Near-infrared absorbing Cu12Sb4S13 and Cu3SbS4 nanocrystals: synthesis, characterization, and photoelectrochemistry.
Near-infrared absorbing Cu12Sb4S13 and Cu3SbS4 nanocrystals: synthesis, characterization, and photoelectrochemistry.
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DOI：
10.1021/ja402702x
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发表时间：
2013-07
影响因子：
15
通讯作者：
J. van Embden;K. Latham;N. Duffy;Y. Tachibana
中科院分区：
文献类型：
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作者：
J. van Embden;K. Latham;N. Duffy;Y. Tachibana
在此，我们提出了四面体铜锑硫化物 (CAS) 纳米晶体 (Cu12Sb4S13) 的新合成方法，它在可见光和近红外区域表现出强吸收。通过配体调节，Cu12Sb4S13 NC 的尺寸可以从 6 nm 增加到 18 nm。通过优化配体化学和最大化锑前体的反应性来实现相纯度。我们对四面体 (Cu12Sb4S13) 和铁锰矿 (Cu3SbS4) NC 的光学和光电特性进行了详细研究。这些NCs被发现具有非常高的吸收系数，达到10(5) cm(-1)，并且四面体和铁磷灰石NCs的带隙分别为1.7和1 eV。采用紫外光电子能谱来确定带位置。在每种情况下，费米能量都位于价带附近，表明是 p 型半导体。研究发现，在 350 °C 的硫蒸气中对四面体 CAS NC 薄膜进行退火可产生纯铁铁铜矿 NC 薄膜，从而为调整这些 NC 薄膜内的晶体结构提供了可能性。无肼未退火薄膜的光电化学表现出强烈的 p 型光响应，在温和照明下测量高达 0.1 mA/cm(2)。总的来说，这些光学特性使 CAS NC 成为薄膜和混合太阳能电池以及一般强近红外吸收剂的优秀新候选者。
Herein, we present the novel synthesis of tetrahedrite copper antimony sulfide (CAS) nanocrystals (Cu12Sb4S13), which display strong absorptions in the visible and NIR. Through ligand tuning, the size of the Cu12Sb4S13 NCs may be increased from 6 to 18 nm. Phase purity is achieved through optimizing the ligand chemistry and maximizing the reactivity of the antimony precursor. We provide a detailed investigation of the optical and photoelectrical properties of both tetrahedrite (Cu12Sb4S13) and famatinite (Cu3SbS4) NCs. These NCs were found to have very high absorption coefficients reaching 10(5) cm(-1) and band gaps of 1.7 and 1 eV for tetrahedrite and famatinite NCs, respectively. Ultraviolet photoelectron spectroscopy was employed to determine the band positions. In each case, the Fermi energies reside close to the valence band, indicative of a p-type semiconductor. Annealing of tetrahedrite CAS NC films in sulfur vapor at 350 °C was found to result in pure famatinite NC films, opening the possibility to tune the crystal structure within thin films of these NCs. Photoelectrochemistry of hydrazine free unannealed films displays a strong p-type photoresponse, with up to 0.1 mA/cm(2) measured under mild illumination. Collectively these optical properties make CAS NCs an excellent new candidate for both thin film and hybrid solar cells and as strong NIR absorbers in general.