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A potential solar absorber material, sputtered kesterite Cu2ZnSnS4 (CZTS) thin film, has been extensively studied in recent years due to its advantageous properties, including the earth abundance of its constituent elements, nontoxicity, suitable band gap, and high absorption coefficient. 2000 nm CZTS thin films were deposited on soda lime glass by...
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Citations
... Semiconducting materials based on Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe), and their derivatives having kesterite structure, have recently attracted considerable attention as promising alternatives to the wellestablished thin film solar cells based on Cu(In,Ga)(S,Se)2 (CIGS) and CdTe (Sharmin et al. 2020, Akcay et al. 2021, Sawa et al. 2024a). This interest is partly due to the constituent elements used in this material, that are not listed as critical raw materials (CRM) (Wadia et al. 2009, Hofmann et al. 2018. ...
... As a result, we used Raman measurement to determine the presence of vibration modes for the CZTS phase in the samples and any other accompanied phases. Figure 3 (b) shows in all samples with different precursor stacking orders, strong vibrational modes located at 338 cm -1 and 288 cm -1 which corresponded to the CZTS phase (Abusnina et al. 2015, Yang et al. 2017, Sharmin et al. 2020). The Raman spectra indicated the formation of singlephase CZTS thin films with no secondary phases detected. ...
Several studies have attempted to overcome the sudden volume expansion of the precursor during sulfurization by the use of oxygen-containing precursors when growing the CZTS absorber. This work demonstrates the influence of precursor stacking orders on the properties of the CZTS thin film absorber layer from DC-sputtered oxygenated precursors for solar cell applications. CZTS absorber layers were prepared from three types of DC-sputtered stacks, namely, Zn-O/Sn/Cu, Sn/Zn-O/Cu, and Sn/Cu/Zn-O. The precursors were sequentially deposited on a soda lime glass (SLG) using DC-magnetron sputtering and annealed in a sulfur and nitrogen ambient. X-ray diffractometry (XRD) and Raman spectroscopy analyses reveal the formation of crystalline kesterite CZTS structure regardless of the precursor stacking order. Atomic force microscope (AFM) analysis showed that CZTS thin films grown from precursor stacks SLG/Zn-O/Sn/Cu and SLG/Sn/Zn-O/Cu had improved morphological properties with densely packed large grains compared to that with stack SLG/Sn/Cu/Zn-O. SLG/Zn-O/Sn/Cu is the best stack among the studied stacking orders since it exhibits large grains in the absorber layer, which is preferential for high-efficiency thin film solar cells. The use of oxygenated precursor with order Sn/Zn-O/Cu promises improved CZTS absorber properties as it exhibits better morphological properties.
... Å) and exhibit a high degree of concordance with the values that have been reported for kesterite structured in CZTS (a = b = 5.450 Å and c = 10.90 Å) [44]. ...
The perovskite crystals formed by methylammonium lead iodide (MAPbI3) have garnered growing interest owing to their exceptional photovoltaic capabilities, economical production process, and ability to be processed in solution. A multitude of techniques have been devised to produce dense and uniform perovskite thin coatings, which are critical for the proper functioning of electronic devices. In order to promote the development of CH3NH3PbI3 perovskite thin films that are uniform, dense, and exceptionally smooth, we present an additive-assisted method utilizing Copper zinc tin sulfide Cu2ZnSnS4 (CZTS) nanoparticles. The surface, optical, morphological, and structural properties were subsequently determined. The mechanisms by which the additive improves the quality of the material during the formation of CH3NH3PbI3 perovskite films are elucidated in this study. These processes are postulated to characterize the crystallization of the films. Using this beneficial technique, a high-quality CH3NH3PbI3 film with a grain size significantly larger than 1.6 μm was effectively manufactured. Additionally, the doping process resulted in enhancements in both absorption and photoluminescence intensity. The addition of CZTS NPs elevated the crystal structures and morphologies of the CH3NH3PbI3 layer to a degree that was comparatively favorable. This was evidenced by the crystallite size of 83 nm and an optical bandgap (Eg) of 1.63 eV, both of which attest to the enhanced quality of the film. With the structure of glass/FTO/TiO2/CH3NH3PbI3:CZTS NPs/spiro-oMeTAD/Au ,the power conversion efficiency (PCE) of the best cell was 15.13% with a fill factor of 66.07%. The results of this study indicate that doping CH3NH3PbI3 solar cells with CZTS NPs is a dependable method for enhancing photovoltaic performance and promoting crystal growth.
... The structural, optical and electrical properties of CZTS depend on the growth conditions and as well as the method used to grow the CZTS thin film. Many deposition techniques have been reported so far regarding deposition of CZTS films like: sol-gel dip coating [6], thermal evaporation [8], sputtering [9], Pulsed Laser deposition [10] and ultrasonic spray pyrolysis [11,12]. There is always an improvised effort for new economics technologies to optimize growth parameters to reduce defects and enhance the quality absorber films. ...
Cu2ZnSnS4 (CZTS) thin films were synthesized on glass substrates via ultrasonic spray pyrolysis method to investigate the influence of solution flow-rate on their physical properties. Solution flow-rate was varied in the range of 10–30 ml/h to analyse its impact on the films. XRD analysis revealed a kesterite phase with a preferred orientation along the (112) plane, which intensified with higher flow-rates. Additionally, structural investigations identified secondary phases of CuxS, Sn2S3, and Cu2SnS3 in the films prepared at a solution flow-rate of 25 ml/h. Raman spectroscopy confirmed the XRD analysis. SEM micrographs indicated compact growth with a slightly rough surface. UV–Vis spectroscopy demonstrated a significant decrease in transmittance, leading to a corresponding reduction in the bandgap value from 2.17 to 0.84 eV as the flow rate increased from 10 to 30 ml/h. The electrical conductivity analysis indicated p-type conductivity, with maximum conductivity value of 2.73 (Ω cm)−1 observed at a flow-rate of 20 ml/h.
... Transition metal ternary sulfides and oxides, such as NiCo 2 S 4 , ZnCo 2 S 4 , MnCo 2 S 4 , CuCo 2 S 4 , and Co 2 SiO 4 exhibit remarkable electronic conduction and low values of band gaps that enhance the electrochemical reaction by expediting the process of charge transfer [17][18][19]. The outstanding features of quaternary Cu 2 ZnSnS 4 (CZTS) semiconducting blend for electronic and optoelectronic applications have emerged as an intriguing advancement over copper indium gallium selenide (CIGS)-based ones such as the excellent adequacy, non-toxicity, expense, and acceptable optoelectrical behaviors [20,21]. CZTS as an environmentally friendly semiconductor compound can www.mrs.org/jmr ...
Cu 2 ZnSnS 4 (CZTS) films were produced in a one-stage depositing spray pyrolysis technique instead of that needed post-sulfurization treatment. X-ray diffraction (XRD) has been used to identify crystal structure of studied films before and after E.B. irradiation. The presence of (112) as a preferred orientation indicates the kesterite phase structure of CZTS films. The energy-dispersive X-ray average data at several points of the film surface assured the homogeneous distribution of the constituent elements in the CZTS film composition. The optical behavior and the optical band-gap values of the studied CZTS films before and after E.B. irradiation have been checked by using the Tauc relation. The optical band-gap values reduced from 1.98 to 1.86 eV when the irradiation doses rose from 0 to 60 kGy. The electrochemical performance of CZTS films, on the two different conductive substrates, was tested by the cyclic voltammetry and electrochemical impedance spectroscopy analysis.
Graphical abstract
... Two kesterite structures plus a stannite unit cell make up the distinct structure known as the PMCA. Out of the three possible structures of CZTS, the kesterite structure is thermodynamically more stable than the rest of the two structures [33]. So it has been chosen above other structures. ...
In the renewable energy sector, solar energy has emerged as a very abundant resource, which has its implementation from very large-scale industries to household uses. The market of solar cells has been monopolized by thick-film Silicon solar cells ever since its initial development. However, with recent advancements, thin film has become the preferred design for solar cells because of several upper hands it proved over the thick cells. CIGS (Copper Indium Gallium Diselenide) and CdS (Cadmium Selenide) have shown tremendous performances in the thin-film sector. But with toxicity and cost factors, these cells are never that feasible. So, CZTS (CuZnSn Sulfide) which has come as a replacement for CIGS, has shown extraordinary photovoltaic nature with very high light absorption characteristics. Further, the constituents of CZTS are abundant in nature which reduces the cost involved. To enhance efficiency, numerous structural and material features have been experimentally modified. The single-junction CZTS solar cell, however, has yet to achieve an efficiency of more than 13%, despite numerous attempts. This article presents a thorough analysis of the advancements made and potential applications for the CZTS thin-film solar cell (TFSC). This manuscript outlines the development of the TFSC, the fabrication process, the design of the TFSC, the defects in the CZTS, and the potential use of the TFSC as a solar cell.
... A number of the A I 2 B II D IV Q 4 sulfides and selenides manifest a direct energy band gap being in the 1.0-1.5 eV range, high absorption coefficients (at least bigger than 10 4 cm -1 ), electrical conductivity of p-type, high conversion powers, etc. [1][2][3][4][5][6][7][8][9][10]. These properties are very attractive for application of the A I 2 B II D IV Q 4 compounds, especially tin-bearing sulfides and selenides, as efficient materials of thin-film solar cell absorbers [2,[11][12][13][14][15][16][17], thermoelectric and photovoltaic semiconductors [18][19][20][21][22], photocatalytic convertors of water splitting to hydrogen gas [4], promising materials for nonlinear optics [23,24] and luminescence applications [25]. Many physicochemical properties of the A I 2 B II SnQ 4 sulfides and selenides can be changed effectively via the formation of solid solutions [26,27] and doping with other chemical elements [28,29], decreasing crystal dimensions to nanosizes [30,31], formation of special vacancies on peculiar crystallography sites or intrinsic defects [32,33] to reach the desirable technological parameters. ...
... The increase in the crystal size of CPTS nanoparticle can be attributed to the replacement of Zn atoms with larger sized atoms of Pd [27]. The number of dislocations in a unit volume of a crystal material can be estimated through its dislocation density d [28], which is given as: ...
... Table 4 summarizes the elements present in these nanoparticles based on their atomic% and the elemental composition of CZTS and CPTS were determined to be Cu 2.4 Zn 0.06 SnS 3.0 and Cu 2.4 Pd 1.03 SnS 3.7 respectively, revealing a Cu rich composition for both nanoparticles [38]. The elemental composition for CPTS nanomaterial is in close range to the ideal configuration of the pristine CZTS material with general composition of Cu 2 ZnSnS 4 [28,39,40]. The elemental composition obtained for CZTS nanoparticle suggest possibility of formation of secondary phases, while the use of Pd atoms to supplant Zn guarantees the formation of the kesterite composition and balanced stoichiometry. ...
... Materials that show high refractive index slow down the speed at which light travels through them [50]. The refractive index (n) of materials can be calculated using Moss relation [28]: ...
... The increase in the crystal size of CPTS nanoparticle can be attributed to the replacement of Zn atoms with larger sized atoms of Pd [27]. The number of dislocations in a unit volume of a crystal material can be estimated through its dislocation density d [28], which is given as: ...
... Table 4 summarizes the elements present in these nanoparticles based on their atomic% and the elemental composition of CZTS and CPTS were determined to be Cu 2.4 Zn 0.06 SnS 3.0 and Cu 2.4 Pd 1.03 SnS 3.7 respectively, revealing a Cu rich composition for both nanoparticles [38]. The elemental composition for CPTS nanomaterial is in close range to the ideal configuration of the pristine CZTS material with general composition of Cu 2 ZnSnS 4 [28,39,40]. The elemental composition obtained for CZTS nanoparticle suggest possibility of formation of secondary phases, while the use of Pd atoms to supplant Zn guarantees the formation of the kesterite composition and balanced stoichiometry. ...
... Materials that show high refractive index slow down the speed at which light travels through them [50]. The refractive index (n) of materials can be calculated using Moss relation [28]: ...
Kesterite materials show excellent optical and semiconductive properties for use as p–type absorber layer in photovoltaic (PV) applications, but they have a high open circuit voltage deficit (Voc,def) due to high antisite defect and secondary phase formation, resulting in poor device performance. This work reports PV cell composed of Cu2PdSnS4 (CPTS) nanoparticles as absorber layer yielding highly improved Voc of 900 mV which is two times that of fabricated pristine Cu2ZnSnS4 (CZTS) PV cell. Improved PV cell parameters such as fill–factor (FF) of 83.4% and power conversion efficiency (PCE) of 1.01% were obtained for CPTS devices which are 3–fold that of pristine CZTS devices. Optical studies revealed enhanced redshift absorption for CPTS nanoparticles. Electrochemical studies shows improved current production, high electron mobility and low charge resistance for CPTS nanoparticles. This study shows that the improved photovoltaic properties can be attributed to enhancement in the bulk properties when Zn atoms are replaced by Pd atoms in kesterite nanomaterials as absorber layer material for PV applications.
... where N a , q, ε 0, ε r, stand for doping density (cm − 3 ), electronic charge (1.60219 × 10 -19 C), permittivity of free space (8.85 × 10 -14 F/cm), and dielectric constant (for CZTS = 13.9) (Sharmin et al., 2020). Area of the cell (cm 2 ), measured capacitance, and applied DC voltage are indicated by A, C, and V, respectively. ...
... This trend may be due to the high amorphous content in these materials. The annealed thin-films had lower lattice strain values than the unannealed samples because their crystal sizes were larger [50,51]. The lattice strain of CCZTS-20 decreased from 82.1 in the unannealed state to 22.1 in the annealed state, while CCZTS-40 decreased from 38.2 to 21.8, CCZTS-60 decreased from 96.1 to 28.0, and CCZTS-80 decreased from 47.1 to 34.0 upon annealing. ...
... These results indicate that annealing at 525 • C significantly reduces the lattice strain of the thin-films. According to the W-H anisotropic uniform deformation energy density model, the number of defects at grain boundaries increases as the crystal size decreases [51]. A stress field is generated when internal pressure is exerted by the surface tension caused by volume defects. ...
... The additional stress at the grain boundaries leads to lattice strain. This may explain why the lattice strain of the annealed thin-films was significantly lower than that of the unannealed thin-films [51] (see Fig. 5a and 5b to visualize the trend between crystal size and lattice strain in the thin-films). ...
