Wet synthesis of Cu2MnSnS4 thin films for photovoltaics: Oxidation control and CdS impact on device performances

Butrichi, F.; Trifiletti, V.; Tseberlidis, G.; Colombo, B.E.G.; Taglietti, F.; Rancan, M.; Armelao, L.; Binetti, S.

doi:10.1016/j.solmat.2024.112924

Solar Energy Materials and Solar Cells

2024

DOI: 10.1016/j.solmat.2024.112924

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Wet synthesis of Cu2MnSnS4 thin films for photovoltaics: Oxidation control and CdS impact on device performances

F. Butrichi,

V. Trifiletti,

G. Tseberlidis

et al.

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Cited by 4 publications

References 56 publications

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A CdS‐Free Alternative TiS₂ Buffer: Toward High‐Performing Cu₂MSnS₄ (M = Co, Mn, Fe, Mg) Solar Cells

Arockiadoss,

Rasu Chettiar,

Linda

et al. 2024

Advcd Theory and Sims

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Cu2MSnS4 (M = Co,Mn,Fe,Mg) are emerging as potential photovoltaic absorbers owing to their exceptional properties. However, a large open‐circuit voltage (VOC) deficit caused by the unfavorable band alignment with the toxic CdS buffer limits their overall efficiency. Therefore, identifying an appropriate alternative buffer is essential for improving performance. Herein, solar cell capacitance simulator in one dimension (SCAPS‐1D) is employed to theoretically design and analyze these emerging solar cells using TiS₂ as a substitute for CdS. The investigation focuses on various parameters, including buffer, absorber, and interface characteristics, to evaluate their impacts on performance. Remarkably, the highest efficiencies achieved with TiS₂ buffers are 27.02%, 27.04%, 30.04%, and 30.26% for Cu2MSnS4 (M = Co,Mn,Fe,Mg), respectively, surpassing CdS by 1.36, 1.76, 1.23, and 1.15 times. The high efficiencies obtained are associated with reduced electron barrier of −0.24 eV, −0.4 eV, −0.04 eV, and 0.08 eV at TiS2/Cu2MSnS4 (M = Co,Mn,Fe,Mg) interface, lower accumulation capacitance, significantly higher built‐in potentials (>1.2 V), lower VOC losses (<0.35 V) and improved recombination resistance in TiS₂ solar cells compared to CdS. Additionally, the study addresses the experimental challenges and strategies necessary for the practical fabrication of TiS2‐based solar cells, providing valuable insights for the photovoltaic community.

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A CdS‐Free Alternative TiS₂ Buffer: Toward High‐Performing Cu₂MSnS₄ (M = Co, Mn, Fe, Mg) Solar Cells

Arockiadoss,

Rasu Chettiar,

Linda

et al. 2024

Advcd Theory and Sims

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Optimization of CZTSe Thin Films Using Sequential Annealing in Selenium and Tin–Selenium Environments

Zaki,

Sava,

Simandan

et al. 2024

Inorg. Chem.

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Cu 2 ZnSnSe 4 (CZTSe) is a promising material for thin-film solar cells due to its suitable band gap, high absorption coefficient, and composition of earth-abundant and nontoxic elements. In this study, we prepared CZTSe thin films from Cu/SnSe 2 and ZnSe stacks using a two-step annealing process. Initially, Cu−Sn−Se (CTSe) films were synthesized by sequential deposition and annealing of Cu and SnSe 2 precursors in either a selenium (Se) or tin−selenium (Sn+Se) atmosphere. After the deposition of a ZnSe layer on top of CTSe films, the stack underwent a second annealing process, again in either a Se or Sn+Se atmosphere, resulting in four distinct annealing combinations: Se→ Se, Sn+Se→Se, Se→Sn+Se, and Sn+Se→Sn+Se. The first annealing step enabled the formation of CTSe, while the second annealing step, performed after ZnSe deposition, led to the formation of the CZTSe phase. Comprehensive characterization including grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and electrical measurements was conducted. GIXRD and Raman analysis revealed kesterite CZTSe phase peaks, with some samples showing a split in the main peak at ∼27°(2θ), indicating the presence of Cu x Se and ZnSe secondary phases. SEM analysis showed the impact of Sn and Se annealing on grain size, with larger grains observed in films annealed in Sn+Se atmospheres, particularly in the second heat treatment process. EDS results displayed consistent elemental composition across samples, with varying Cu/(Zn+Sn), Zn/Sn and Se/metal ratios influencing the band gap values from 1.09 to 1.63 eV. Hall measurements indicated p-type conductivity with carrier concentrations between 10 16 and 10 23 cm −3 . These results highlight the effectiveness of our two-step annealing process, particularly the Sn+Se atmosphere, in optimizing CZTSe thin films for potential use in high-efficiency thin-film solar cells.

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Optimized hot injection and HCl purification for high quality Cu₂ZnSnS₄ nanoparticles

Husien,

Tseberlidis,

Trifiletti

et al. 2025

Nanoscale Adv.

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Wet synthesis of Cu2MnSnS4 thin films for photovoltaics: Oxidation control and CdS impact on device performances

Cited by 4 publications

References 56 publications

A CdS‐Free Alternative TiS₂ Buffer: Toward High‐Performing Cu₂MSnS₄ (M = Co, Mn, Fe, Mg) Solar Cells

A CdS‐Free Alternative TiS₂ Buffer: Toward High‐Performing Cu₂MSnS₄ (M = Co, Mn, Fe, Mg) Solar Cells

Optimization of CZTSe Thin Films Using Sequential Annealing in Selenium and Tin–Selenium Environments

Optimized hot injection and HCl purification for high quality Cu₂ZnSnS₄ nanoparticles

Contact Info

Product

Resources

About

Wet synthesis of Cu2MnSnS4 thin films for photovoltaics: Oxidation control and CdS impact on device performances

Cited by 4 publications

References 56 publications

A CdS‐Free Alternative TiS2 Buffer: Toward High‐Performing Cu2MSnS4 (M = Co, Mn, Fe, Mg) Solar Cells

A CdS‐Free Alternative TiS2 Buffer: Toward High‐Performing Cu2MSnS4 (M = Co, Mn, Fe, Mg) Solar Cells

Optimization of CZTSe Thin Films Using Sequential Annealing in Selenium and Tin–Selenium Environments

Optimized hot injection and HCl purification for high quality Cu2ZnSnS4 nanoparticles

Contact Info

Product

Resources

About

A CdS‐Free Alternative TiS₂ Buffer: Toward High‐Performing Cu₂MSnS₄ (M = Co, Mn, Fe, Mg) Solar Cells

A CdS‐Free Alternative TiS₂ Buffer: Toward High‐Performing Cu₂MSnS₄ (M = Co, Mn, Fe, Mg) Solar Cells

Optimized hot injection and HCl purification for high quality Cu₂ZnSnS₄ nanoparticles