气-固反应法原位制备硫锡化合物及其结构和形貌表征

气-固反应法原位制备硫锡化合物及其结构和形貌表征

陈文涛¹，张晓娜¹，李 晖^1*，贺 蒙^2，3，4*

1. (1.北京工业大学固体微结构与性能研究所，北京100124；2.国家纳米科学中心，中国科学院纳米系统与多级次制造重点实验室，北京100190；3.中国科学院大学物理科学学院，北京101408；4.天目湖先进储能技术研究院，江苏溧阳213300）

摘  要  利用氩气载入的二硫化碳（CS₂）蒸汽作为硫源，SnO₂粉末作为锡源，通过调控反应温度，分别原位制备了三种不同的硫锡化合物：SnS₂、Sn₂S₃和SnS。用金属Sn粉代替SnO₂作为锡源，可在更低的反应温度下获得了SnS产物。利用X射线衍射（XRD）仪和扫描电子显微镜（SEM）分别对反应产物进行了显微结构的表征。本文所提出的这种利用气相与固体材料反应原位制备硫锡化合物的方法有望用于基于硫锡化合物的器件制备中，简化制备工艺。

关键词   原位反应；二硫化碳；硫化亚锡；二硫化锡；三硫化二锡；硫化亚锡纳米片层

中图分类号：TG115.21⁺5.3  文献标识码：A    doi:10.3969/j.issn.1000-6281.2019.04.004

In-situpreparation of tin sulfides by gas-solid reaction and their structural, morphological characterizations

CHEN Wen-tao¹，ZHANG Xiao-na¹，LI Hui^1*，HE Meng^2，3，4*

（1.Institute of Microstructure and Property of Advanced Materials，Beijing University of Technology，Beijing 100124；2. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190；3.School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 101408；4.Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang Jiangsu 213300, China）

Abstract  Three kinds of tin sulfides (SnS₂, Sn₂S₃ and SnS) werein-situ prepared by using carbon disulfide (CS₂) vapor carried by flowing Ar as a sulfur source to react with SnO₂ powder at various temperatures. SnS were also prepared at lower temperatures by using Sn metal instead of SnO₂ as tin source. The structure and morphology of the products were characterized with X-ray powder diffraction (XRD) and scanning electron microscopy (SEM), respectively. The method proposed in this study can convert the tin oxide and/or tin metal directly to tin sulfides, and then will facilitate greatly the fabrication of devices based on tin sulfides. In addition, CS₂, which was used as the sulfur source in this work, has a great advantage over sulfur powder or H₂S gas, which is commonly used in chemical vapor deposition of sulfides. Using CS₂ as sulfur source not only facilitates the control of experimental parameters, but also avoids the use of highly toxic and explosive gases.

Keywords  In-situ reaction；carbon disulfide；tin monosulfide；tin disulfide；tin sesquisulfide；SnS nanosheets

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[1] BURTON L A , COLOMBARA D , ABELLON R D , et al. Synthesis, characterisation and electronic structure of single crystal SnS, Sn₂S₃ and SnS₂[J]. Chemistry of Materials, 2013, 25(24):4908-4916.

[2] KHOT K V , GHANWAT V B , BAGADE C S , et al. Synthesis of SnS₂ thin film via non vacuum arrested precipitation technique for solar cell application[J]. Materials Letters, 2016,180:23-26.

[3] MARY S A , KARTHARINAL P I , JOHNSON J S , et al.  Substrate temperature influence on the optical and electrical properties of spray deposited Sn₂S₃ thin films[J]. Optik - International Journal for Light and Electron Optics, 2016，130:245-254.

[4] 唐圣明，陈思琴，熊幸果. 硅传感器反应离子刻蚀的观察[J]. 电子显微学报，2000，19(4):583-584.

[5] 李忠，邹凯.  CdS/CdTe异质结复合薄膜的制备及其性能表征[J]. 电子显微学报，2014，33(4):324-329.

[6] REDDY K T R , REDDY P P . Structural studies on SnS films grown by a two-stage process[J]. Materials Letters, 2002, 56(1/2):0-111.

[7] KHADRAOUIM，BENRAMDANEN，MATHIEU C，et al. Optical and electrical properties of Sn₂S₃ thin films grown by spray pyrolysis[J]. Solid State Communications, 2010, 150(5):297-300.

[8] SHAMA A A , ZEYADA H M . Electronic dielectric constants of thermally evaporated SnS thin films[J]. Optical Materials, 2003, 24(3):555-561.

[9] GHOSH B , DAS M , BANERJEE P , et al. Fabrication of vacuum-evaporated SnS/CdS heterojunction for PV applications[J]. Solar Energy Materials and Solar Cells, 2008, 92(9):1099-1104.

[10] ZHENG D S. High-performance near-infrared photodetectors based on p‑Type SnX (X = S, Se) nanowires grown via chemical vapor deposition[J].  ACS Nano, 2018, 12(7):7239-7245.

[11] CHALAPATHI U , POORNAPRAKASH B , PARK S H . Chemically deposited cubic SnS thin films for solar cell applications [J]. Solar Energy, 2016, 139:238-248.

[12] SINSERMSUKSAKUL P , SUN L , LEE S W , et al.  Overcoming efficiency limitations of SnS-based solar cells[J]. Advanced Energy Materials, 2014, 4(15):1400496.

[13] BAI Y, ZONG X, YU H , et al. Scalable low-cost SnS₂ nanosheets as counter electrode building blocks for dye-sensitized solar cells[J]. Chemistry, 2014, 20(28):8670-8676.

[14] GÜNERI E, GÖDE F, BOYARBAY B, et al. Structural and optical studies of chemically deposited Sn₂S₃ thin films[J]. Materials Research Bulletin, 2012, 47(11):3738-3742.

[15] ARORA S K, PATEL D H, AGARWAL M K. Vapour growth of SnS₂ single crystals[J]. Journal of Crystal Growth, 1993, 131(s 1/2):268–270.

[16] PRICE L S , PARKIN I P , HARDY A M E , et al.  Atmospheric pressure chemical vapor deposition of tin sulfides (SnS, Sn₂S₃, and SnS₂ ) on glass[J]. Cheminform, 2010, 30(40): 1792-1799.

[17] 余凌竹，鲁建，路姣，等.  常压化学气相沉积法制备SnO₂微纳米材料及其催化发光性质研究[J]. 电子显微学报，2016，35(6):482-489.

[18] AVELLANEDA D , KRISHNAN B , RODRIGUEZ A C , et al. Heat treatments in chemically deposited SnS thin films and their influence in CdS/SnS photovoltaic structures[J]. Journal of Materials Science: Materials in Electronics, 2015, 26(8):5585-5592.

[19] SAROJA A M , PUNITHAVATHY I K，JEYAKUMAR S J，et al.  Effect of Co doping on the physical properties of Sn₂S₃ thin film[J].  Journal of Materials Science: Materials in Electronics, 2017，28:11464-11472.

[20] MALAQUIAS J , FERNANDES P A , SALOMÉP M P, et al.  Assessment of the potential of tin sulphide thin films prepared by sulphurization of metallic precursors as cell absorbers[J]. Thin Solid Films, 2011, 519(21):7416-7420.

[21] GARCIA-ANGELMO A R , NAIR M T S , NAIR P K . Evolution of crystalline structure in SnS thin films prepared by chemical deposition[J].  Solid State Sciences, 2014, 30:26-35.

[22] ZHANG H , BALAJI Y , NALIN M A , et al. Formation mechanism of 2D SnS₂ and SnS by chemical vapor deposition using SnCl₄ and H₂S[J]. Journal of Materials Chemistry C，2018，6（23）：6172-6178.

[23] VOZNYi A , KOSYAK V , GRASE L, et al.  Formation of SnS phase obtained by thermal vacuum annealing of SnS₂, thin films and its application in solar cells[J]. Materials Science in Semiconductor Processing，2018，79:32-39.

[24] 程涌，文义明，吴伟，等. 场发射扫描电镜在现代河流沉积石英颗粒表面形态特征研究中的应用[J]. 电子显微学报，2017，36(5):457-465.