Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics
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 dis...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
AIP Publishing LLC
2018-10-01
|
| Series: | AIP Advances |
| Online Access: | http://dx.doi.org/10.1063/1.5051407 |
| _version_ | 1811237036476071936 |
|---|---|
| author | Chao Li Haili Song Yawei Shen Yifeng Wang Yan Cheng Ruijuan Qi Shiyou Chen Chungang Duan Rong Huang |
| author_facet | Chao Li Haili Song Yawei Shen Yifeng Wang Yan Cheng Ruijuan Qi Shiyou Chen Chungang Duan Rong Huang |
| author_sort | Chao Li |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-12T12:18:45Z |
| format | Article |
| id | doaj.art-4e223655d48642058b95fcecbcade1d1 |
| institution | Directory Open Access Journal |
| issn | 2158-3226 |
| language | English |
| last_indexed | 2024-04-12T12:18:45Z |
| publishDate | 2018-10-01 |
| publisher | AIP Publishing LLC |
| record_format | Article |
| series | AIP Advances |
| spelling | doaj.art-4e223655d48642058b95fcecbcade1d12022-12-22T03:33:21ZengAIP Publishing LLCAIP Advances2158-32262018-10-01810105322105322-810.1063/1.5051407068810ADVEvolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramicsChao Li0Haili Song1Yawei Shen2Yifeng Wang3Yan Cheng4Ruijuan Qi5Shiyou Chen6Chungang Duan7Rong Huang8Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200062, ChinaCollege of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, ChinaCollege of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, ChinaKey Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200062, ChinaThe 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.http://dx.doi.org/10.1063/1.5051407 |
| spellingShingle | Chao Li Haili Song Yawei Shen Yifeng Wang Yan Cheng Ruijuan Qi Shiyou Chen Chungang Duan Rong Huang Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics AIP Advances |
| title | Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics |
| title_full | Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics |
| title_fullStr | Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics |
| title_full_unstemmed | Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics |
| title_short | Evolution of cation ordering and crystal defects controlled by Zn substitutions in Cu2SnS3 ceramics |
| title_sort | evolution of cation ordering and crystal defects controlled by zn substitutions in cu2sns3 ceramics |
| url | http://dx.doi.org/10.1063/1.5051407 |
| work_keys_str_mv | AT chaoli evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT hailisong evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT yaweishen evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT yifengwang evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT yancheng evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT ruijuanqi evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT shiyouchen evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT chungangduan evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics AT ronghuang evolutionofcationorderingandcrystaldefectscontrolledbyznsubstitutionsincu2sns3ceramics |