• Korean Journal of Materials Research
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• v.23 no.3
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• pp.183-189
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• 2013

$Cu_2ZnSn(S,Se)_4$ material is receiving an increased amount of attention for solar cell applications as an absorber layer because it consists of inexpensive and abundant materials (Zn and Sn) instead of the expensive and rare materials (In and Ga) in $Cu(In,Ga)Se_2$ solar cells. We were able to achieve a cell conversion efficiency to 4.7% by the selenization of a stacked metal precursor with the Cu/(Zn + Sn)/Mo/glass structure. However, the selenization of the metal precursor results in large voids at the absorber/Mo interface because metals diffuse out through the top CZTSe layer. To avoid the voids at the absorber/Mo interface, binary selenide compounds of ZnSe and $SnSe_2$ were employed as a precursor instead of Zn and Sn metals. It was found that the precursor with Cu/$SnSe_2$/ZnSe stack provided a uniform film with larger grains compared to that with $Cu_2Se/SnSe_2$/ZnSe stack. Also, voids were not observed at the $Cu_2ZnSnSe_4$/Mo interface. A severe loss of Sn was observed after a high-temperature annealing process, suggesting that selenization in this case should be performed in a closed system with a uniform temperature in a $SnSe_2$ environment. However, in the experiments, Cu top-layer stack had more of an effect on reducing Sn loss compared to $Cu_2Se$ top-layer stack.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.134-137
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• 2009

Commercially available elemental powders of Cu, Zn, Sn and Se were employed for crystallizing a stannite-type $Cu_2ZnSnSe_4$ compound by means of solid state reaction. $Cu_2ZnSnSe_4$ reaction chemistry was also modeled based on differential-thermal analysis and X-ray powder diffraction results. It was observed that Se tends to react preferably with Cu to form CuSe and $CuSe_2$ phases at low reaction temperature. The formation of $Cu_5Zn_8$ intermetallic phase was found to be the intermediate reaction path for the binary ZnSe formation. A solid state reaction at $320^{\circ}C$ reacted elemental powderst obinary selenides of CuSe, ZnSe and SnSe completely. The crystallization of $Cu_2ZnSnSe_4$ was was detected to begin at $300^{\circ}C$ and its weight fraction increased with an increase of reaction temperature, which most probably formed from the reaction between $Cu_2SnSe_3$ and ZnSe.

• New & Renewable Energy
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• v.3 no.4
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• pp.54-62
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• 2007

In this paper, we report the research highlight on the preparation and characterization of Indium-free $Cu_2ZnSnSe_4$ and Indium-reduced $CulnZnSe_2$ thin films in order to seek the viability of these absorber materials to be applied in thin film solar cells. The films of $Cu_2ZnSnSe_4\;and\;CulnZnSe_2$ were prepared using mixed binary chalcogenides powders. It was observed that Cu concentration was a function of substrate temperature as well as CuSe mole ratio in the target. Under an optimized condition, $Cu_2ZnSnSe_4\;and\;CulnZnSe_2$ thin films grew with strong [112]. [220/204] and [312/116] reflections. Both $Cu_2ZnSnSe_4\;and\;CulnZnSe_2$ films were found to exhibit a high absorption coefficient of $104^4cm^{-1}\;Cu_2ZnSnSe_4$ film showed a band gap of 1.5eV which closes to the optimum band gap of an ideal solar absorber for a solar cell. On the other side, an increase of optical band gap from 1.0 to 1.25eV was found to be proportional with an increase of Zn concentration in the $CulnZnSe_2$ film. All films in this study revealed a p-type semiconductor characteristic.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2331-2334
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• 2014

$Cu_2SnSe_3$ (CTSe) and $Cu_2ZnSnSe_4$ (CZTSe) nanoparticles were synthesized by sonochemical reactions under multibubble sonoluminescence (MBSL) conditions. First, $Cu_2SnSe_3$ nanoparticles were synthesized by the sonochemical method with an 85% yield, using CuCl, $SnCl_2$, and Se. Second, ZnSe was coated on the CTSe nanoparticles by the same method. Then, they were transformed into CZTSe nanoparticles of 5-7 nm diameters by heating them at $500^{\circ}C$ for 1 h. The ratios between Zn and Sn could be controlled from 1 to 3.75 by adjusting the relative concentrations of CTSe and ZnSe. With relatively lower Zn:Sn ratios (0.75-1.26), there are mostly CZTSe nanoparticles but they are believed to include very small amount of CTS and ZnSe particles. The prepared nanoparticles show different band gaps from 1.36 to 1.47 eV depending on the Zn/Sn ratios. In this sonochemical method without using any toxic or high temperature solvents, the specific stoichiometric element Zn/Sn ratios in CZTSe were controllable on demand and their experimental results were always reproducible in separate syntheses. The CZTSe nanoparticles were investigated by using X-ray diffractometer, a UV-Vis spectrophotometer, scanning electron microscope, Raman spectroscopy, and a high resolution-transmission electron microscope.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.270-273
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• 2007

In this report, Indium-free and Indium-reduced thin film materials for solar absorber were studied in order to search alternative materials for thin film solar cell. The films of $Cu_2ZnSnSe_4$ and $Cu_2ZnSnSe_2$ were deposited using mixed binary chalcogenides powders. From the film bulk analysis result, it is observed that Cu concentration is a function of substrate temperature as well as CuSe mole ratio in the target. Under optimized conditions, $Cu_2ZnSnSe_4$ and $Cu_2ZnSnSe_2$ thin films grow with strong (112), (220/204) and (312/116) reflections. Films are found to exhibit a high absorption coefficient of $10^4$ $cm^{-1}$. $Cu_2ZnSnSe_4$ film shows a 1.5 eV band gap. On the other side, an increasing of optical band gap from 1.0 eV to 1.25 eV ($CuInSnSe_2$) is found to be proportional with an increasing of Zn concentration. All films have a p-type semiconductor characteristic with a carrier concentration in the order of $10^{14}$ $cm^{-3}$, a mobility about $10^1$ $cm^{2{\cdot}-1.}S^{-1}$ and a resistivity at the range of $10^2-10^6$ ${\Omega}{\cdot}m$.

• Current Photovoltaic Research
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• v.10 no.2
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• pp.39-48
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• 2022

A Se-containing Cu/SnSe₂/ZnSe precursor was employed to introduce S to the precursor to form Cu₂ZnSn(S,Se)₄ (CZTSSe) film. The morphology of CZTSSe films strongly varied with two different pre-annealing environments: S and N₂. The CZTSSe film with S pre-annealing showed a dense morphology with a smooth surface, while that with N₂ pre-annealing showed a porous film with a plate-shaped grains on the surface. CuS and Cu₂Sn(S,Se)₃ phases formed during the S pre-annealing stage, while SnSe and Cu₂SnSe₃ phases formed during the N₂ pre-annealing stage. The SnSe phase formed during N₂ pre-annealing generated SnS₂ phase that had plate shape and severely aggravated the morphology of CZTSSe film. The power conversion efficiency of the CZTSSe solar cell with S pre-annealing was low (1.9%) due to existence of Zn(S.Se) layer between CZTSSe and Mo substrate. The results indicated that S pre-annealing of the precursor was a promising method to achieve a good morphology for large area application.

• Current Photovoltaic Research
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• v.3 no.3
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• pp.97-100
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• 2015

The kesterite $Cu_2ZnSnSe_4$ (CZTSe) thin film solar cells were synthesized by selenization of sputtered Cu/Sn/Zn metallic precursors on Mo coated soda lime glass substrate in Ar atmosphere. Cu/Sn/Zn metallic precursors were deposited by DC magnetron sputtering process with 30 W power at room temperature. As-deposited metallic precursors were placed in a graphite box with Se pellets and selenized using rapid thermal processing furnace at various temperature ($480^{\circ}C{\sim}560^{\circ}C$) without using a toxic $H_2Se$ gas. Effects of Selenization temperature on the morphological, crystallinity, electrical properties and cell efficiency were investigated by field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD), J-V measurement system and solar simulator. Further details about effects of selenization temperature on CZTSe thin films will be discussed.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.85.2-85.2
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• 2010

$Cu_2ZnSnSe_4$ (CZTSe) is one of candidate to alternate $Cu(In,Ga)Se_2$ as solar absorber material for solar cell. The expensive elements of In and Ga are replaced by Zn and Sn, respectively to lower the material cost. In this study we fabricated CZTSe thin film by selenization of single precursor layer consisted metallic constituent. Precursor compositions ratio were selected to have Cu-poor and Zn-rich content and prepared by RF magnetron sputtering. Thermal processing was applied to introduce selenium into as-deposited films at temperatures ranging from 350 to 500 for time up to 120 minutes. Single precursor films showed amorphous structure and consist of individual elements of Cu, Zn, and Sn. It was confirmed by XRD analysis that synthesis of CZTSe compound is occurred from lower temperature process, although concurrently additional phases such as binary cooper selenides are also existed. The quality of CZTSe crystal was improved as temperature increased. We also investigated the optical and electrical properties of as-selenized CZTSe as well.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.85-87
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• 2009

Despite the success of $Cu(In,Ga)Se_2$ (CIGS) based PV technology now emerging in several industrial initiatives, concerns about the cost of In and Ga are often expressed. It is believed that the cost of those elements will eventually limit the cost reduction of this technology. one candidate to replace CIGS is $Cu_2ZnSnSe_4$ (CZTSe), fabricated by co-evaporation technique. Effects of substrate temperature of $Cu_2ZnSnSe_4$ absorber layer on the performance of thin films solar cells were investigated. As substrate temperature increased, the grain size of $Cu_2ZnSnSe_4$ films increased presumably. At a optimal condition of substrate temperature is $320^{\circ}C$, the solar cell shows a conversion efficiency of 1.79% with $V_{OC}$ of 0.213V, JSC of $16.91mA/cm^2$ and FF of 49.7%.

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.86.2-86.2
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• 2015

Cu2ZnSn(S,Se)4 thin film solar cells have been fabricated using sputtered Cu/Sn/Zn metallic precursors on Mo coated sodalime glass substrate without using a toxic H2Se and H2S atmosphere. Cu/Sn/Zn metallic precursors with various thicknesses were prepared using DC magnetron sputtering process at room temperature. As-deposited metallic precursors were sulfo-selenized inside a graphite box containing S and Se pellets using rapid thermal processing furnace at various sulfur to selenium (S/Se) compositional ratio. Thin film solar cells were fabricated after sulfo-selenization process using a 65 nm CdS buffer, a 40 nm intrinsic ZnO, a 400 nm Al doped ZnO, and Al/Ni top metal contact. Effects of sulfur to selenium (S/Se) compositional ratio on the microstructure, crystallinity, electrical properties, and cell efficiencies have been studied using X-ray diffraction, Raman spectroscopy, field emission scanning electron microscope, I-V measurement system, solar simulator, quantum efficiency measurement system, and time resolved photoluminescence spectrometer. Our fabricated Cu2ZnSn(S,Se)4 thin film solar cell shows the best conversion efficiency of 9.24 % (Voc : 454.6 mV, Jsc : 32.14 mA/cm2, FF : 63.29 %, and active area : 0.433 cm2), which is the highest efficiency among Cu2ZnSn(S,Se)4 thin film solar cells prepared using sputter deposited metallic precursors and without using a toxic H2Se gas. Details about other experimental results will be discussed during the presentation.