Influence of reaction conditions on the properties of solution-processed Cu<sub>2</sub>ZnSnS<sub>4</sub> nanocrystals

Qu, Yongtao; Zoppi, Guillaume; Miles, Robert; Beattie, Neil

doi:10.1088/2053-1591/1/4/045040

Cited by 25 publications

(26 citation statements)

References 31 publications

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“…The quenched sample exhibits three weak diffraction peaks marked by asterisks shown in Figure (a) in addition to the primary peaks. These belong to wurtzite CZTS co‐existing in the nanoparticle ink because metastable wurtzite CZTS has insufficient time to complete the transformation to the more stable kesterite phase when the reaction temperature cools rapidly . XRD patterns of the hot and prolonged samples have a similar pattern to kesterite CZTS with no obvious secondary phases observed.…”

Section: Resultsmentioning

confidence: 99%

“…CZTS nanoparticles were fabricated using a hot‐injection method described previously . Four types of nanoparticle inks were prepared by varying key reaction parameters: temperature, time or cooling mode.…”

Section: Methodsmentioning

confidence: 99%

“…The doping levels are of fundamental importance as they determine the optoelectronic behavior of devices. We have recently developed an experimental procedure to tune the properties of CZTS nanoparticles via the chemical reaction conditions . Wurtzite CZTS was formed at lower temperature whereas Cu 2 SnS 3 (CTS) was present in the nanoparticles at higher temperature.…”

Section: Introductionmentioning

confidence: 99%

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The role of nanoparticle inks in determining the performance of solution processed Cu₂ZnSn(S,Se)₄ thin film solar cells

Zoppi

Beattie

2016

Progress in Photovoltaics

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Cu 2 ZnSnS 4 (CZTS) nanoparticle inks synthesized by the injection of metal precursors into a hot surfactant offer an attractive route to the fabrication of Earth-abundant Cu 2 ZnSn(S,Se) 4 (CZTSSe) thin film photovoltaic absorber layers. In this work it is shown that the chemical reaction conditions used to produce CZTS nanoparticle inks have a fundamental influence on the performance of thin film solar cells made by converting the nanoparticles to large CZTSSe grains in a selenium rich atmosphere and subsequent cell completion. The reaction time, temperature and cooling rate of the nanoparticle fabrication process are found to affect doping level, secondary phases and crystal structure respectively. Specifically, prolonging the reaction offers a new route to increase the concentration of acceptor levels in CZTSSe photovoltaic absorbers and results in higher device efficiency through an increase in the open circuit voltage and a reduction in parasitic resistance. Quenching the reaction by rapid cooling introduces a wurtzite crystal structure in the nanoparticles which significantly degrades the device performance, while elevating the reaction temperature of the nanoparticle synthesis introduces a secondary phase Cu 2 SnS 3 in the nanoparticles and results in the highest cell efficiency of 6.26%. This is correlated with increased doping in the CZTSSe absorber and the results demonstrate a route to controlling this parameter.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The role of nanoparticle inks in determining the performance of solution processed Cu₂ZnSn(S,Se)₄ thin film solar cells

Zoppi

Beattie

2016

Progress in Photovoltaics

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“…CZTSSe films were prepared from CZTS nanoparticle inks. Firstly, CZTS nanoparticles were fabricated using a well-established hot-injection method following our previously published procedure 31,32 . The resulting nanoparticle inks were then deposited on molybdenum substrates via spin coating to form the CZTS precursor thin film with a thickness of ∼1 µm.…”

Section: Methodsmentioning

confidence: 99%

Defect limitations in Cu2ZnSn(S, Se)4 solar cells utilizing an In2S3 buffer layer

Campbell

Gibbon

et al. 2020

Journal of Applied Physics

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Alternative n-type buffer layer such as In 2 S 3 have been proposed as Cd-free alternative in kesterite Cu 2 ZnSn(S,Se) 4 (CZTSSe) solar cells. In this study, optical and electronic characterisation techniques together with device analysis and simulation were used to assess nanoparticle-based CZTSSe absorbers and solar cells with CdS and In 2 S 3 buffers. Photoluminescence spectroscopy indicated CZTSSe absorbers with In 2 S 3 buffer had a lower density of detrimental non-radiative defects and a higher concentration of copper vacancies V Cu + , responsible for p-type conductivity in CZTSSe, in comparison to the absorber with CdS buffer. Capacitance-voltage (C-V) measurements revealed the In 2 S 3 buffer-based CZTSSe devices had a three times higher apparent doping density and a consequently narrower space charge region than devices with a CdS layer. This resulted in poorer collection of photo-generated charge carriers in the near-IR region despite a more favourable band alignment as determined by X-ray photoelectron and inverse photoelectron spectroscopy. The presence of interfacial defect states in In 2 S 3 devices as determined by C-V and biased quantum efficiency measurements are also responsible for the loss in open-circuit voltage compared with reference devices with CdS.

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“…Although there are many reports of CZTS nanocrystals synthesized by the hot-injection method, the inuence of the injection temperature on the nanocrystal nucleation and growth has not been extensively investigated so far. 19 Besides that, it is still unclear which size of the NCs is better suited for solar cells fabrication. Previously reported recipes based on this technique usually result in nanocrystals with an average size of 7-20 nm.…”

Section: Introductionmentioning

confidence: 99%

Metal acetate based synthesis of small-sized Cu₂ZnSnS₄ nanocrystals: effect of injection temperature and synthesis time

et al. 2017

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We report the colloidal synthesis of small-sized Cu 2 ZnSnS 4 (CZTS) nanocrystals (NCs) via a hot-injection method using zinc and tin acetates in combination with copper acetylacetonate as metal precursors. A systematic investigation of the influence of the injection temperature in the range from 190 C to 300 C on the size distribution, composition and phase purity of CZTS nanocrystals has been performed. It has been found that temperature plays the key role in changing of the metal sources reactivity and influences the final composition of the nanocrystals. The mechanism of nanocrystal formation has been investigated by Raman spectroscopy of aliquots of their solutions. It starts from the formation of a Cu 2Àx S phase as a core followed by the incorporation of Zn 2+ and Sn 4+ atoms into its structure regardless of injection temperature. † Electronic supplementary information (ESI) available: TEM image for the sample obtained with lower amount of oleylamine; TEM images of Cu 2Àx S, CTS, ZnS and Sn x S y nanocrystals obtained with same reaction conditions as CZTS nanocrystals; temperature dependence of Cu/Sn and Zn/Sn ratios of NCs synthesized with weight-in ratio of Zn/Sn ¼ 1.2; evolution of Raman signal of CTS nanocrystals with increasing of the growth time at 225 C; Raman spectrum of nanocrystals synthesized at different injection temperatures measured with UV excitation laser; absorption coefficient of CZTS nanocrystals in conjunction with model. See

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Influence of reaction conditions on the properties of solution-processed Cu₂ZnSnS₄ nanocrystals

Cited by 25 publications

References 31 publications

The role of nanoparticle inks in determining the performance of solution processed Cu₂ZnSn(S,Se)₄ thin film solar cells

The role of nanoparticle inks in determining the performance of solution processed Cu₂ZnSn(S,Se)₄ thin film solar cells

Defect limitations in Cu2ZnSn(S, Se)4 solar cells utilizing an In2S3 buffer layer

Metal acetate based synthesis of small-sized Cu₂ZnSnS₄ nanocrystals: effect of injection temperature and synthesis time

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Influence of reaction conditions on the properties of solution-processed Cu2ZnSnS4 nanocrystals

Cited by 25 publications

References 31 publications

The role of nanoparticle inks in determining the performance of solution processed Cu2ZnSn(S,Se)4 thin film solar cells

The role of nanoparticle inks in determining the performance of solution processed Cu2ZnSn(S,Se)4 thin film solar cells

Defect limitations in Cu2ZnSn(S, Se)4 solar cells utilizing an In2S3 buffer layer

Metal acetate based synthesis of small-sized Cu2ZnSnS4 nanocrystals: effect of injection temperature and synthesis time

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Resources

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Influence of reaction conditions on the properties of solution-processed Cu₂ZnSnS₄ nanocrystals

The role of nanoparticle inks in determining the performance of solution processed Cu₂ZnSn(S,Se)₄ thin film solar cells

The role of nanoparticle inks in determining the performance of solution processed Cu₂ZnSn(S,Se)₄ thin film solar cells

Metal acetate based synthesis of small-sized Cu₂ZnSnS₄ nanocrystals: effect of injection temperature and synthesis time