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Recent Advances in the Kesterite-Based Thin Film Solar Cell Technology: Role of Ge

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Recent Advances in Thin Film Photovoltaics

Part of the book series: Advances in Sustainability Science and Technology ((ASST))

Abstract

Research on the kesterite (Cu2ZnSn(S,Se)4), CZT(S,Se)-based thin film solar cell has been substantially increasing throughout the past decade, reaching the forefront of the photovoltaic (PV) research community. Major advances have been reported at various levels, from the fundamental understanding of the material properties to improvements in the device performances and its exploration for applications other than photovoltaics. Being free of critical raw materials (CRMs), the kesterite-based PV technology was expected to supersede the chalcopyrite CIGS compound as the reference chalcogenide absorber, yet the conversion efficiency at the laboratory scale has been stalling in recent years with devices not able to breach the 13% efficiency mark. An abnormally large Voc deficit has been pointed out as the main limitation in the kesterite-based thin film solar cells. The origin of this deficit remained for a long time a subject of debate within the community, with various reasons being cited such as native defects existing in the kesterite material itself, as well as a poor morphology and highly defective interfaces (front and back) in the device structure. A broad range of methodologies were developed to address those issues, involving alternative back contact materials, compound alloying, as well as the use of electron transport layers or innovative doping and passivation strategies, but the challenge to reduce the Voc deficit remains unsolved so far. Following a string of landmark theoretical and experimental studies, the community has recently converged toward the idea that the problem associated with the structural disorder arising from the cationic substitution within the kesterite structure was in all likelihood the main limitation of devices voltage, and that the conversion efficiency could only be improved by markedly mitigating the influence of the resulting defects. To overcome this limitation, various theoretical and experimental studies have proposed replacing the unstable cationic species with other more stable candidate elements. The substitution of Cu by Ag, Zn by Cd, and Sn by Si/Ge could possibly suppress the observed cationic disorder and hence reduce the observed Voc deficit. Among the different suggested candidates, Ge has been identified as the most promising option for replacement of Sn in the standard CZT(S,Se). Sn is known to exhibit a change in its oxidation state, thus creating deep defects within the band gap and inducing band tailing effects; its substitution is therefore the most sought-after. Owing to its CRM-free constituents and freedom to tune the optical band gap from ~1.4 eV (Cu2ZnGeSe4) to ~2.2 eV (Cu2ZnGeS4), Ge kesterite is an attractive compound for application in single junction solar cells as well as wide band gap top cell in Si-based tandem solar cell devices. In this chapter, we review the different strategies employed to overcome the bottlenecks of kesterite-based solar cells until now, from the doping/partial substitution of Sn with Ge in (CZT(S,Se)) up to a complete replacement leading to the realization of Sn-free CZGSe thin film solar cells. In addition to this state of the art, a complete assessment of the limitations reported by different studies will be proposed. A specific emphasis will be placed on the description of the Ge-substituted kesterite fundamental properties explored by both theoretical and experimental methods. Finally, approaches to improve the device efficiency for single junction solar cells as well as the feasibility of realizing much anticipated tandem devices with Si will be discussed.

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Acknowledgements

Authors very well acknowledge the funding received through the INFINITE CELL project (H2020-MSCA-RISE-2017 777968) and CUSTOM-ART(Grant Agreement no. 952982). Marcel Placidi acknowledges the financial support from the Spanish Ministry of Science, Innovation, and Universities within the Ramón y Cajal Program (RYC-2017-23758). The authors from the IREC belong to the SEMS (Solar Energy Materials and Systems) Consolidated Research Group of the “Generalitat de Catalunya” (ref. 2017 SGR 862).

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  1. Solar Energy Materials and Systems Laboratory, Catalonia Institute for Energy Research (IREC), Jardins de les Dones de Negre 1, Sant Adrià de Besòs, 08930, Barcelona, Spain

    Kunal J. Tiwari, Sergio Giraldo & Marcel Placidi

  2. Electronic Engineering Department, Photovoltaic Group, Universitat Politècnica de Catalunya, C J. Girona 31, 08034, Barcelona, Spain

    Marcel Placidi, Zacharie Jehl Li-Kao & Edgardo Saucedo

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Correspondence to Edgardo Saucedo .

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Editors and Affiliations

  1. School of Electronics Engineering, Kalinga Institute of Industrial Technology (Deemed to be University), Bhubaneswar, India

    Udai P. Singh

  2. Savitribai Phule Pune University, Pune, India

    Nandu B. Chaure

Appendix

Appendix

CZT(S,Se):

Cu2ZnSn(S,Se)4.

CZTS:

Cu2ZnSnS4.

CZTSe:

Cu2ZnSnSe4.

CZGSe:

Cu2ZnGeSe4.

CZG(S,Se):

Cu2ZnGeSxSe4-x.

CRM:

Critical raw materials.

Voc:

Open circuit voltage.

STEM:

Scanning transmission electron microscopy.

HAADF:

High angle annular dark field.

EELS:

Electron energy loss spectroscopy.

SEM:

Scanning electron microscope.

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Tiwari, K.J., Giraldo, S., Placidi, M., Jehl Li-Kao, Z., Saucedo, E. (2022). Recent Advances in the Kesterite-Based Thin Film Solar Cell Technology: Role of Ge. In: Singh, U.P., Chaure, N.B. (eds) Recent Advances in Thin Film Photovoltaics. Advances in Sustainability Science and Technology. Springer, Singapore. https://doi.org/10.1007/978-981-19-3724-8_3

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  • DOI: https://doi.org/10.1007/978-981-19-3724-8_3

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  • Publisher Name: Springer, Singapore

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  • Online ISBN: 978-981-19-3724-8

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