Synthesis of magnetic doped kesterite single crystals

Podsiadło, S.; Bialoglowski, Maciej; Fadaghi, Mohammad; Gȩbicki, W.; Jastrzębski, Cezariusz; Żero, Elżbieta; Trzybiński, Damian; Woźniak, Krzysztof

doi:10.1002/crat.201400435

Cited by 17 publications

(5 citation statements)

References 14 publications

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“…In the Raman spectrum ( Figure 3 a), the presence of a pure phase of germanium-derived kesterite is confirmed by its typical peaks for all the different germanium–tin concentrations examined. 27 − 29 In particular, as described by Garcia-Llamas and coworkers in their accurate Raman study of germanium-substituted CZTS with different compositions, it is possible to appreciate the main peak split ( Figure 3 b), generated by the coexistence of Sn and Ge atoms into the crystal structure, when the Ge/Sn ratio reaches 70:30. 27 , 30 , 31 After that ratio, the doublet reunifies in a sole signal shifted to higher wavenumbers, as demonstrated also by the convolution of the main peak shown in Figure 3 c. Finally, the characteristic peaks of other known detrimental phases are not detectable in the spectra.…”

Section: Results and Discussionmentioning

confidence: 87%

Band-Gap Tuning Induced by Germanium Introduction in Solution-Processed Kesterite Thin Films

et al. 2022

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In the last few decades, the attention of scientific community has been driven toward the research on renewable energies. In particular, the photovoltaic (PV) thin-film technology has been widely explored to provide suitable candidates as top cells for tandem architectures, with the purpose of enhancing current PV efficiencies. One of the most studied absorbers, made of earth-abundant elements, is kesterite Cu 2 ZnSnS 4 (CZTS), showing a high absorption coefficient and a band gap around 1.4–1.5 eV. In particular, thanks to the ease of band-gap tuning by partial/total substitution of one or more of its elements, the high-band-gap kesterite derivatives have drawn a lot of attention aiming to find the perfect partner as a top absorber to couple with silicon in tandem solar cells (especially in a four-terminal architecture). In this work, we report the effects of the substitution of tin with different amounts of germanium in CZTS-based solar cells produced with an extremely simple sol–gel process, demonstrating how it is possible to fine-tune the band gap of the absorber and change its chemical–physical properties in this way. The precursor solution was directly drop-cast onto the substrate and spread with the aid of a film applicator, followed by a few minutes of gelation and annealing in an inert atmosphere. The desired crystalline phase was obtained without the aid of external sulfur sources as the precursor solution contained thiourea as well as metal acetates responsible for the in situ coordination and thus the correct networking of the metal centers. The addition of KCl in dopant amounts to the precursor solution allowed the formation of well-grown compact grains and enhanced the material quality. The materials obtained with the optimized procedure were characterized in depth through different techniques, and they showed very good properties in terms of purity, compactness, and grain size. Moreover, solar-cell prototypes were produced and measured, exhibiting poor charge extraction due to heavy back-contact sulfurization as studied in depth and experimentally demonstrated through Kelvin probe force microscopy.

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Section: Results and Discussionmentioning

confidence: 87%

Band-Gap Tuning Induced by Germanium Introduction in Solution-Processed Kesterite Thin Films

et al. 2022

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“…In literature, some reports can be found claiming kesterite as the crystal structure for Cu 2 MnSnS 4 . However, most studies assume that Cu 2 MnSnS 4 attains the stannite crystal structure based on results from neutron diffraction, where the stannite symmetry group

I \overset{4}{true} 2 m

yields a slightly better fit to the neutron diffraction data compared to the kesterite symmetry group

I \overset{4}{true}

.…”

Section: Resultsmentioning

confidence: 99%

Structural and Electronic Properties of Cu₂MnSnS₄ from Experiment and First‐Principles Calculations

Rudisch

Espinosa-García

Osório-Guillén

et al. 2019

Physica Status Solidi (b)

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Cu 2 MnSnS 4 shares several promising properties with the widely investigated Cu 2 ZnSnS 4 for photovoltaic applications such as containing only earth abundant and non-toxic elements, and suitable absorption characteristics for absorber materials. Thin film Cu 2 MnSnS 4 samples with various cation compositions are co-sputtered reactively followed by a high temperature anneal. Formation of Cu 2 MnSnS 4 and co-existence of several secondary phases is verified by XRD and Raman. Our investigation of the crystal structure based on first-principles DFT confirms that stannite crystal structure is preferred over kesterite, although, further verification considering cation disorder is needed. The direct band gap of Cu 2 MnSnS 4 is calculated as 1.52 eV (1.62 eV) for stannite (kesterite), which coincides with the range of the measured band gaps from spectrophotometry of 1.42-1.59 eV. After further annealing treatments below 240 C, the absorption shows reversible changes: the band gap blue-shifts and the Urbach tail energy is reduced. It is concluded that, just like Cu 2 ZnSnS 4 , disorder also occurs in Cu 2 MnSnS 4 . The implications of our findings are discussed and related to the current understanding of cation disorder in Cu 2 ZnSnS 4 and related compounds. Furthermore, for the first time first-principles DFT investigations are presented for the thiospinel Cu 2 MnSn 3 S 8 which is observed experimentally as a secondary phase in Sn-rich Cu 2 MnSnS 4 thin films.

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“…As mentioned above, Mn provides relevant abundance to annual production ratio, therefore p-type Cu 2 MnSnS 4 (CMTS) is also a good candidate as cheap chalcogenide PV absorber layer. CMTS was investigated above all as single crystal (Podsiadlo et al, 2015) or nanocrystal (Cui et al, 2012; Liang et al, 2012) for the diluted magnetic semiconductor characteristic, while, in the last few years, some papers reported on CMTS thin films for PV applications (Chen et al, 2015a,b, 2016a; Wang et al, 2015; Prabhakar et al, 2016; Le Donne et al, 2017; Marchionna et al, 2017; Yu et al, 2017). Wang et al (2015) obtained stannite CMTS thin films by sulfurization of different precursor (Cu,Sn)S/MnS and (Cu,Sn,Mn)S films, all deposited on glass by chemical methods.…”

Section: Emerging Earth-abundant Chalcogenide Pv Absorbersmentioning

confidence: 99%

New Earth-Abundant Thin Film Solar Cells Based on Chalcogenides

2019

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At the end of 2017 roughly 1.8% of the worldwide electricity came from solar photovoltaics (PV), which is foreseen to have a key role in all major future energy scenarios with an installed capacity around 5 TW by 2050. Despite silicon solar cells currently rule the PV market, the extremely more versatile thin film-based devices (mainly Cu(In,Ga)Se 2 and CdTe ones) have almost matched them in performance and present room for improvement. The low availability of some elements in the present commercially available PV technologies and the recent strong fall of silicon module price below 1 $/W p focused the attention of the scientific community on cheap earth-abundant materials. In this framework, thin film solar cells based on Cu 2 ZnSnS 4 (CZTS) and the related sulfur selenium alloy Cu 2 ZnSn(S,Se) 4 (CZTSSe) were strongly investigated in the last 10 years. More recently, chalcogenide PV absorbers potentially able to face TW range applications better than CZTS and CZTSSe due to the higher abundance of their constituting elements are getting considerable attention. They are based on both MY 2 (where M = Fe, Cu, Sn and Y = S and/or Se) and Cu 2 XSnY 4 (where X = Fe, Mn, Ni, Ba, Co, Cd and Y = S and/or Se) chalcogenides. In this work, an extensive review of emerging earth-abundant thin film solar cells based on both MY 2 and Cu 2 XSnY 4 species is given, along with some considerations on the abundance and annual production of their constituting elements.

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Synthesis of magnetic doped kesterite single crystals

Cited by 17 publications

References 14 publications

Band-Gap Tuning Induced by Germanium Introduction in Solution-Processed Kesterite Thin Films

Band-Gap Tuning Induced by Germanium Introduction in Solution-Processed Kesterite Thin Films

Structural and Electronic Properties of Cu₂MnSnS₄ from Experiment and First‐Principles Calculations

New Earth-Abundant Thin Film Solar Cells Based on Chalcogenides

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Synthesis of magnetic doped kesterite single crystals

Cited by 17 publications

References 14 publications

Band-Gap Tuning Induced by Germanium Introduction in Solution-Processed Kesterite Thin Films

Band-Gap Tuning Induced by Germanium Introduction in Solution-Processed Kesterite Thin Films

Structural and Electronic Properties of Cu2MnSnS4 from Experiment and First‐Principles Calculations

New Earth-Abundant Thin Film Solar Cells Based on Chalcogenides

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Product

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Structural and Electronic Properties of Cu₂MnSnS₄ from Experiment and First‐Principles Calculations