Preparation of Cu2ZnSnS4 thin films by sulfurization of stacked metallic layers

Araki, Hideki; Mikaduki, Aya; Kubo, Yuki; Sato, Tatsuhiro; Jimbo, Kazuo; Maw, Win Shwe; Katagiri, Hironori; Yamazaki, Makoto; Oishi, Keiji; Takeuchi, Akiko

doi:10.1016/j.tsf.2008.09.058

Cited by 206 publications

(109 citation statements)

References 7 publications

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“…Several methods have been used in the fabrication of CZTS thin film absorber layers, such as atomic beam sputtering [5], e-beam evaporation [6], thermal evaporation [7], magnetron sputtering [8][9][10][11], electrodeposition [12,13], spray pyrolysis deposition [14,15], pulsed laser deposition [16], etc. Most of these techniques were carried out using rigid substrates such as bilayer molybdenum (Mo) coated soda lime glass (SLG).…”

Section: Introductionmentioning

confidence: 99%

Growth of Cu2ZnSnS4 absorber layer on flexible metallic substrates for thin film solar cell applications

et al. 2015

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In this work, Cu 2 ZnSnS 4 (CZTS) absorber layers were fabricated using a two-stage process. Sequentially deposited Cu-Zn-Sn thin film layers on metallic foils were annealed in an Ar + S 2(g) atmosphere. We aimed to investigate the role of flexible titanium and molybdenum foil substrates in the growth mechanism of CZTS thin films. The Raman spectra and X-ray photoelectron spectroscopy analyses of the sulfurized thin films revealed that, except for the presence of Sn-based secondary phases, nearly pure CZTS thin films were obtained. Additionally, the intense and sharp X-ray diffraction peak from the (112) plane provided evidence of good crystallinity. Electron dispersive spectroscopy analysis indicated sufficient sulfur content but poor Zn atomic weight percentage in the films. Absorption and band-gap energy analyses were carried out to confirm the suitability of CZTS thin films as the absorber layer in solar cell applications. Hall effect measurements showed the p-type semiconductor behavior of the CZTS samples. Moreover, the back contact behavior of these metallic flexible substrates was investigated and compared. We detected formation of cracks in the CZTS layer on the molybdenum foils, which indicates the incompatibility of molybdenum's thermal expansion coefficient with the CZTS structure. We demonstrated the application of the magnetron sputtering technique for the fabrication of CZTS thin films on titanium foils having lightweight, flexible properties and suitable for roll-to-roll manufacturing for high throughput fabrication. Titanium foils are also cost competitive compared to molybdenum foils.

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Section: Introductionmentioning

confidence: 99%

Growth of Cu2ZnSnS4 absorber layer on flexible metallic substrates for thin film solar cell applications

et al. 2015

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“…In general, CZTS is formed by two independent processes of precursor formation and post thermal treatment. [7][8][9][10][11][12][13] These two processes are performed using two sets of equipment. A formation with a single set of equipment is very advantageous to achieve a low-cost manufacturing.…”

Section: Related Contentmentioning

confidence: 99%

Suppression of Cu₂₋ _x S formation in Cu₂ZnSnS₄ by tin incorporation using molecular beam epitaxy system

Nishida¹,

Murayama²,

Takeuchi³

et al. 2018

Jpn. J. Appl. Phys.

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A Cu 2 ZnSnS 4 (CZTS) thin film was fabricated by co-evaporation of its constituents (Cu, Zn, Sn, and S) and subsequent annealing in S-flux using molecular beam epitaxy system. Two Sn crucible temperatures were considered, 1,010 and 1,020°C. The Raman spectrum of the sample exhibited the main peaks at 336 cm %1 attributed to CZTS and 472 cm %1 attributed to Cu 2%x S. The annealing temperature that yielded CZTS with a lower amount of Cu 2%x S was in the range of 380-420°C. The peaks of the Cu 2%x S phase were not observed in the sample fabricated at the Sn crucible temperature of 1,020°C and annealed at 420°C. The suppression of the Cu segregation near the surface, yielded a suppression of the Cu 2%x S phase, as revealed by the Raman spectra. The increase of the Sn ratio, achieved by increasing the crucible temperature, contributed to the suppression of the Cu 2%x S phase and improvement of the CZTS crystalline quality.

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“…Despite these limitations, reasonably successful film deposition and device fabrication have been demonstrated for both vacuum and solution-based deposition approaches. Several groups have reported the fabrication of CZTS thin films using a variety of methods such as sulfurization [8], electrodeposition [9,10] RF sputtering [11] and co-evaporation [2]. Kim et al achieved a 12,7% efficient Cu 2 ZnSn(Se,S) 4 device [12] fabricated from CZTSSe films prepared using a hydrazine-based pure solution approach and employing an In 2 S 3 /CdS double-emitter on CZTSSe absorbers upon annealing under optimized conditions.…”

Section: Introductionmentioning

confidence: 99%

Fabrication of solar cells based on Cu₂ZnSnS₄prepared from Cu₂SnS₃synthesized using a novel chemical procedure

et al. 2016

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Solar cells based on kesterite-type Cu2ZnSnS4 (CZTS) thin films were fabricated using a chemical route to prepare the CZTS films, consisting in sequential deposition of Cu2SnS3 (CTS) and ZnS thin films followed by annealing at 550 • C in nitrogen atmosphere. The CTS compound was prepared in a one-step process using a novel chemical procedure consisting of simultaneous precipitation of Cu2S and SnS2 performed by diffusion membranes assisted CBD (chemical bath deposition) technique. Diffusion membranes were used to optimize the kinetic growth through a moderate control of release of metal ions into the work solution. As the conditions for the formation in one step of the Cu2SnS3 compound have not yet been reported in literature, special emphasis was put on finding the parameters that allow growing the Cu2SnS3 thin films by simultaneous precipitation of Cu2S and SnS2. For that, we propose a methodology that includes numerical solution of the equilibrium equations that were established through a study of the chemical equilibrium of the system SnCl2, Na3C6H5O7·2H2O, CuCl2 and Na2S2O3·5H2O. The formation of thin films of CTS and CZTS free of secondary phases grown with a stoichiometry close to that corresponding to the Cu2SnS3 and Cu2ZnSnS4 phases, was verified through measurements of X-ray diffraction (XRD) and Raman spectroscopy. Solar cell with an efficiency of 4.2%, short circuit current of 16.2 mA/cm 2 and open-circuit voltage of 0.49 V was obtained.

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Preparation of Cu2ZnSnS4 thin films by sulfurization of stacked metallic layers

Cited by 206 publications

References 7 publications

Growth of Cu2ZnSnS4 absorber layer on flexible metallic substrates for thin film solar cell applications

Growth of Cu2ZnSnS4 absorber layer on flexible metallic substrates for thin film solar cell applications

Suppression of Cu₂₋ _x S formation in Cu₂ZnSnS₄ by tin incorporation using molecular beam epitaxy system

Fabrication of solar cells based on Cu₂ZnSnS₄prepared from Cu₂SnS₃synthesized using a novel chemical procedure

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Preparation of Cu2ZnSnS4 thin films by sulfurization of stacked metallic layers

Cited by 206 publications

References 7 publications

Growth of Cu2ZnSnS4 absorber layer on flexible metallic substrates for thin film solar cell applications

Growth of Cu2ZnSnS4 absorber layer on flexible metallic substrates for thin film solar cell applications

Suppression of Cu2− x S formation in Cu2ZnSnS4 by tin incorporation using molecular beam epitaxy system

Fabrication of solar cells based on Cu2ZnSnS4prepared from Cu2SnS3synthesized using a novel chemical procedure

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Suppression of Cu₂₋ _x S formation in Cu₂ZnSnS₄ by tin incorporation using molecular beam epitaxy system

Fabrication of solar cells based on Cu₂ZnSnS₄prepared from Cu₂SnS₃synthesized using a novel chemical procedure