel techniques. Measurements were made using a combination of variable-angle spectroscopic ellipsometry and spectroradiometry. The optical constants were then extracted using physical and spectral models appropriate to each material. Optical indices of the underlying transparent conductors, determined in separate studies, were fixed in the models of this work. The optical models frequently agree well with independent physical measurements of film structure, particularly surface roughness by atomic force microscopy. Inhomogeneity due to surface roughness, gradient composition, and phase separation are common in both the transparent conductors and electrochromics, resulting sometimes in particularly complex models for these materials. Complete sets of data are presented over the entire solar spectrum for a range of colored states. This data is suitable for prediction of additional optical properties such as oblique transmittance and design of complete electrochromic devices.

}, doi = {10.1016/S0927-0248(97)00222-5}, author = {Michael D. Rubin and Klaus von Rottkay and Shi-Jie Wen and Nilg{\"u}n {\"O}zer and Jonathan L. Slack} } @article {12140, title = {Optical and Electrochemical Characteristics of Niobium Oxide Films Prepared by Sol-Gel Process and Magnetron Sputtering: A Comparison}, journal = {Solar Energy Materials and Solar Cells}, volume = {40}, number = {4}, year = {1995}, month = {08/1996}, pages = {285-296}, chapter = {285}, abstract = {

Electrochromic niobia (Nb205) coatings were prepared by the sot-gel spin-coating and d.c. magnetron sputtering techniques. Parameters were investigated for the process fabrication of sol-gel spin coated Nb205 films exhibiting high coloration efficiency comparable with that d.c. magnetron sputtered niobia films. X-ray diffraction studies (XRD) showed that the sot-gel deposited and magnetron sputtered films heat treated at temperatures below 450{\textdegree}C, were amorphous, whereas those heat treated at higher temperatures were slightly crystalline. X-ray photoelectron spectroscopy (XPS) studies showed that the stoichiometry of the films was Nb205. The refractive index and electrochromic coloration were found to depend on the preparation technique. Both films showed low absorption and high transparency in the visible range. We found that the n, k values of the sot-gel deposited films to be lower than for the sputtered films. The n and k values were n = 1.82 and k = 3 {\texttimes} 10-3, and n = 2.28 and k = 4 {\texttimes} 10-3 at 530 urn for sot-gel deposited and sputtered films, respectively. The electrochemical behavior and structural changes were investigated in 1 M LiC104/propylene carbonate solution. Using the electrochemical measurements and X-ray photoelectron spectroscopy, the probable electrode reaction with the lithiation and delithiation is Nb2O5 + x Li+ + x e- <-> LixNb205. Cyclic voltametric (CV) measurements showed that both Nb205 films exhibits electrochemical reversibility beyond 1200 cycles without change in performance. {\textquotedblleft}In situ{\textquotedblright} optical measurement revealed that those films exhibit an electrochromic effect in the spectral range 300 \< λ \< 2100 nm but remain unchanged in the infrared spectral range. The change in visible transmittance was 40\% for 250 nm thick electrodes. Spectroelectrochemical measurements showed that spin coated films were essentially electrochemically equivalent to those prepared by d.c. magnetron sputter deposition.

}, keywords = {D.C. magnetron sputtering, electrochromism, Niobia, optical properties, sol-gel deposition}, doi = {10.1016/0927-0248(95)00147-6}, author = {Nilg{\"u}n {\"O}zer and Carl M Lampert and Michael D. Rubin} } @conference {12141, title = {Optical and Electrochemical Properties of Sol-gel Spin Coated CeO2-TiO2 Films}, booktitle = {SPIE Meeting}, year = {1995}, month = {07/1995}, address = {San Diego, CA}, abstract = {

The optical and electrochemical properties of sol-gel spin coated Ce02-TiO2 (50\% CeO2) films were investigated for electrochrornic applications. The coating solutions were prepared by using mixed organic-inorganic | Ti(OC2H5)4 and Ce(NH4)2 (NO3)6 | precursors. X-ray diffraction studies showed the sol-gel spin-coated films were composed of an amorphous matrix of titanium oxide containing nanocrystallites of cerium oxide. The coating solar transmission value was Ts=0.8 (250 nm thick). The refractive index and the extinction coefficient were derived from transmittance measurements in the UV-VIS-NIR regions. These films had refractive index value of n=2.18 and extinction coefficient value of k=8x10-4 at λ=550 nm. Cyclic voltametric measurements showed reversible electrochemical insertion of lithium ions in a CeO2-TiO2/LiClO4-propylene carbonate electrochemical cell. During cycling the films maintain high optical transmittance. Spectrophotometric and electrochemical investigations performed on CeO2-TiO2 films revealed that these films are suitable as an optically passive counter-electrode in lithium electrochromic devices.

}, keywords = {cerium oxide-titanium oxide, counter electrode, electrochemical properties, electrochromic device, optical properties, sol-gel deposition}, author = {Nilg{\"u}n {\"O}zer and Selmar DeSouza and Carl M Lampert} } @conference {12149, title = {Optical Indices of the Tin-doped Indium Oxide and Tungsten Oxide Electrochromic Coatings}, booktitle = {Material Research Society Symposium }, volume = {403}, year = {1995}, pages = {551-556}, abstract = {

Thin films of tin-doped indium oxide are widely used for transparent conductors. One application of In2O3:Sn (ITO) is transparent contacts for electrochromic electrodes. Optical design of electrochromic devices requires knowledge of the optical constants for each layer from the near ultraviolet and visible to the mid infrared. Determination of the optical constants of the electrochromic layer cannot be made in isolation; a complete device or at least a half-cell including a layer of ITO is required to change the optical state of the electrochromic material. Measurements on ITO were made using variable-angle spectral ellipsometry, and spectral transmittance and reflectance. A series of structural models were fit to this data. The problem is complicated because of inhomogeneity in the films, variability in the manufacturing process, and sensitivity to environmental conditions. The spectral dependency was modeled by a single Lorentz oscillator and a Drude free-electron component. This data was then used as the basis for a model to extract the optical constants for a tungsten oxide electrochromic film.

}, author = {Klaus von Rottkay and Michael D. Rubin and Nilg{\"u}n {\"O}zer} }