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氧化锌及掺镓氧化锌薄膜的合成、表征及其在染料敏化太阳能电池中的应用。

Synthesis and characterization of ZnO and ZnO:Ga films and their application in dye-sensitized solar cells.

作者信息

de Souza Gonçalves Agnaldo, Davolos Marian Rosaly, Masaki Naruhiko, Yanagida Shozo, Morandeira Ana, Durrant James R, Freitas Jilian Nei, Nogueira Ana Flávia

机构信息

Instituto de Química, Universidade Estadual Paulista-UNESP, Araraquara, SP, Brazil.

出版信息

Dalton Trans. 2008 Mar 21(11):1487-91. doi: 10.1039/b716724e. Epub 2008 Feb 12.

Abstract

Highly crystalline ZnO and Ga-modified zinc oxide (ZnO:Ga) nanoparticles containing 1, 3 and 5 atom% of Ga3+ were prepared by precipitation method at low temperature. The films were characterized by XRD, BET, XPS and SEM. No evidence of zinc gallate formation (ZnGa2O4), even in the samples containing 5 atom% of gallium, was detected by XRD. XPS data revealed that Ga is present into the ZnO matrix as Ga3+, according to the characteristic binding energies. The particle size decreased as the gallium level was increased as observed by SEM, which might be related to a faster hydrolysis reaction rate. The smaller particle size provided films with higher porosity and surface area, enabling a higher dye loading. When these films were applied to dye-sensitized solar cells (DSSCs) as photoelectrodes, the device based on ZnO:Ga 5 atom% presented an overall conversion efficiency of 6% (at 10 mW cm(-2)), a three-fold increase compared to the ZnO-based DSSCs under the same conditions. To our knowledge, this is one of the highest efficiencies reported so far for ZnO-based DSSCs. Transient absorption (TAS) study of the photoinduced dynamics of dye-sensitized ZnO:Ga films showed that the higher the gallium content, the higher the amount of dye cation formed, while no significant change on the recombination dynamics was observed. The study indicates that Ga-modification of nanocrystalline ZnO leads to an improvement of photocurrent and overall efficiency in the corresponding device.

摘要

通过低温沉淀法制备了含有1%、3%和5%原子比Ga³⁺的高结晶度ZnO和Ga改性氧化锌(ZnO:Ga)纳米颗粒。通过XRD、BET、XPS和SEM对薄膜进行了表征。XRD未检测到镓酸锌(ZnGa₂O₄)形成的迹象,即使在含5%原子比镓的样品中也是如此。XPS数据表明,根据特征结合能,Ga以Ga³⁺的形式存在于ZnO基体中。SEM观察到,随着镓含量的增加,粒径减小,这可能与更快的水解反应速率有关。较小的粒径使薄膜具有更高的孔隙率和表面积,从而能够负载更多的染料。当将这些薄膜用作染料敏化太阳能电池(DSSC)的光电极时,基于5%原子比ZnO:Ga的器件在10 mW cm⁻²光照下的整体转换效率为6%,与相同条件下基于ZnO的DSSC相比提高了三倍。据我们所知,这是迄今为止报道的基于ZnO的DSSC的最高效率之一。对染料敏化ZnO:Ga薄膜光致动力学的瞬态吸收(TAS)研究表明,镓含量越高,形成的染料阳离子量越高,而复合动力学未观察到显著变化。该研究表明,纳米晶ZnO的Ga改性导致相应器件中光电流和整体效率的提高。

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