Antimony sulfide (Sb₂S₃) is an emerging earth-abundant semiconductor for photoelectrochemical (PEC) water reduction. The anisotropic nature of Sb₂S₃ is responsible for its direction-dependent carrier transport efficiency. In general, photogenerated carriers transfer more efficiently along the [hk1] orientation than along the [hk0] orientation. However, the synthesis of a Sb₂S₃ film with precisely controlled [hk1] orientation is still very challenging. Herein, a completely [hk1]-oriented Sb₂S₃ film is prepared by sulfurizing an Ag/Sb bimetallic precursor film deposited using dual-source electron-beam evaporation. A sliver-induced crystal growth model is proposed to elucidate the formation mechanism of the [hk1]-oriented Sb₂S₃ film. Mechanistic studies reveal that the [hk1]-oriented Sb₂S₃ film has a lower defect density, a lower bulk and surface recombination, and better carrier transport efficiency in comparison to those of a randomly oriented Sb₂S₃ film. As a result, a photocathode based on the [hk1]-oriented Sb₂S₃ film delivers a high photocurrent density of 9.4 mA cm^–2 at 0 V versus RHE and a high applied bias photon-to-current efficiency of 1.2% in a neutral electrolyte. Our work not only demonstrates the effectiveness of the crystal orientation of a Sb₂S₃ film for PEC water splitting but also provides a strategy for crystal orientation engineering of stibnite-type semiconductors for solar energy conversion applications.

中文翻译：

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调整 Sb2S3 薄膜的晶体取向以实现高效的光电化学减水

硫化锑 (Sb ₂ S ₃ ) 是一种新兴的地球资源丰富的半导体，用于光电化学 (PEC) 水还原。_{Sb 2} S ₃的各向异性性质是其与方向相关的载流子传输效率的原因。一般来说，光生载流子沿[ hk 1] 方向的传输比沿[ hk 0] 方向的传输效率更高。然而，合成具有精确控制的[ hk 1] 取向的Sb ₂ S ₃薄膜仍然非常具有挑战性。这里，完全[ hk 1]取向的Sb ₂ S ₃薄膜是通过硫化使用双源电子束蒸发沉积的 Ag/Sb 双金属前体薄膜制备的。为了阐明[ hk 1] 取向Sb ₂ S ₃薄膜的形成机理，提出了一种银诱导晶体生长模型。机理研究表明，与随机取向的Sb ₂ S _{3薄膜相比，[} hk 1]取向的Sb ₂ S ₃薄膜具有较低的缺陷密度、较低的体积和表面复合以及更好的载流子传输效率。结果，基于[ hk 1]取向的Sb ₂ S _{3的光电阴极}相对于 RHE，薄膜在 0 V 时可提供 9.4 mA cm ^–2的高光电流密度，并在中性电解质中提供 1.2% 的高偏置光子电流效率。我们的工作不仅证明了 Sb ₂ S ₃薄膜的晶体取向对 PEC 水分解的有效性，而且还为太阳能转换应用中辉锑矿型半导体的晶体取向工程提供了策略。