锂离子注入对V2O5薄膜光吸收的影响

采用真空蒸发经热处理制备了Ｖ２Ｏ５薄膜,使用二电极恒流法从１Ｍ／ＬＬｉＣｌＯ４的ＰＣ电解质溶液向Ｖ２Ｏ５薄膜注入锂离子,形成ＬｉｘＶ２Ｏ５（０≤ｘ≤０．５４）,测量了Ｖ２Ｏ５薄膜近垂直反射和透射光谱,计算了光吸收系数。Ｘ射线衍射分析表明薄膜为微晶结构。吸收系数与光子能量关系曲线中存在两个不同的变化区域,光子能量较高部分,（αｈν）１２与ｈν有线性关系;较低部分,吸收光谱存在一个尾巴。这两个区域的分界能量取决于电子和锂离子的注入量。研究结果表明Ｖ２Ｏ５薄膜阳极电致变色起源于吸收边缘的移动,而阴极电致变色则来源于小极化子的吸收     

低温热处理氧化钨电致变色薄膜的制备与性质

低温热处理氧化钨电致变色薄膜的制备与性质;电致变色;溶胶 凝胶法;聚乙烯醇;氧化钨     

Syntheses,electrochemical and spectroelectrochemical characterization of benzothiadiazole and benzoselenadiazole based random copolymers

Three novel donor-acceptor-donor type random copolymers based on benzothiadiazole (BTh) and benzoselenadiazole (BSe) were synthesized via Pd (0) catalyzed Suzuki polycondensation reaction. The two acceptor units were coupled with electron rich moieties which are carbazole (CZ), fluorene (FL) and silafluorene (SiFL). Monomers were characterized using ¹H and ¹³C-NMR spectroscopy. The number and weight average molecular weights of the polymers were calculated using gel permeation chromatography (GPC). All three polymers were electrochemically and spectroelectrochemically characterized. PBThBSeCZ, PBThBSeFL and PBThBSeSiFL showed only p-dopable character and their doping/dedoping potentials were determined as 1.4 V/1.2 V, 1.53 V/1.27 V and 1.8 V/1.3 V, respectively. Corresponding HOMO energy levels were calculated as ?5.85 eV, ?6.05 eV and ?6.15 eV whereas LUMO energy levels were found to be ?3.67 eV, ?3.84 eV and ?3.77 eV, respectively. PBThBSeCZ had lower HOMO level and band gap than PBThBSeFL and PBThBSeSiFL due to its increased electron donating capability of nitrogen atom in carbazole unit.     

Novel aromatic polyamides and polyimides functionalized with 4‐tert‐butyltriphenylamine groups

A new triphenylamine‐containing diamine monomer, 4,4′‐diamino‐4″‐tert‐butyltriphenylamine, was successfully synthesized by the cesium fluoride‐mediated N,N‐diarylation of 4‐tert‐butylaniline with 4‐fluoronitrobenzene, followed by the reduction of the nitro group. The obtained diamine monomer was reacted with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to produce two series of novel triphenylamine‐based polyamides and polyimides with pendent tert‐butyl substituents. Most of the polymers were readily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylacetamide (DMAc), and could be solution cast into tough and flexible polymer films. These polymers showed high glass transition temperatures between 282 and 320 °C, and they were fairly stable up to a temperature above 450 °C (for polyamides) or 500 °C (for polyimides). These polymers exhibited UV absorption maxima around 308 to 361 nm. The photoluminescence spectra of the polyamides in DMAc exhibited a peak emission wavelength in the blue at 421–433 nm. Cyclic voltammograms of polyamides and polyimides showed an oxidation wave at 1.0–1.1 V versus Ag/AgCl in an acetonitrile solution. All the polyamides and polyimides exhibited excellent reversibility of electrochromic characteristics by continuous several cyclic scans between 0.0 and 1.1–1.3 V, with a color change from the original pale yellowish neutral form to the green or blue oxidized forms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4579–4592, 2006     

Effects of solvent and electrolyte on the electrochromic behavior and degradation of chemically prepared polyaniline-poly(vinyl alcohol) composite films

Effects of solvent and electrolyte on the electrochromic behavior and degradation of polyaniline in nonaqueous aprotic media, as well as its electrochemical redox and degradation mechanisms, were investigated with chemically prepared polyaniline-poly (vinyl alcohol) composite films and polyaniline homogeneous films. Visible and FT-IR absorption spectra of the polyaniline films, oxidized electrochemically at various polarization potentials, showed that the mechanisms in aprotic media involved two successive oxidation processes. In contrast to aqueous systems, the higher oxidation process involved further anion insertion without deprotonation, and the degradation was due to partial formation of the electrochemically inactive quinonediimine structure at excessive polarization potentials. From investigations of solvent and electrolyte effects, it is suggested that the electrochromic behavior and degradation of polyaniline are influenced by the electron-donating and accepting ability of solvents, acceptor strength of electrolyte cations, and the nucleophilic character of electrolyte anions. It was also suggested that some anions like as well as protons, are constrained in the PVA matrix by specific electrostatic interactions and steric effects to improve the stability of polyaniline in the highly oxidized state. © 1994 John Wiley & Sons, Inc.     

Solid-state anion migration in the anodic oxidation of lutetium diphthalocyanine

The solid-state anion-migration mechanism proposed recently to account for the results of moving-boundary measurements on lutetium diphthalocyanine films was confirmed by quantitative radiotracer experiments using chloride and sulfate electrolytes. The same mechanism was independently demonstrated for these anions and for bromide by semiquantitative energy-dispersive x-ray spectroscopy. The red oxidation product containing chloride ion decomposed gradually in ambient air, while that containing sulfate or bisulfate appeared to be stable. This paper was presented in part at the 21st Electronic Materials Conference in Boulder, Colorado, June 27, 1979.     

Robust Triplatinum Redox-Chromophore for a Post-Synthetic Color-Tunable Electrochromic System

An electrochromic system showing ease of color tunability has been constructed using a triple-decker Pt^II complex [Pt₃(μ₃-pydt)₂(bpy)₃]²⁺ (H₂pydt=2,6-pyridinedithiol, bpy=2,2′-bipyridine). The divalent complex undergoes electrochemically quasi-reversible two-electron transfer coupled with the coordination/dissociation of axial ligands, forming higher valent Pt(+2.67) species [Pt₃X₂(μ₃-pydt)₂(bpy)₃]²⁺ (X=Cl⁻, Br⁻, and SCN⁻). These higher valent species exhibit characteristic colors ranging from red to cyan depending on the counter anion X⁻ of the electrolyte. The triple-decker structure provides a novel multicolor electrochromic system with favorable stability and reversibility. Theoretical calculations indicate that the colors of the Pt(+2.67) species are tunable by the trans influence of the axial ligand X⁻. This novel strategy of post-synthetic color-tuning using triplatinum systems should enable the facile preparation of colorful electrochromic devices without any complicated procedures, which may find application in flexible displays, optical devices, and sensors.     

Spray‐processable thiazolothiazole‐based copolymers with altered donor groups and their electrochromic properties

Two novel thiazolo[5,4‐d]thiazole containing donor–acceptor type alternating copolymers, poly[2‐(5‐(2‐decyl‐2H‐benzo[d][1,2,3]triazol‐4‐yl)thiophen‐2‐yl)‐5‐(thiophen‐2‐yl)thiazolo[5,4‐d]thiazole] (BTzTh) and poly[2‐(5‐(2‐decyl‐2H‐benzo[d][1,2,3]triazol‐4‐yl)furan‐2‐yl)‐5‐(furan‐2‐yl)thiazolo[5,4‐d]thiazole] (BTzFr) were synthesized by Stille coupling polymerization and their electrochemical and electrochromic properties were explored. Electrochemical activities of the spray‐casted polymer films were determined by cyclic voltammetry. To evaluate the effect of thiophene and furan moieties on the optical properties of the copolymers, spectroelectrochemistry studies were performed. To examine the switching abilities, copolymer films were subjected to a double potential step chronoamperometry in their local maximum absorptions. Both thiazolothiazole‐containing copolymers showed multichromic properties with low band‐gap values 1.7 and 1.9 eV for BTzTh and BTzFr, respectively. The decent electrochromical properties together with solution processability make them important candidates for electrochromic applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3901–3906     

Soluble,redox‐active,and blue‐emitting poly(amide‐hydrazide)s and poly(amide‐1,3,4‐oxadiazole)s containing pyrenylamine units

Two new aromatic poly(amide‐hydrazide)s (PAHs)‐bearing electroactive pyrenylamine units in the backbone were prepared from the phosphorylation polycondensation reactions of N,N‐di(4‐carboxyphenyl)‐1‐aminopyrene ( 1 ) with p‐aminobenzoyl hydrazide (p‐ABH) and m‐aminobenzoyl hydrazide (m‐ABH), respectively. The PAHs could be further cyclodehydrated into the corresponding poly(amide‐1,3,4‐oxadiazole)s in the range of 300–400 °C in the solid film state. All the hydrazide and oxadiazole polymers were soluble in many polar organic solvents and could afford flexible and strong films via solution casting. The poly(amide‐1,3,4‐oxdiazole)s had high glass‐transition temperatures (294–309 °C) and high thermal stability (10% weight‐loss temperature in excess of 520 °C). The dilute solutions of all the hydrazide and oxadiazole polymers showed strong fluorescence with emission maxima around 457–459 nm in the blue region. Copolymers obtained from the polycondensation of equimolar mixture of diacid 1 and 4,4′‐oxydibenzoic acid with p‐ABH or m‐ABH exhibited a significantly increased fluorescence quantum efficiency in comparison with the homopolymers. Cyclic voltammetry results indicated that all the hydrazide and oxadiazole polymers exhibited an ambipolar (n‐ and p‐doping processes) and electrochromic behavior. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.