†Department of Chemistry and Biochemistry, ‡Department of Materials Science and Engineering, and §California NanoSystems Institute, University of California, Los Angeles, California 90095, United States.
ACS Nano. 2015 Apr 28;9(4):4398-405. doi: 10.1021/acsnano.5b00886. Epub 2015 Apr 13.
Low-temperature solution-processable electronic materials are of considerable interest for large-area, low-cost electronics, thermoelectrics, and photovoltaics. Using a soluble precursor and suitable solvent to formulate a semiconductor ink is essential for large-area fabrication of semiconductor thin films. To date, it has been shown that hydrazine can be used as a versatile solvent to process a wide range of inorganic semiconductors. However, hydrazine is highly toxic and not suitable for large-scale manufacturing. Here we report a binary mixed solvent of amine and thiol for effective dispersion and dissolution of a large number of inorganic semiconductors including Cu2S, Cu2Se, In2S3, In2Se3, CdS, SnSe, and others. The mixed solvent is significantly less toxic and safer than hydrazine, while at the same time offering the comparable capability of formulating diverse semiconductor ink with a concentration as high as >200 mg/mL. We further show that such ink material can be readily processed into high-performance semiconducting thin films (Cu2S and Cu2Se) with the highest room-temperature conductivity among solution-based materials. Furthermore, we show that complex semiconductor alloys with tunable band gaps, such as CuIn(S(x)Se(1-x))2 (0 ≤ x ≤ 1), can also be readily prepared by simply mixing Cu2S, Cu2Se, In2S3, and In2Se3 ink solutions in a proper ratio. Our study outlines a general strategy for the formulation of inorganic semiconductor ink for low-temperature processing of large-area electronic thin films on diverse substrates and can greatly impact diverse areas including flexible electronics, thermoelectrics, and photovoltaics.
低温溶液处理电子材料对于大面积、低成本电子学、热电学和光伏学具有重要意义。使用可溶性前体和合适的溶剂来配制半导体墨水对于大面积制造半导体薄膜至关重要。迄今为止,已经表明肼可以用作一种通用溶剂来处理广泛的无机半导体。然而,肼具有高度毒性,不适合大规模制造。在这里,我们报告了一种胺和硫醇的二元混合溶剂,可有效分散和溶解大量无机半导体,包括 Cu2S、Cu2Se、In2S3、In2Se3、CdS、SnSe 等。与肼相比,混合溶剂的毒性要小得多,安全性更高,同时还具有配制浓度高达>200mg/mL 的各种半导体墨水的可比能力。我们进一步表明,这种油墨材料可以很容易地加工成高性能半导体薄膜(Cu2S 和 Cu2Se),其室温电导率在基于溶液的材料中最高。此外,我们表明,通过简单地按适当比例混合 Cu2S、Cu2Se、In2S3 和 In2Se3 油墨溶液,也可以很容易地制备具有可调带隙的复杂半导体合金,例如 CuIn(S(x)Se(1-x))2(0 ≤ x ≤ 1)。我们的研究概述了一种用于低温处理大面积电子薄膜的无机半导体油墨配方的通用策略,可极大地影响包括柔性电子学、热电学和光伏学在内的多个领域。