su20 - cu3vo4复合薄膜的合成及其光电性能

V. Smilyk, Sergii Fomaniyk, G. Kolbasov, Igor Rysetskiy, Michael Danilov
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引用次数: 0

摘要

采用电化学合成方法制备cu20 - cu3vo4薄膜。通过对铜和钒离子的极化曲线和Pourbaix图的分析,可以分析薄膜沉积过程中可能发生的反应。在0 ~ -0.2V电位范围内,工作溶液中主要析出的是带有Cu3VO4杂质的单价氧化铜Cu2O。同时,近电极层存在两个相互竞争的过程,即Cu2O形成反应导致的酸化和Cu2O与HVO42-化学相互作用导致的碱化。过量OH-离子的生成会抑制Cu3VO4的生成反应速率,加速Cu2O的生成反应。因此,与Cu2O相比,Cu3VO4的沉积程度较小。因此,为了提高Cu3VO4的产率,我们尝试降低沉积电流,根据文献,这有助于降低电极层附近pH变化的影响。其中,众所周知,改变pH时的临界电流极限从5 mA/cm2以上开始。对于薄膜的合成,选择了高达1 mA/cm2的电流,这有助于生成Cu3VO4 - Cu2O复合材料,这一点从x射线图的分析中得到了进一步证实。结果表明,其光电化学性能与热处理条件有关。这是通过在空气和氩气中退火的样品中量子产率的光谱特征和光电流值的差异来表示的。利用x射线相分析方法,确定了在氩气中热处理有助于形成Cu3VO4和Cu2O复合材料,而在空气中热处理则主要形成CuO和V2O5氧化物的混合物。在空气中退火的薄膜中,由于宽带氧化物化合物的影响,光电化学电流的量子产率值较小,光谱依赖性较窄。在光电流量子产率的光谱曲线上,由于Eg = 1.5 eV的钒酸铜的贡献,导致光谱延伸到可见光区域。光电流量子输出光谱和x射线图分析表明,薄膜结构中单价铜的增加有助于光电流在450-600nm波长范围内以-0.2的相对电位增长。hse在2次。这表明氩气热处理对提高Cu3VO4和Cu2O复合材料光电阴极的效率有积极的影响。
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SYNTHESIS AND PHOTOELECTROCHEMICAL PROPERTIES OF SU2O-CU3VO4 COMPOSITE FILMS
Cu2O-Cu3VO4 films were obtained by elect­rochemical synthesis. The analysis of polarization curves and Pourbaix diagrams for copper and vanadium ions made it possible to analyze the possible reactions that occur during the deposition of films. At potentials from 0  to -0.2V, mainly monovalent copper oxide Cu2O with Cu3VO4 impurities precipitated in the working solution. At the same time, there are two competing processes of acidification of the near-electrode layer as a result Cu2O formation reaction and alkalinization as a result of the chemical interaction of Cu2O with HVO42-. The formation of an excess of OH- ions can inhibit the reaction rate of the formation of  Cu3VO4, accelerating the reaction of the formation of Cu2O. Thus, deposition of Cu3VO4 will take place to a lesser extent compared to Cu2O. Accordingly, to increase the yield of  Cu3VO4, an attempt was made to reduce the deposition current, which, according to literature, helps to reduce the effect of the pH change near the electrode layer. Where, as known the critical current limit at change pH starts from  5 or more mA/cm2. For the synthesis of the films, a current of up to 1 mA/cm2 selected, which contributed to the production of the Cu3VO4 - Cu2O composite, as was established further from the analysis of X-ray patterns. It is shown that their photoelectrochemical pro­perties depend on the heat treatment conditions. This is expressed by the difference in the spectral characteristics of the quantum yield and the value of the photocurrent in the samp­les annealed in air and argon. Using the X-ray phase analysis method, it was established that heat treatment in argon contributes to the formation of a Cu3VO4 and Cu2O composite, in contrast to heat treatment in air, where a mixture of CuO and V2O5 oxides is mainly formed. In the film annealed in air due to impact of wide-band oxide compounds, a smaller value of the quantum yield of the photoelectrochemical current and a narrower spectral dependence were observed. The stretching of the spectrum into the region of visible light on the spectral curves of the photocurrent quantum yield is caused by the contribution of copper vanadate with Eg = 1.5 eV. Analysis of photo­current quantum output spectra and X-ray patterns showed that an increase in monovalent copper in the film structure contributes to the growth of photocurrent in the wavelength range of 450-600nm at a potential of -0.2 relative. h.s.e in 2 times. This indicates a positive effect of heat treatment in argon on increasing the efficiency of photocathodes based on a composite of Cu3VO4 and Cu2O for photoelectrochemical cells.
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