Charge Dynamics as Probed by Small Signal-Modulated Photocurrent and Impedance Spectroscopy of Metal Vanadate Semiconductors and Alloys

IF 3.8

ACS Applied Optical Materials Pub Date : 2025-07-25 DOI:10.1021/acsaom.5c00154

Juan Carlos Expósito-Gálvez, Abhishek Rawat, Krishnan Rajeshwar* and Gerko Oskam*,

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Abstract

This study presents the combined and complementary use of two techniques, namely, intensity modulated photocurrent spectroscopy (IMPS) and photoelectrochemical impedance spectroscopy (PEIS) for the study of partially or wholly replacing copper with an alkaline earth metal (Mg, Ca) in a metavanadate compound matrix (MV₂O₆). To this end, the three reference compounds (CuV₂O₆, CaV₂O₆, MgV₂O) and two alloy compositions (Mg_0.1Cu_0.9V₂O₆ and Ca_0.1Cu_0.9V₂O₆), obtained from a solution combustion technique, were screen-printed on fluorine-doped tin oxide glass (FTO) substrates. Wavelength discrimination for optical excitation of these semiconductor samples was provided by using high-power LED (front-side) illumination with different wavelengths, UV (λ = 370 nm), blue (λ = 455 nm), green (λ = 535 nm), and red (λ = 670 nm). A nonunity photogeneration yield of mobile charge carriers was seen in a trend reminiscent of previous data on binary oxides or even for other types of ternary copper oxides from other laboratories. The dynamic aspects of charge transfer and carrier recombination are discussed using the combined IMPS-PEIS data along with other optical (e.g., diffuse reflectance spectroscopy) and photoelectrochemical data.

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用小信号调制光电流和阻抗谱探测金属钒酸盐半导体和合金的电荷动力学

本研究结合并互补了两种技术，即强度调制光电流谱（IMPS）和光电化学阻抗谱（PEIS），研究了在偏绿酸盐化合物基质（MV2O6）中部分或全部用碱土金属（Mg, Ca）替代铜。为此，通过溶液燃烧技术获得了三种参考化合物（CuV2O6、CaV2O6、MgV2O）和两种合金成分（Mg0.1Cu0.9V2O6和Ca0.1Cu0.9V2O6），并将其丝网印刷在掺氟氧化锡玻璃（FTO）衬底上。采用不同波长的高功率LED（正面）照明，紫外（λ = 370 nm）、蓝色（λ = 455 nm）、绿色（λ = 535 nm）和红色（λ = 670 nm），为半导体样品的光激发提供波长判别。移动电荷载流子的非统一光生产率的趋势让人想起以前的二元氧化物数据，甚至其他实验室的其他类型的三元铜氧化物。利用综合的imp - peis数据以及其他光学（如漫反射光谱）和光电化学数据，讨论了电荷转移和载流子复合的动态方面。

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来源期刊

ACS Applied Optical Materials 材料科学-光学材料-

CiteScore

1.10

自引率

0.00%

发文量

期刊介绍： ACS Applied Optical Materials is an international and interdisciplinary forum to publish original experimental and theoretical including simulation and modeling research in optical materials complementing the ACS Applied Materials portfolio. With a focus on innovative applications ACS Applied Optical Materials also complements and expands the scope of existing ACS publications that focus on fundamental aspects of the interaction between light and matter in materials science including ACS Photonics Macromolecules Journal of Physical Chemistry C ACS Nano and Nano Letters.The scope of ACS Applied Optical Materials includes high quality research of an applied nature that integrates knowledge in materials science chemistry physics optical science and engineering.