• Korean Journal of Materials Research
• /
• v.29 no.9
• /
• pp.553-558
• /
• 2019

$Cu_2ZnSn(S,Se)_4(CZTSSe)$ thin film solar cells areone of the most promising candidates for photovoltaic devices due to their earth-abundant composition, high absorption coefficient and appropriate band gap. The sputtering process is the main challenge to achieving high efficiency of CZTSSe solar cells for industrialization. In this study, we fabricated CZTSSe absorbers on Mo coated soda lime glass using different pressures during the annealing process. As an environmental strategy, the annealing process is performed with S and Se powder, without any toxic $H_2Se$ and/or $H_2S$ gases. Because CZTSSe thin films have a very narrow stable phase region, it is important to control the condition of the annealing process to achieve high efficiency of the solar cell. To identify the effect of process pressure during the sulfo-selenization, we experiment with varying initial pressure from 600 Torr to 800 Torr. We fabricate a CZTSSe thin film solar cell with 8.24 % efficiency, with 435 mV for open circuit voltage($V_{OC}$) and $36.98mA/cm^2$ for short circuit current density($J_{SC}$), under a highest process pressure of 800 Torr.

• Korean Journal of Materials Research
• /
• v.31 no.11
• /
• pp.619-625
• /
• 2021

Cu₂ZnSn(S,Se)₄ (CZTSSe) based thin-film solar cells have attracted growing attention because of their earth-abundant and non-toxic elements. However, because of their large open-circuit voltage (V_oc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)₂ (CIGS) and CdTe based solar cells. One of the main causes of this large V_oc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 ℃ to 540 ℃ during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

• Current Photovoltaic Research
• /
• v.11 no.3
• /
• pp.67-74
• /
• 2023

The earth-abundant element-based Cu₂ZnSn(S,Se)₄ (CZTSSe) thin film solar cells (TFSCs) have attracted greater attention in the photovoltaic (PV) community due to their rapid development in device power conversion efficiency (PCE) >13%. In the present work, we demonstrated the fine-tuning of the bandgap in the CZTSSe TFSCs by altering the sulfur (S) to the selenium (Se) chalcogenide ratio. To achieve this, the CZTSSe absorber layers are fabricated with different S/(S+Se) ratios from 0.02 to 0.08 of their weight percentage. Further compositional, morphological, and optoelectronic properties are studied using various characterization techniques. It is observed that the change in the S/(S+Se) ratios has minimal impact on the overall Cu/(Zn+Sn) composition ratio. In contrast, the S and Se content within the CZTSSe absorber layer gets altered with a change in the S/(S+Se) ratio. It also influences the overall absorber quality and gets worse at higher S/(S+Se). Furthermore, the device performance evaluated for similar CZTSSe TFSCs showed a linear increase and decrease in the open circuit voltage (V_oc) and short circuit current density (J_sc) of the device with an increasing S/(S+Se) ratio. The external quantum efficiency (EQE) measured also exhibited a linear blue shift in absorption edge, increasing the bandgap from 1.056 eV to 1.228 eV, respectively.

• Economic and Environmental Geology
• /
• v.8 no.1
• /
• pp.1-23
• /
• 1975

The subject of this study deals with phase relations between stannite ($Cu_2FeSnS_4$) and sphalerite (${\beta}-ZnS$)/wurtzite (${\alpha}-ZnS$). The phase relations were systematically investigated from liquidus temperature to $400^{\circ}C$ under controlled conditions. ${\beta}-stannite$ (tetragonal) is stable up to $706{\pm}5^{\circ}C$, where it inverts to a high-temperature polymorph ${\alpha}-stannite$ (cubic) melting congruently at $867{\pm}5^{\circ}C$. Sphalerite (cubic, ${\beta}-ZnS$) inverts at $1013{\pm}3^{\circ}C$ to wurtzite, which is the hexagonal hightemperature polymorph of ZnS. Between ${\alpha}-stannite$ and sphalerite a complete solid solution series exists above approximately $870^{\circ}C$ up to solidus temperature. The melting temperature of ${\alpha}-stannite$ rises towards sphalerite and reaches a maximum at $1074{\pm}3^{\circ}C$, which is the peritectic with the composition of 91 wt. % sphalerite and 9 wt. % ${\alpha}-stannite$. At this temperature, wurtzite takes only 5wt. % ${\alpha}-stannite$ in solid solution which decreases with increasing temperature. The inverson temperature of ${\alpha}/{\beta}-stannite$ is lowered with increasing amounts of sphalerite in solid solution down to $614{\pm}7^{\circ}C$, which is the eutectoid with the composition of 13 wt. % sphalerite and 87 wt. % ${\alpha}-stannite$. Here, ${\beta}-stannite$ contains only 10wt. % sphalerite in solid solution. With decreasing temperature, the ranges of the solid solution on both sides of the system narrow. The phase relations in the above pure system changed due to the FeS impurities in the sphalerite solid solution. The eutectoid increased from $614{\pm}7^{\circ}C$ up to $695{\pm}5^{\circ}C$ (5 wt. % FeS) and $700{\pm}5^{\circ}C$ (10wt. % FeS), while the peritectic decreased from $1074{\pm}3^{\circ}C$ down to $1036{\pm}3^{\circ}C$ (wt. %FeS) and $987{\pm}3^{\circ}C$ (10wt. %FeS). A most notable change is the appearance of non-binary regions. An important feature is the combination of this study system with the experimental results reported by Sprinfer (1972). If a stannite-kesterite solid solution is used in the place of stannite as a bulk composition, the inversion temperature is lowered to less than $400^{\circ}C$ which belongs to temperatures of the hydrothermal region.