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氧化锌:钛的原子层沉积:生长机制及其在硅纳米线太阳能电池中作为高效透明导电氧化物的应用

ALD of ZnO:Ti: Growth Mechanism and Application as an Efficient Transparent Conductive Oxide in Silicon Nanowire Solar Cells.

作者信息

Coutancier Damien, Zhang Shan-Ting, Bernardini Simone, Fournier Olivier, Mathieu-Pennober Tiphaine, Donsanti Frédérique, Tchernycheva Maria, Foldyna Martin, Schneider Nathanaelle

机构信息

Institut Photovoltaı̈que d'Ile-de-France (IPVF), 18 Boulevard Thomas Gobert, 91120 Palaiseau, France.

CNRS, UMR 9006, Institut Photovoltaı̈que d'Ile-de-France (IPVF), 18 Boulevard Thomas Gobert, 91120 Palaiseau, France.

出版信息

ACS Appl Mater Interfaces. 2020 May 6;12(18):21036-21044. doi: 10.1021/acsami.9b22973. Epub 2020 Apr 23.

Abstract

In the quest for the replacement of indium tin oxide (ITO), Ti-doped zinc oxide (TZO) films have been synthesized by atomic layer deposition (ALD) and applied as an n-type transparent conductive oxide (TCO). TZO thin films were obtained from titanium (IV) -propoxide (TTIP), diethyl zinc, and water by introducing TiO growth cycle in a ZnO matrix. Process parameters such as the order of precursor introduction, the cycle ratio, and the film thickness were optimized. The as-deposited films were analyzed for their surface morphology, elemental stoichiometry, optoelectronic properties, and crystallinity using a variety of characterization techniques. The growth mechanism was investigated for the first time by quartz crystal microbalance measurements. It evidenced different insertion modes of titanium depending on the precursor introduction, as well as the etching of Zn-Et surface groups by TTIP. Resistivity as low as 1.2 × 10 Ω cm and transmittance >80% in the visible range were obtained for 72-nm-thick films. Finally, the first application of ALD-TZO as TCO was reported. TZO films were successfully implemented as top electrodes in silicon nanowire solar cells. The unique properties of TZO combined with conformal coverage realized by the ALD technique make it possible for the cell to show almost flat external quantum efficiency (EQE) response, surpassing the bell-like EQE curve seen in devices with a sputtered ITO top electrode.

摘要

在寻求替代氧化铟锡(ITO)的过程中,通过原子层沉积(ALD)合成了掺钛氧化锌(TZO)薄膜,并将其用作n型透明导电氧化物(TCO)。通过在ZnO基体中引入TiO生长循环,由四异丙醇钛(TTIP)、二乙基锌和水获得了TZO薄膜。对诸如前驱体引入顺序、循环比和薄膜厚度等工艺参数进行了优化。使用多种表征技术对沉积后的薄膜进行了表面形貌、元素化学计量、光电性能和结晶度分析。首次通过石英晶体微天平测量研究了生长机理。结果表明,根据前驱体引入的不同,钛的插入模式不同,并且TTIP会蚀刻Zn-Et表面基团。对于72nm厚的薄膜,获得了低至1.2×10Ω·cm的电阻率和在可见光范围内大于80%的透过率。最后,报道了ALD-TZO作为TCO的首次应用。TZO薄膜成功地用作硅纳米线太阳能电池的顶电极。TZO的独特性能与ALD技术实现的保形覆盖相结合,使得电池能够呈现几乎平坦的外量子效率(EQE)响应,超过了具有溅射ITO顶电极的器件中所见的钟形EQE曲线。

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