Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations
Vanadium doped indium sulphide, In _2 S _3 :V, is studied as a potential absorber material for intermediate band (IB) solar cells. Based on electronic considerations, it is usually assumed that V occupies octahedrally coordinated In sites, although geometrical considerations would favour tetrahedral...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
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IOP Publishing
2023-01-01
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| Series: | JPhys Energy |
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| Online Access: | https://doi.org/10.1088/2515-7655/acd95b |
| _version_ | 1797810349820346368 |
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| author | Elaheh Ghorbani Martin Schiller Hans H Falk Leonard A Wägele Stefanie Eckner Francesco d’Acapito Roland Scheer Karsten Albe Claudia S Schnohr |
| author_facet | Elaheh Ghorbani Martin Schiller Hans H Falk Leonard A Wägele Stefanie Eckner Francesco d’Acapito Roland Scheer Karsten Albe Claudia S Schnohr |
| author_sort | Elaheh Ghorbani |
| collection | DOAJ |
| description | Vanadium doped indium sulphide, In _2 S _3 :V, is studied as a potential absorber material for intermediate band (IB) solar cells. Based on electronic considerations, it is usually assumed that V occupies octahedrally coordinated In sites, although geometrical considerations would favour tetrahedral In sites. In this study, we therefore combined experimental x-ray diffraction and x-ray absorption spectroscopy with ab initio theoretical calculations of both $\mathrm{\alpha}$ and $\mathrm{\beta}$ phase to elucidate the incorporation of V in In _2 S _3 :V thin films grown with different V content and different growth temperatures. Comparing shape and position of the measured and calculated x-ray absorption edge of V, comparing experimentally determined and calculated V–S bond lengths, and evaluating the calculated heat of solution of V on different lattice sites all indicate that V is incorporated on octahedral rather than tetrahedral sites in the In _2 S _3 matrix. For this material system, the electronic benefit of octahedral coordination thus outweighs the mechanical stress of the associated lattice relaxation. Finally, we studied the electronic structure of V-substituted $\mathrm{\alpha}$ - $\mathrm{In_2S_3}$ using hybrid density functional calculations and find that for a concentration of 1.9 at %, V on octahedrally coordinated In sites forms an empty IB isolated from valence band and conduction band (CB). By increasing the V content to 3.8 at %, however, the gap between IB and CB closes, which results in a reduction of the band gap. This differs from the electronic structure calculated for $\mathrm{\beta}$ - $\mathrm{In_2S_3}$ :V and clearly demonstrates that both crystal structure and V incorporation site affect the resulting electronic material properties. |
| first_indexed | 2024-03-13T07:06:25Z |
| format | Article |
| id | doaj.art-488fd841e2fa4b71af29d55fb53cb803 |
| institution | Directory Open Access Journal |
| issn | 2515-7655 |
| language | English |
| last_indexed | 2024-03-13T07:06:25Z |
| publishDate | 2023-01-01 |
| publisher | IOP Publishing |
| record_format | Article |
| series | JPhys Energy |
| spelling | doaj.art-488fd841e2fa4b71af29d55fb53cb8032023-06-06T08:07:39ZengIOP PublishingJPhys Energy2515-76552023-01-015303500310.1088/2515-7655/acd95bElucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculationsElaheh Ghorbani0https://orcid.org/0000-0002-4037-1602Martin Schiller1Hans H Falk2https://orcid.org/0000-0002-9019-7614Leonard A Wägele3Stefanie Eckner4Francesco d’Acapito5https://orcid.org/0000-0003-2207-6113Roland Scheer6Karsten Albe7https://orcid.org/0000-0003-4669-8056Claudia S Schnohr8https://orcid.org/0000-0002-3688-7104Fachgebiet Materialmodellierung, Institut für Materialwissenschaft , TU Darmstadt, 64287 Darmstadt, GermanyFelix-Bloch-Institut für Festkörperphysik, Universität Leipzig , Linnéstraße 5, 04103 Leipzig, Germany; Martin-Luther-Universität Halle-Wittenberg, Institut für Physik , 06099 Halle, GermanyFelix-Bloch-Institut für Festkörperphysik, Universität Leipzig , Linnéstraße 5, 04103 Leipzig, GermanyMartin-Luther-Universität Halle-Wittenberg, Institut für Physik , 06099 Halle, GermanyFelix-Bloch-Institut für Festkörperphysik, Universität Leipzig , Linnéstraße 5, 04103 Leipzig, GermanyCNR-IOM-OGG c/o ESRF LISA CRG , 71 Avenue des Martyrs, 38043 Grenoble, FranceMartin-Luther-Universität Halle-Wittenberg, Institut für Physik , 06099 Halle, GermanyFachgebiet Materialmodellierung, Institut für Materialwissenschaft , TU Darmstadt, 64287 Darmstadt, GermanyFelix-Bloch-Institut für Festkörperphysik, Universität Leipzig , Linnéstraße 5, 04103 Leipzig, GermanyVanadium doped indium sulphide, In _2 S _3 :V, is studied as a potential absorber material for intermediate band (IB) solar cells. Based on electronic considerations, it is usually assumed that V occupies octahedrally coordinated In sites, although geometrical considerations would favour tetrahedral In sites. In this study, we therefore combined experimental x-ray diffraction and x-ray absorption spectroscopy with ab initio theoretical calculations of both $\mathrm{\alpha}$ and $\mathrm{\beta}$ phase to elucidate the incorporation of V in In _2 S _3 :V thin films grown with different V content and different growth temperatures. Comparing shape and position of the measured and calculated x-ray absorption edge of V, comparing experimentally determined and calculated V–S bond lengths, and evaluating the calculated heat of solution of V on different lattice sites all indicate that V is incorporated on octahedral rather than tetrahedral sites in the In _2 S _3 matrix. For this material system, the electronic benefit of octahedral coordination thus outweighs the mechanical stress of the associated lattice relaxation. Finally, we studied the electronic structure of V-substituted $\mathrm{\alpha}$ - $\mathrm{In_2S_3}$ using hybrid density functional calculations and find that for a concentration of 1.9 at %, V on octahedrally coordinated In sites forms an empty IB isolated from valence band and conduction band (CB). By increasing the V content to 3.8 at %, however, the gap between IB and CB closes, which results in a reduction of the band gap. This differs from the electronic structure calculated for $\mathrm{\beta}$ - $\mathrm{In_2S_3}$ :V and clearly demonstrates that both crystal structure and V incorporation site affect the resulting electronic material properties.https://doi.org/10.1088/2515-7655/acd95bIn2S3indium sulphidevanadiumlocal structurethin filmsx-ray absorption spectroscopy |
| spellingShingle | Elaheh Ghorbani Martin Schiller Hans H Falk Leonard A Wägele Stefanie Eckner Francesco d’Acapito Roland Scheer Karsten Albe Claudia S Schnohr Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations JPhys Energy In2S3 indium sulphide vanadium local structure thin films x-ray absorption spectroscopy |
| title | Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations |
| title_full | Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations |
| title_fullStr | Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations |
| title_full_unstemmed | Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations |
| title_short | Elucidating the local structure of V substitutes in In2S3 as potential intermediate band material by x-ray absorption spectroscopy and first principles calculations |
| title_sort | elucidating the local structure of v substitutes in in2s3 as potential intermediate band material by x ray absorption spectroscopy and first principles calculations |
| topic | In2S3 indium sulphide vanadium local structure thin films x-ray absorption spectroscopy |
| url | https://doi.org/10.1088/2515-7655/acd95b |
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