TY - JOUR
T1 - Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics
AU - Li, Chao
AU - Song, Haili
AU - Shen, Yawei
AU - Wang, Yifeng
AU - Cheng, Yan
AU - Qi, Ruijuan
AU - Chen, Shiyou
AU - Duan, Chungang
AU - Huang, Rong
N1 - Publisher Copyright:
© 2018 Author(s).
PY - 2018/10/1
Y1 - 2018/10/1
N2 - The microstructures of a series of Cu2ZnxSn1-xS3 (x = 0, 0.05, 0.10, 0.15,0.20) ceramic samples are investigated by a combination of selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), high-angle annular dark-field imaging (HAADF) and X-ray energy dispersive spectroscopy (EDS) techniques. The pure Cu2SnS3 sample takes the monoclinic structure with the ordering of eight 3Cu-Sn and four 2Cu-2Sn clusters, which obey the octet rule. With the increase of Zn substitution, unique mosaic-type nanostructures comprising well-defined cation-disordered domains coherently bonded to a surrounding network phase with semi-ordered cations are formed in the matrix grains. The atomic structures of the semi-ordered phases are revealed as CuInS2-like phase (Zn < 5 atom%), Cu6ZnSn3S10 (Cu2SnS3: ZnS = 3:1) and Cu4ZnSn2S7 (Cu2SnS3: ZnS = 2:1), respectively. These ordered structures derive from the zinc blende structure (201) superlattice of -(Cu-S)2(Zn-S)(Sn-S)- in the kesterite Cu2ZnSnS4 (Cu2SnS3:ZnS = 1:1). Meanwhile, point defects, dislocations, stacking faults, and finally Cu2-xS nanoprecipitates are formed sequentially to compromise the excessive Cu ions when the Zn contents increase from 5 atom% to 20 atom%. Understanding of the concurrence and evolution of the cation ordering and crystal defects are important to tailor their microstructures and physical properties in the Cu-Zn-Sn-S quaternary system.
AB - The microstructures of a series of Cu2ZnxSn1-xS3 (x = 0, 0.05, 0.10, 0.15,0.20) ceramic samples are investigated by a combination of selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), high-angle annular dark-field imaging (HAADF) and X-ray energy dispersive spectroscopy (EDS) techniques. The pure Cu2SnS3 sample takes the monoclinic structure with the ordering of eight 3Cu-Sn and four 2Cu-2Sn clusters, which obey the octet rule. With the increase of Zn substitution, unique mosaic-type nanostructures comprising well-defined cation-disordered domains coherently bonded to a surrounding network phase with semi-ordered cations are formed in the matrix grains. The atomic structures of the semi-ordered phases are revealed as CuInS2-like phase (Zn < 5 atom%), Cu6ZnSn3S10 (Cu2SnS3: ZnS = 3:1) and Cu4ZnSn2S7 (Cu2SnS3: ZnS = 2:1), respectively. These ordered structures derive from the zinc blende structure (201) superlattice of -(Cu-S)2(Zn-S)(Sn-S)- in the kesterite Cu2ZnSnS4 (Cu2SnS3:ZnS = 1:1). Meanwhile, point defects, dislocations, stacking faults, and finally Cu2-xS nanoprecipitates are formed sequentially to compromise the excessive Cu ions when the Zn contents increase from 5 atom% to 20 atom%. Understanding of the concurrence and evolution of the cation ordering and crystal defects are important to tailor their microstructures and physical properties in the Cu-Zn-Sn-S quaternary system.
UR - http://www.scopus.com/inward/record.url?scp=85055437386&partnerID=8YFLogxK
U2 - 10.1063/1.5051407
DO - 10.1063/1.5051407
M3 - 文章
AN - SCOPUS:85055437386
SN - 2158-3226
VL - 8
JO - AIP Advances
JF - AIP Advances
IS - 10
M1 - 105322
ER -