Phase equilibria in the Cu2S–ZnS–SnS2 system

Olekseyuk, I. D.; Dudchak, I.V.; Піскач, Л. В.

doi:10.1016/j.jallcom.2003.08.084

Cited by 326 publications

(192 citation statements)

References 9 publications

(13 reference statements)

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“…In the material system Cu-Zn-Sn-S the Sn-containing compounds can be tin sulfides, copper tin sulfides, or copper tin alloys. 23,24 The evolution of the Cu K␣ fluorescence during the heating experiment on the precursor Mo/SnS/CuS in Fig. 3 indicates that there is no loss of Cu from the films.…”

Section: Discussionmentioning

confidence: 95%

On the Sn loss from thin films of the material system Cu–Zn–Sn–S in high vacuum

Weber

Mainz

Schock

2010

Journal of Applied Physics

349

192

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In this paper the Sn loss from thin films of the material system Cu-Zn-Sn-S and the subsystems Cu-Sn-S and Sn-S in high vacuum is investigated. A combination of in situ x-ray diffractometry and x-ray fluorescence ͑XRF͒ at a synchrotron light source allowed identifying phases, which tend to decompose and evaporate a Sn-containing compound. On the basis of the XRF results a quantification of the Sn loss from the films during annealing experiments is presented. It can be shown that the evaporation rate from the different phases decreases according to the order SnS → Cu 2 SnS 3 → Cu 4 SnS 4 → Cu 2 ZnSnS 4 . The phase SnS is assigned as the evaporating compound. The influence of an additional inert gas component on the Sn loss and on the formation of Cu 2 ZnSnS 4 thin films is discussed.

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Section: Discussionmentioning

confidence: 95%

On the Sn loss from thin films of the material system Cu–Zn–Sn–S in high vacuum

Weber

Mainz

Schock

2010

Journal of Applied Physics

349

192

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“…This has led to a view that the amount of S incorporated into CZTS depends only on the amount of metallic elements, assuming sufficient S is available. 38 This is the assumption underlying the representation of the samples on the quasi-ternary phase diagram shown in Figure 2. It has been shown that for these CZTS polycrystals this assumption has limited validity.…”

Section: Resultsmentioning

confidence: 99%

“…A study of the quasi-ternary Cu 2 S-ZnS-SnS 2 system at 400 C has shown that, apart from the narrow region at the centre of the plot, there are always additional phases present alongside CZTS. 38 For regions which are Cu-poor, the secondary phases are expected to include Cu 2 ZnSn 3 S 8 and ZnS; regions which are Zn-poor may be expected to have CuSnS, Cu 2 ZnSn 3 S 8 , and Cu 2 S; regions which are Zn-rich may be expected to have ZnS. 39 Looking at the composition of the samples in Table I, as represented on the phase diagram in Figure 2, they may be placed into four broad groups: group (i) C1, C2, and C3-stoichiometric (noting that C1 and C2 have a S excess); group (ii) C4-Cu-poor, Zn-rich, Sn-rich; group (iii) C5, C6, and C7-Cu-poor, Zn-rich, Sn-poor; and group (iv) C8 Cu-rich, Zn-poor.…”

Section: Sample Preparation and Measurementsmentioning

confidence: 99%

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Halliday

Claridge

Goodman

et al. 2013

Journal of Applied Physics

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The growth of Cu2ZnSnS4 (CZTS) polycrystals from solid state reaction over a range of compositions, including the regions which produce the highest efficiency photovoltaic devices, is reported. X-ray measurements confirm the growth of crystalline CZTS. Temperature and intensity dependent photoluminescence (PL) measurements show an increase in the energy of the main CZTS luminescence peak with both increasing laser power and increasing temperature. Analysis of the PL peak positions and intensity behavior demonstrates that the results are consistent with the model of fluctuating potentials. This confirms that the polycrystals are heavily doped with the presence of a large concentration of intrinsic defects. The behavior of the main luminescence feature is shown to be qualitatively similar over a broad range of compositions although the nature and amount of secondary phases vary significantly. The implications for thin-film photovoltaic devices are discussed.

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“…4 It was shown theoretically and experimentally that there is only a narrow existence region of single phase kesterite in the equilibrium phase diagram which supports the formation of secondary phases. 5,6 Zinc sulfide (ZnS) is the most stable binary phase with a high negative enthalpy of formation of À205 kJ mol À1 . 7 Therefore, its formation can be expected in nonequilibrium processes such as physical vapor deposition (PVD) or rapid thermal annealing (RTA) of precursor layers.…”

mentioning

confidence: 99%

Determination of secondary phases in kesterite Cu2ZnSnS4 thin films by x-ray absorption near edge structure analysis

Just

Lützenkirchen‐Hecht

Frahm

et al. 2011

Applied Physics Letters

112

110

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Secondary phases in Cu2ZnSnS4 (CZTS) are investigated by x-ray absorption spectroscopy. Evaluating the x-ray absorption near edge structure at the sulfur K-edge, we show that secondary phases exhibit sufficiently distinct features to allow their quantitative determination with high accuracy. We are able to quantify the ZnS fraction with an absolute accuracy of ±3%, by applying linear combination analysis using reference spectra. We find that even in CZTS thin films with [Sn]/[Zn] ≈ 1, a significant amount of ZnS can be present. A strong correlation of the ZnS-content with the degradation of the electrical performance of solar cells is observed.

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Phase equilibria in the Cu2S–ZnS–SnS2 system

Cited by 326 publications

References 9 publications

On the Sn loss from thin films of the material system Cu–Zn–Sn–S in high vacuum

On the Sn loss from thin films of the material system Cu–Zn–Sn–S in high vacuum

Luminescence of Cu2ZnSnS4 polycrystals described by the fluctuating potential model

Determination of secondary phases in kesterite Cu2ZnSnS4 thin films by x-ray absorption near edge structure analysis

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