Phosphine-Free Synthesis and Characterization of Cubic-Phase Cu2SnTe3 Nanocrystals with Optical and Optoelectronic Properties
Phosphine-Free Synthesis and Characterization of Cubic-Phase Cu2SnTe3 Nanocrystals with Optical and Optoelectronic Properties
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具有光学和光电性能的立方相 Cu2SnTe3 纳米晶的无磷合成和表征
DOI：
10.1021/acs.chemmater.5b02743
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发表时间：
2015-09
影响因子：
8.6
通讯作者：
Yang, Qing
中科院分区：
文献类型：
--
作者：
Wang, Wenliang;Feng, Wenling;Ding, Tao;Yang, Qing
近年来，铜基多组分硫族化合物半导体纳米碳材料由于其尺寸和组成可调的性质以及在太阳能电池、1、2热电器件等方面的应用受到了广泛的关注。3 - 5特别地，在这些胶体半导体NC中，铜基I2-IV-VI 3三元化合物，例如Cu 2SnS 3、Cu 2GeSe 3和Cu 2SnSe 3，由于它们的可调带隙、高光吸收系数和空穴迁移率6 - 8，已经被深入研究并应用于锂离子电池9和光伏器件。7然而，与Cu_2MX_3（M= Ge，Sn，X= S，Se）相比，单分散、均匀的Cu_2SnTe_3纳米晶的合成仍然是一个很大的挑战，因此其进一步的表征和应用也受到限制。一个可能的原因可能在于缺乏简单和良性的方法，采用反应性匹配的前体生长的均匀的Cu 2SnTe 3 NC。据我们所知，没有关于通过基于溶液的途径进行的Cu 2SnTe 3 NC的制备的报道。虽然Cu 2SnTe 3晶体是在高温固相反应中合成的，但10，11这种耗能且耗时的方法通常会导致产品具有不规则、大尺寸和尺寸分布以及不受控制的聚集体形成，这将限制其潜在应用。另一方面，不同种类的金属碲化物NC的溶液合成主要依赖于对空气敏感的烷基膦（如TOP或TBP），1，12− 14，这对环境有害。因此，探索一种新的环境友好的方法来合成具有单分散和均匀尺寸的高质量的Cu 2SnTe 3 NCs是非常期望的。幸运的是，最近的进展表明，热注射合成可以作为一个多功能的方法来制备高品质的单分散和均匀的尺寸的纳米粒子。1，13− 16这鼓励我们通过这种热注入策略合成Cu 2SnTe 3 NCs。在此，我们首次开发了一种简单、绿色、温和、低成本的合成Cu 2SnTe 3纳米晶的方法。在我们的新策略中，Te前体通过将TeO 2溶解在1-十二烷乙烷中来制备，避免使用昂贵且有毒的烷基膦，在210 C的氩气气氛下将其快速注入Cu-Sn络合物溶液中以产生Cu 2SnTe 3 NC（详细信息的支持信息）。众所周知，热注入法最显著的特征之一是将结晶形核和生长阶段分开。17− 19利用这些优点，所得Cu 2SnTe 3 NC几乎是单分散的，尺寸均匀，平均直径约为25 nm（图S1）。这种新的合成策略有望为开发其他金属碲化物纳米结构的通用路线开辟新途径。通过X射线衍射（XRD）、能量色散X射线能谱（EDS）和X射线光电子能谱（XPS）测量确定合成的Cu 2SnTe 3 NC的相、组成和氧化态。如图1a所示，样品在25.7、29.7、42.6、50.2、61.6、67.8和77.6处的XRD峰与双晶结构的Cu 2SnTe 3的（111）、（200）、（220）、（311）、（400）、（331）和（422）面良好一致。（JCPDS No. 89-2881，立方，a= B= c= 6.04 μ m），20个。立方Cu 2SnTe 3 NC的相应示意性晶体结构显示在图1 B中。值得注意的是，Cu+和Sn 4+离子占据相同的位置。EDS谱图显示仅存在Cu、Sn、Te、Mo和C，并且存在...
In recent years, copper-based multicomponent chalcogenide semiconducting NCs have received considerable attention owing to their size-and composition-tunable properties and applications in solar cell, 1, 2 thermoelectric devices. 3− 5 In particular, among these colloidal semiconductor NCs, the copper-based I2− IV− VI3 ternary compounds, such as Cu2SnS3, Cu2GeSe3, and Cu2SnSe3 due to their tunable band gap, high optical absorption coefficients, and hole mobilities 6− 8 have been intensively investigated and applied in lithium ion battery 9 and photovoltaic devices. 7 However, in comparison with Cu2MX3 (M= Ge, Sn, X= S, Se), synthesis of monodisperse and uniform Cu2SnTe3 NCs still remains a big challenge, and therefore their further characterization and application are also restricted. A possible reason may lie in the lack of simple and benign methods that employed reactivity-matching precursors for the growth of the homogeneous Cu2SnTe3 NCs. To the best of our knowledge, there is no report on the preparation of Cu2SnTe3 NCs performed by solution-based routes. Although Cu2SnTe3 crystals have been synthesized in high temperature solid-state reaction, 10, 11 this energy-intensive and time-consuming method usually resulted in products with irregular, large size and size distribution and uncontrolled aggregate formation, which would limit their potential applications. On the other hand, the solution synthesis of different kinds of metal telluride NCs mainly relies on air-sensitive alkylphosphines (such as TOP or TBP), 1, 12− 14 which is harmful to the environment. Thus, to explore a new environmentally benign method for synthesizing high-quality Cu2SnTe3 NCs with monodisperse and uniform size is highly desirable. Fortunately, recent progress reveals that the hot-injection synthesis can act as a versatile methodology for the preparation of high-quality NCs with monodisperse and uniform size. 1, 13− 16 This encourages us to synthesize Cu2SnTe3 NCs via such a hot-injection strategy. Herein, we have developed a facile, green, mild, and costeffective route to synthesize Cu2SnTe3 NCs for the first time. In our new strategy, the Te precursor is prepared by dissolving TeO2 in 1-dodecanethiol, avoiding the use of expensive and toxic alkylphosphines, which is rapidly injected into Cu− Sn complex solution under argon atmosphere at 210 C to produce Cu2SnTe3 NCs (Supporting Information for details). It is well-known that one of the most distinctive features of the hot-injection method is the separation of the nanocrystal nucleation and growth stages. 17− 19 Taking advantage of these merits, as a result, the as-obtained Cu2SnTe3 NCs are nearly monodisperse and uniform size with an average diameter of around 25 nm (Figure S1). This new synthetic strategy is expected to open new avenues for the development of a versatile route for other metal telluride nanostructures. The phase, composition, and oxidation states of the synthesized Cu2SnTe3 NCs are determined by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) measurements. As displayed in Figure 1 a, the XRD peaks of the sample at 25.7, 29.7, 42.6, 50.2, 61.6, 67.8, and 77.6 are in good agreement with (111),(200),(220),(311),(400),(331), and (422) planes of the cubic-structured Cu2SnTe3 (JCPDS No. 89-2881, cubic, a= b= c= 6.04 Å), 20 respectively. The corresponding schematic crystal structure of cubic Cu2SnTe3 NCs is displayed in Figure 1 b. It is worth noting that Cu+ and Sn4+ ions occupy the same position. The EDS spectrum shows the presence of only Cu, Sn, Te, Mo, and C and the existence of …
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