Improved Cu(In,Ga)(S,Se)2 thin film solar cells by surface sulfurization

Nakada, Tokio; Ohbo, Hiroki; Watanabe, Takayuki; Nakazawa, Hikaru; Matsui, Masahiro; Kunioka, Akio

doi:10.1016/s0927-0248(97)00054-8

Cited by 100 publications

(65 citation statements)

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“…Although Se depletion of CIGSe surfaces due to vacuum annealing has not been reported for temperatures below 600°C, 15 temperatures in the range of the used substrate temperature for our In 2 S 3 deposition are applied to re-evaporate Se caps from CIGSe. 16 Furthermore, similar S/Se substitution processes have been observed upon CIGSe exposure to H 2 S atmosphere at high temperatures 17 and after low-temperature chemical bath deposition of CdS. 18 Note that the calculated layer thicknesses for the 1/64-and 1/32-In 2 S 3 /CIGSe samples are-within the error barsidentical.…”

Section: ͑͒supporting

confidence: 57%

Nondestructive depth-resolved spectroscopic investigation of the heavily intermixed In2S3/Cu(In,Ga)Se2 interface

Bär

Barreau

Couzinié-Devy

et al. 2010

Applied Physics Letters

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͑͒The chemical structure of the interface between a nominal In 2 S 3 buffer and a Cu͑In, Ga͒Se 2 ͑CIGSe͒ thin-film solar cell absorber was investigated by soft x-ray photoelectron and emission spectroscopy. We find a heavily intermixed, complex interface structure, in which Cu diffuses into ͑and Na through͒ the buffer layer, while the CIGSe absorber surface/interface region is partially sulfurized. Based on our spectroscopic analysis, a comprehensive picture of the chemical interface structure is proposed. ͓͔ Cu͑In, Ga͒Se 2 ͑CIGSe͒ thin-film solar cells with an n + -ZnO/i-ZnO/CdS/CIGSe/Mo/glass device structure have reached efficiencies of 20%.1 To replace the CdS layer by a nontoxic, more transparent buffer, and the conventionally used chemical bath deposition by a technique allowing inline processing, In 2 S 3 layers have been deposited by physical vapor deposition, 2 sputtering, 3 atomic layer deposition, 4 and spray ion layer gas reaction. 5The In 2 S 3 /CIGSe interface has been previously investigated by different destructive depth-profiling techniques, 2,6 high-resolution transmission electron microscopy and energy dispersive x-ray analysis, 7 and x-ray photoelectron spectroscopy ͑XPS͒. 4,8,9 At ͑post-͒deposition annealing temperatures necessary for high device efficiencies ͑200-250°C͒, a pronounced diffusion of Cu and Na from the CIGSe/Mo/glass substrate into the nominal In 2 S 3 buffer layer was found in these studies. However, a complete picture of the chemical interface structure is still missing. In this paper, we will report on the characterization of the In 2 S 3 /CIGSe interface by a combination of nondestructive techniques ͓XPS and soft x-ray emission spectroscopy ͑XES͔͒, deliberately varying the probing depth. Our measurements result in a depth-resolved picture of the interface in unprecedented detail.In 2 S 3 /CIGSe structures were prepared at IMN on Mo/ glass substrates. 10 The absorber layers were dipped in NH 3 solution ͑1 M, room temperature, 1 min͒ prior to the In 2 S 3 buffer layer deposition by thermal coevaporation of elemental indium and sulfur at 200°C substrate temperature. To vary the In 2 S 3 thickness, different deposition times were used. The standard 80 nm buffer used in solar cells is prepared in 10 min ͑called "1/1" in the following͒. For reference, an In 2 S 3 layer, different In 2 S 3 : Cu standards, and a CuInS 2 ͑CIS͒ absorber 11 were deposited on Mo/glass substrates. After preparation, all samples were sealed in polyethylene bags filled with dry N 2 and desiccant for transport. At UNLV the samples were transferred into the analysis chamber ͑base pressure Ͻ5 ϫ 10 −10 mbar͒ without air exposure. XPS was performed using Mg K ␣ and Al K ␣ excitation and a Specs PHOIBOS 150 MCD electron analyzer ͑calibrated according to Ref. 12͒. Subsequently, XES was performed at the ALS using the soft x-ray fluorescence endstation of Beamline 8.0.XPS survey spectra ͑not shown͒ show all expected absorber photoemission lines, Na-related peaks, and only minor spectral contributions of C-and O-co...

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Section: ͑͒supporting

confidence: 57%

Nondestructive depth-resolved spectroscopic investigation of the heavily intermixed In2S3/Cu(In,Ga)Se2 interface

Bär

Barreau

Couzinié-Devy

et al. 2010

Applied Physics Letters

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“…This clearly differs from the results of the surface sulfurization of a CIGS thin film. 24 Specifically, a 30 min thermal treatment of a CIGS thin film at 550…”

Section: Resultsmentioning

confidence: 99%

The Effect of Sulfurization Temperature on CuIn(Se,S)₂Solar Cells Synthesized by Electrodeposition

Kim

Kwon

Lee

et al. 2014

J. Electrochem. Soc.

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The properties of thin film solar cells based on electrodeposited CuIn(Se,S)2 were investigated. The proposed solar cell fabrication method involves a single-step CuInSe2 thin film electrodeposition followed by sulfurization in a tube furnace to form a CuIn(Se,S)2 quaternary phase. A sulfurization temperature of 450–550°C significantly affected the performance of the CuIn(Se,S)2 thin film solar cell in addition to its composition, grain size and bandgap. Sulfur(S) substituted for selenium(Se) at increasing rates with higher sulfurization temperature, which resulted in an increase in overall bandgap of the CuIn(Se,S)2 thin film. The highest conversion efficiency of 3.12% under air mass (AM) 1.5 illumination was obtained from the 500°C-sulfurized solar cell. The highest External Quantum Efficiency (EQE) was also observed at the sulfurization temperature of 500°C.

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“…It has been demonstrated that sulfurization of coevaporated CIGSe in an H 2 S atmosphere can result in formation of a S/Se graded CIGSSe and improved device performance from 15.6 to 17 % as a consequence [4,5]. It has also been shown that an improvement from 14.5% to 16% efficiency can be obtained by annealing with elemental sulfur [6].…”

Section: Introductionmentioning

confidence: 99%

Sulfurization of Co-Evaporated Cu(In,Ga)Se₂ as a Postdeposition Treatment

Larsen

Keller

Lundberg

et al. 2018

IEEE J. Photovoltaics

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Improved Cu(In,Ga)(S,Se)2 thin film solar cells by surface sulfurization

Cited by 100 publications

References 1 publication

Nondestructive depth-resolved spectroscopic investigation of the heavily intermixed In2S3/Cu(In,Ga)Se2 interface

Nondestructive depth-resolved spectroscopic investigation of the heavily intermixed In2S3/Cu(In,Ga)Se2 interface

The Effect of Sulfurization Temperature on CuIn(Se,S)₂Solar Cells Synthesized by Electrodeposition

Sulfurization of Co-Evaporated Cu(In,Ga)Se₂ as a Postdeposition Treatment

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Improved Cu(In,Ga)(S,Se)2 thin film solar cells by surface sulfurization

Cited by 100 publications

References 1 publication

Nondestructive depth-resolved spectroscopic investigation of the heavily intermixed In2S3/Cu(In,Ga)Se2 interface

Nondestructive depth-resolved spectroscopic investigation of the heavily intermixed In2S3/Cu(In,Ga)Se2 interface

The Effect of Sulfurization Temperature on CuIn(Se,S)2Solar Cells Synthesized by Electrodeposition

Sulfurization of Co-Evaporated Cu(In,Ga)Se2 as a Postdeposition Treatment

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The Effect of Sulfurization Temperature on CuIn(Se,S)₂Solar Cells Synthesized by Electrodeposition

Sulfurization of Co-Evaporated Cu(In,Ga)Se₂ as a Postdeposition Treatment