Next Article in Journal
Harmonic Generation in Biased Semiconductor Superlattices
Next Article in Special Issue
Physical Mechanisms of Intermolecular Interactions and Cross-Space Charge Transfer in Two-Photon BDBT-TCNB Co-Crystals
Previous Article in Journal
MWCNTs Composites-Based on New Chemically Modified Polysulfone Matrix for Biomedical Applications
Previous Article in Special Issue
Optical Characterization and Prediction with Neural Network Modeling of Various Stoichiometries of Perovskite Materials Using a Hyperregression Method
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Nanomaterials
Volume 12
Issue 9
10.3390/nano12091503
nanomaterials-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Synthesis and Characterization of Cu2ZnSnSe4 by Non-Vacuum Method for Photovoltaic Applications

by
Meenakshi Sahu
1,2,
Vasudeva Reddy Minnam Reddy
3,
Bharati Patro
4,
Chinho Park
2,*,
Woo Kyoung Kim
3,* and
Pratibha Sharma
1,*
1
Department of Energy Science and Engineering, Indian Institute of Technology Bombay Powai, Mumbai 400076, India
2
Korea Institute of Energy Technology (KENTECH), 200 Hyukshin-ro, Naju 58330, Korea
3
School of Chemical Engineering, Yeungnam University, Gyeongsan 38541, Korea
4
Centre for Research in Nanotechnology and Sciences, Indian Institute of Technology Bombay Powai, Mumbai 400076, India
*
Authors to whom correspondence should be addressed.
Nanomaterials 2022, 12(9), 1503; https://doi.org/10.3390/nano12091503
Submission received: 24 March 2022 / Revised: 21 April 2022 / Accepted: 26 April 2022 / Published: 28 April 2022
(This article belongs to the Special Issue Performance of Nanocomposite for Optoelectronic Applications)
Browse Figures
Review Reports Versions Notes

Abstract

:
Wet ball milling was used for the synthesis of Cu2ZnSnSe4 (CZTSe) nanoparticles with a kesterite structure. The prepared nanoparticles were used for ink formulation. Surfactants and binders were added to improve the ink stability, prevent agglomeration, and enhance ink adhesion. The films deposited via spin coating were annealed at different temperatures using a rapid thermal processing system in the presence of selenium powder in an inert environment. Analytical techniques, such as X-ray diffraction, Raman spectroscopy, and Fourier-transform infrared spectroscopy, were used to confirm the formation of CZTSe nanoparticles with a single-phase, crystalline kesterite structure. Field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to study the surface morphology and chemical composition of the thin films before and after annealing, with and without the sodium solution. The optoelectrical properties were investigated using ultraviolet-visible spectroscopy and Hall measurements. All the prepared CZTSe thin films exhibited a p-type nature with an optical bandgap in the range of 0.82–1.02 eV. The open-circuit voltage and fill factor of the CZTSe-based devices increased from 266 to 335 mV and from 37.79% to 44.19%, respectively, indicating a decrease in the number of recombination centers after Na incorporation.

Graphical Abstract

1. Introduction

The quaternary inorganic semiconductor Cu2ZnSnSe4 (CZTSe) has unique optical and electrical properties. Consequently, they have emerged as ideal solar cell absorbers, replacing Cu(In, Ga)Se2 (CIGS) and CdTe-based thin-film photovoltaic devices [1,2]. Thus far, CZTSe layers have been deposited using several vacuum- and nonvacuum-based methods. Solar cells built using CZTSe layers fabricated via thermal co-evaporation and direct current (DC) sputtering exhibit power conversion efficiencies (PCE) of 11.6% and 11.95%, respectively [3,4]. Another method to induce CZTSe layer-growth is via the stacking and subsequent selenization of metallic layers. This process has been shown to form materials with a PCE of 9.7% [5]. CZTSe layers grown using solution-based processes have exhibited a PCE of 10.1% [6]. CZTSe thin films developed via the electrochemical route exhibited a PCE of up to 8% [7]. Therefore, CZTSe photovoltaic devices may be capable of attaining high PCE values at a low cost, making CZTSe a promising material for the large-scale production of photovoltaic devices.
Recently, nanoparticle inks prepared using mechanochemical milling have gained considerable attention over other nonvacuum-based processes as a simple, low-cost, and eco-friendly alternative. The nanoparticle-based thin film fabrication process involves the preparation and subsequent deposition of nanoparticle inks, followed by annealing (selenization) in the presence of Se vapor or H2Se gas. This procedure is used to prepare a variety of compound materials in numerous applications [8,9,10,11]. Shyju et al. (2015) synthesized CZTS and CZTSe thin films in a single-step, ball milling process and studied their physical properties [12]. Tiwari et al. (2017) studied the thermoelectric properties of CZTSe [9]. Malar et al. (2017) explored the effect of milling conditions on the phase purity of CZTSe thin films using Raman spectroscopy [13]. In 2020, Goyal and Malar obtained single-phase CZTSe and investigated its photo-response [14]. Liu et al. (2020) fabricated an SLG/Mo/CZTSe/CdS/i-ZnO/ZnO:Al(AZO)/Al photovoltaic device with an efficiency of 0.18% [15].
Recently, researchers have demonstrated the effective passivation of the grain boundaries in CZTSe absorber layers with the incorporation of alkali metals, particularly sodium, [16,17,18]. Incorporating alkali metals not only passivates the grain boundaries, surface, and defects but also enhances the crystal quality and carrier concentration of the CZTSe absorber layers [19,20,21,22]. Tampo et al. (2020) investigated the impact of Na incorporation in the CZTSe thin film on the morphological and photovoltaic properties as a function of sodium doping [16]. Kim et al. reported the approach for passivation of grain boundaries and defects in the CZTSe samples with and without Na incorporation [17]. Recently, Rehan et al. systematically examined the effects of sodium doping on the performance of CZTSe solar cells thru different sodium incorporation pathways, such as in-situ sodium doping before and after growing thin films [18].
Herein, we present a simple, cost-effective, and environmentally-friendly technique for the preparation of CZTSe nanoparticles and ink materials using a wet mechanochemical process. Thin films were deposited using formulated ink and sodium solutions via the spin-coating method. The post-annealing effects on the spin-coated CZTSe thin films with and without a sodium solution were characterized using X-ray diffraction (XRD), Raman spectroscopy, field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), ultraviolet-visible (UV-Vis) spectroscopy, and Hall measurements. The photovoltaic properties of the spin-coated CZTSe thin films were analyzed based on their current density—voltage (J-V) characteristics.

2. Materials and Methods

All elemental powders of copper (≥99.5%), zinc (≥99.5%), tin (≥99.5%), and selenium (≥99.99%) as well as chemical reagents, such as 1-butanol (≥99.0%), methyl ethyl ketone (MEK, ≥99.0), Tween-80 (chemically pure grade), and cadmium sulfate (≥99.0%), were purchased from Sigma-Aldrich (Saint Louis, MO, USA). Ethanol (≥99.8%), sodium borohydride (chemically pure grade), and polyethylene glycol (PEG-400, extra pure grade) were purchased from Fluka (Shin-Dong, Korea), Daejung (Siheung-si, Korea) and Samchun Chemicals (Seoul, Korea), respectively. Thiourea (chemically pure grade) and ammonia solution (chemically pure grade) were obtained from Duksan, Seoul, Korea. All chemicals were used as received without further purification. Commercially available Mo-coated soda-lime glass (SLG) (DKG Co., Daegu, Korea) with a thickness of 0.5 mm and resistivity of ~1.0 Ω/sq was used for the thin film preparation.
The as-deposited thin films without and with sodium solution were named Se0 and Se0_Na, while the thin films annealed at 500 °C, 520 °C, and 550 °C without and with sodium solution were named Se1, Se2, Se3 and Se1_Na, Se2_Na, Se3_Na, respectively. As fabricated photovoltaic devices using the above annealed thin films were named SC-Se1, SC-Se2, SC-Se3, SC-Se1_Na, SC-Se2_Na, and SC-Se3_Na.
A detailed description of the preparation of CZTSe nanopowders and ink (Figure S1), and fabrication of corresponding thin films and photovoltaic devices was given in our previous report [23] and electronic supplementary information (ESI). Material and device characterization techniques employed in this study were summarized in ESI as well.

3. Result and Discussion

3.1. Zeta Potential and DLS

The dispersion stability profile and hydrodynamic size of the CZTSe ink nanoparticles were determined using zeta potential (dip cell) and dynamic light scattering (DLS) techniques. The results are shown in Figure 1a,b. A mean zeta potential higher than ±30 mV was observed, thereby confirming the stability of the CZTSe nanocrystals in the prepared ink [24,25]. The negative zeta potential suggests the presence of Se2− ions on the surface of the nanoparticles [26]. The average hydrodynamic size of the CZTSe nanocrystals was 913 nm.

3.2. Grazing-Incidence X-ray Diffraction (GI-XRD) Analysis

The XRD diffraction patterns of the as-synthesized CZTSe nanocrystals (Se0, Se1, Se2, Se3, Se0-Na, Se1_Na, Se2_Na, and Se3_Na) are depicted in Figure 2a (without thin sodium layers) and Figure 2b (with thin sodium layers). Sharp XRD diffraction peaks are observed at approximately 2θ = 27.19°, 45.25°, and 53.49°, corresponding to d-spacings of approximately 3.276 Å, 2.002 Å, and 1.711 Å, which are attributed to the (112), (204), and (312) planes of the CZTSe kesterite crystal structure (JCPDS card no. 00-052-0868), respectively. Various weak peaks at 2θ = 17.34°, 21.98°, 31.75°, 65.94°, and 72.65°, corresponding to the (101), (110), (008), and (332) planes of the annealed CZTSe samples, respectively, were also observed. In addition to the characteristic peaks of the CZTSe absorber, the primary XRD peak of Mo was detected at 2θ = 40.53° (110) as an internal standard, indicating a well-aligned sample height. All the annealed CZTSe samples exhibited polycrystallinity. No characteristic diffraction peaks of secondary phases were found in any of the prepared CZTSe samples with or without sodium. This confirms the formation of a single-phase for all synthesized CZTSe samples.
Structural properties, such as crystallite size, dislocation density, strain, and lattice constants, of the CZTSe samples, were determined using the XRD diffraction pattern as described in our previous study [23]. The data are summarized in Table S1. The determined lattice constants (a = b = ~5.47 Å and c = ~11.34 Å) correspond well with the standard lattice constant values of the kesterite CZTSe material (a = b = 5.69 Å and c = 11.33 Å) (JCPDS card no. 00-052-0868). Tetragonal distortion (c/2a ratio of 1) was observed in all CZTSe samples. These results correspond well with the literature values and further confirm the kesterite structure [14,27]. Using the Debye–Scherrer formula, the crystallite size was estimated to be in the range of 9–45 nm, whereas the average crystallite size obtained using the Williamson–Hall method was approximately 7–50 nm. Smaller crystallite sizes along with higher dislocation densities and strains were observed for the as-synthesized CZTSe as well as Se0 (before annealing). A decrease in the crystallite size and an increase in the strain and dislocation density with increasing temperature were observed, indicating poor crystallinity (Table S1, ESI). The strain of all CZTSe samples showed a negative slope, which suggests lattice compression toward the c-axis (Table S1) [23,28]. The relative intensity ratios of I(112)/I(204) and I(112)/I(312) for Se1 and Se1_Na were observed to be higher than the standard values [I(112)/I(204) = 2.63, and I(112)/I(312) = 5.0] (Table S2). The relative intensity ratios for the other prepared samples possessed either moderate (Se0, Se2, and Se0_Na) or lower (Se3 and Se3_Na) values compared with those of the standard. A higher intensity ratio indicates that [112] is the preferred orientation for the sample annealed at a lower temperature. This is probably owing to the growth of the MoSe2 layer, which mainly affects the texturization of the CZTSe material [29,30].
Notably, the CZTSe XRD diffraction patterns overlap with those of Cu2Se, ZnSe, and Cu2SnSe3. Consequently, the phase purity of CZTSe cannot be confirmed using XRD alone. Raman spectroscopy was, therefore, used to obtain further insights into the phase of the fabricated material.

3.3. Raman Analysis

Raman scattering technique was used to confirm the phase purity of all the prepared CZTSe samples, as shown in Figure 3a–e. Peaks were identified at Raman shifts of 187 and 234 cm−1 for the as-synthesized CZTSe and Se0 samples, respectively (Figure 3a,b). The intense vibrational bands for the annealed samples (Se1, Se2, and Se3) at different temperatures were observed at ~171, ~193, and ~234 cm−1 (Figure 3c–e) [15]. It is currently unknown why two Raman peaks appeared in the samples before annealing, although this has been previously reported [31,32]. The broadening and change in position of the peaks might be due to a change in crystallinity and internal lattice stress [12,33].
The intense vibrational bands at Raman shifts of 171, 193, and 234 cm−1 belong to the CZTSe kesterite phase [15]. The strong bands at 171 and 193 cm−1 were attributed to the A1 symmetry mode, which correlates to the vibration of chalcogenide (selenium) atoms within the lattice [14]. The peak at 234 cm−1 belongs to the B-symmetry mode. These results are comparable to previously reported CZTSe kesterite Raman peaks [13,15,34]. Raman peaks for other secondary phases, such as binary and ternary phases (e.g., ZnSe and Cu2SnSe3), have been reported and are summarized in Table S3. The absence of characteristic peaks of the secondary phases in the Raman spectra for the CZTSe confirmed the formation of a single phase. Raman spectroscopy offers key information to enable the successful characterization of the stannite and kesterite structures of the CZTSe materials. The peaks at 209, 226, 232, and 254 cm−1 are suggestive of a stannite structure, contrary to the kesterite structure (at 150–200 (171, 187), 216, 230, and 239 cm−1). The corresponding peaks at 171, 193, and 234 cm−1 of the annealed samples closely resembled the kesterite structure. Despite the peaks at 193 and 234 cm−1 being close to the peaks at 209 and 232 cm−1 of the stannite structure, no peaks were observed at 254 cm−1. These results confirm the formation of single-phase CZTSe kesterite.

3.4. FT-IR Analysis

The FT-IR spectra of the CZTSe samples, PEG-400, and Tween-80 in the range of 400–4000 cm−1 are shown in Figure 4a,b. Major FT-IR peaks were observed at approximately 3300, 1700, 1600, and 986 cm−1 for samples CZTSe, Se0 and Se1. Additionally, a weak absorption band of metal selenide can be observed in the range of 550–400 cm−1 for samples CZTSe, Se0 and Se1 [35,36]. The FT-IR peaks of pure PEG-400 [37] and Tween-80 [38] were observed at approximately 3600, 2900, 1452, 1245, 940, and 800 cm−1 (Figure 4a). The band at wavenumber ~2900 cm−1 corresponds to the C–H stretching vibrations of the –CH2 group, and the peak at 1245 cm−1 is attributed to C–O stretching vibrations. The peak at 1452 cm−1 corresponds to the C–H bending vibrations of the –CH2 group. However, asymmetrical bending vibrations of CH3 were observed. The peak near 900 cm−1 corresponds to C–O–C symmetrical stretching. A characteristic peak at 1735 cm−1 corresponding to the C=O group was observed in the FT-IR spectrum of Tween-80. The band at approximately 600 cm−1, attributed to the secondary phase (ZnSe), was absent in both Se0 and Se1. The spectra of the Se0 showed absorption bands in regions similar to those of Tween-80 and PEG-400. A possible explanation for this might be that the organic molecules (solvents, binder, and surfactant) used in the ink possess similar FT-IR absorption profiles.
The FT-IR peaks in a similar region were observed for Se2 and Se3 at wave numbers of approximately 3300, 1700, 1600, and 984 cm−1, and these observed peaks are well-match with the unannealed samples. A weak vibrational band of metal selenide was observed in the spectrum at 550–400 cm−1 in the as-synthesized Se2 and Se3 samples [35,36]. However, characteristic peaks ~600 cm−1 for ZnSe were not observed, further confirming the formation of single-phase CZTSe [39]. The peak at ~3400 cm−1 is attributed to the chalcogen-rich (selenium-rich) composition. The bands at approximately 1600–900 cm−1 belong to the bending and stretching vibrational frequencies of oxygen. These bands arise from hygroscopic materials and surface-adsorbed moisture; that is, H2O and CO2 molecules, contributing O-H and C-O-associated peaks in the FT-IR spectrum [39]. FT-IR analysis also confirms the presence of a pure phase in all prepared CZTSe samples.

3.5. FE-SEM and EDS Analyses

The effects of annealing and sodium incorporation on the surface morphology of the CZTSe samples were investigated using FE-SEM. The morphology and cross-sectional images along with the EDS data of Se0, Se1, Se2, and Se3 without a sodium layer are presented in Figure 5, Figure 6, Figure S2 and Figure S4, respectively. Figures S2 and S3 show FE-SEM images of Se0 and Se0_Na thin films, respectively. The surface images show that the Se0 and Se0_Na thin films consisted of nanoparticles and organic residues (PEG-400 and Tween-80), suggesting that the organic additives used for the effective spin coating of the ink were not completely eliminated during the pre-heating step. The minimum temperature for decomposing these molecules into vaporized phases has been reported to be approximately 250 °C [40,41]. FE-SEM images of the Se0 and Se0_Na thin films showed several voids with small grain sizes on the surfaces. FE-SEM images of the Se1, Se2, and Se3 thin films are presented in Figure 5, Figure 6 and Figure S4, respectively. During annealing, the organic molecules can be thermally broken down into smaller components and vaporized at high temperatures (500–550 °C). However, some voids with discontinuous grain growth were observed on the surfaces of the samples prepared using this annealing process. Similar surface properties of thin films prepared using nanoparticle ink have also been observed in previous studies [42].
The impact of sodium incorporation on the morphology of the Se1_Na, Se2_Na, and Se3_Na thin films was investigated using FE-SEM, as shown in Figure 7, Figure 8 and Figure S5. The surface images show that Se1_Na, Se2_Na, and Se3_Na thin films were non-homogenous, with pinholes and voids, and demonstrated varying grain sizes with discontinuous growth. Although the surface morphology of the thin films is uneven and non-compact, it can aid in evaporating organic materials and reducing carbon residues from the bottom of thin films [43]. The thicknesses of the CZTSe thin films with and without the sodium layer as well as before and after annealing was observed to be in the range of 900 nm to 2.0 μm. Significantly, surface imperfections, such as cracks, voids, and holes, in thin films can increase the series resistance, leading to recombination sites and/or leakage paths in photovoltaic devices.
The formation of a MoSe2 layer near the interface of the absorber and rare contact layers was observed in the cross-sectional images of all annealed CZTSe samples. Similar to the surface properties of the CZTSe, voids, cracks, and holes were detected on the surface of the thin films during grain growth at different annealing temperatures. These voids, cracks, and holes likely provided channels for the selenium vapors to diffuse. The MoSe2 layers in Se1, Se2, and Se3 thin films had a thickness of 95, 109, and 178 nm, respectively. In the case of the Se1_Na, Se2_Na, and Se3_Na thin films, the MoSe2 layers had a thickness of 278, 317, and 377 nm, respectively. The thickness of the MoSe2 layer was observed to increase with increasing annealing temperature for all CZTSe samples. This may have resulted from the enhanced Se diffusion owing to the poor surface morphology.
SEM-EDS was used to investigate the chemical composition of the CZTSe; the findings are summarized in Table 1, Tables S4 and S5. The chemical composition profiles of all CZTSe samples were slightly different from each other. A trend with an increasing ratio of Se/(Cu + Zn + Sn) in the CZTSe samples was observed, indicating the substantial incorporation of selenium into the thin films prepared without sodium. The CZTSe thin films prepared with sodium showed an initial decrease, followed by an increase in the Se/(Cu + Zn + Sn) ratio with increasing temperature. The ratios of Cu/(Zn + Sn) and Zn/Sn for all CZTSe samples showed a moderate deviation from the stoichiometric value.

3.6. Bulk XRD of Cu2ZnSnSe4 Thin Films

To confirm the formation of MoSe2 at the interface of CZTSe and Mo in the prepared thin films, bulk XRD measurements were conducted. As shown in Figure 9a,b, in addition to the characteristic peaks of the CZTSe thin films, sharp peaks corresponding to Mo were identified at 2θ ≈ 40.56° (110) and 73.62° (211), and slightly broad MoSe2 peaks were observed at 2θ ≈ 31.79° (100) and 56.36° (110). [44,45]. The relative intensity of the XRD peaks of MoSe2 increased with increasing annealing temperature, presumably because of the enhanced selenization of Mo at high temperatures.

3.7. Optical Properties

The bandgap of the CZTSe samples was determined by plotting (αhv)x as a function of incident photon energy (hv, eV) (Equation (1)). The linear portion of the spectrum in the high-absorption regime was then extrapolated, yielding the bandgap at the intercept with the photon energy axis [46]:
α h v = A h v − E g x
Where α, h, v, and Eg are the absorption coefficient, Planck’s constant, light frequency, and optical bandgap (eV), respectively. A and x are both constants. The x value depends on the direct or indirect transition of semiconductor materials. A UV-Vis-NIR spectrophotometer was used to obtain the transmission spectra of the thin films. The absorption coefficient was evaluated using Equation (2) [42]:
α = 1 d ln 1 T
where α is the absorption coefficient, and d and T are the thickness and transmittance of the CZTSe thin film, respectively.
The optical properties of the prepared CZTSe samples were evaluated using transmission spectra in the range of 300–2500 nm, as shown in Figure 10a. The optical properties of semiconductor materials are strongly influenced by surface morphology, explaining the differences in optical properties of CZTSe absorber samples before and after annealing at various temperatures [46]. The optical bandgap values were estimated to be in the range of 0.82–1.02 eV (Figure 10b), which corresponds with the values reported in previous publications [14,15,27,47].

3.8. Electrical Properties

The Hall effect using the Van der Pauw method (with a magnetic field intensity of 0.55 T under ambient conditions) was used to investigate the electrical properties. To investigate the impact of annealing and sodium incorporation on the electrical properties, CZTSe thin films were prepared as previously reported [23]. The results are summarized in Table 2.
The carrier concentration and mobility of CZTSe samples were measured to be 6.14 × 1017–1.61 × 1019 cm−3 and 1.13–6.71 cm2/V·s, respectively. These values are similar to published reports (1015 cm−3–1019 cm−3 and 0.1–10 cm2/V·s, respectively) [12,48,49,50]. Relatively high resistivities (0.1 to 5.8 Ω·cm) were measured, possibly resulting from the uneven grain growth and the porous nature of the thin films. Se3_Na exhibited the highest carrier concentration and lowest resistivity with moderate mobility, although void formation and isolated grain growth were observed in the thin film. All CZTSe samples showed p-type conductivity. Although slight variations in the electrical properties of the CZTSe samples were observed when compared with the reported values of mobility (0.1–10 cm2/V·s), carrier density (1015–1019 cm−3), and resistivity (10−2–10 Ω·cm) [12,27,51,52], however, improvement can be expected by increasing the quality of the films (Table 2).
The results from various analytical techniques, including GI-XRD, Raman, FT-IR spectroscopy, FE-SEM-EDS, UV-Vis-NIR spectrophotometry, and the Van der Pauw measurements, suggest that CZTSe thin films prepared using the nanoparticle ink method can potentially be used as absorber layers to fabricate photovoltaic devices.

3.9. Photovoltaic Analysis: J-V Characteristic

The CZTSe absorber layers with and without sodium were integrated into the photovoltaic device in the traditional configuration of SLG/Mo/CZTSe:Na or CZTSe/CdS/i-ZnO/AZO/Ni-Ag. The photovoltaic performance for all CZTSe photovoltaic devices, where the total active area of each device was 0.40 cm2, (measured under 1 sun, AM1.5 irradiation conditions) is presented in Figure 11a and Table 3. Se2 and Se1_Na exhibited the best results among all devices. Se2 had the maximum efficiency (ƞ = 0.16%) and short-circuit current density (Jsc = 1.62 mA/cm2), while Se1_Na showed the highest open current-voltage (Voc = 335 mV) and fill factor (FF = 44.19%). However, the photovoltaic performance of the CZTSe devices (with and without sodium) fabricated in this study was significantly lower compared with that of pure CZTSe devices fabricated using the vacuum-based technique [3,53] and toxic hydrazine-based method [6,54]. The possible reasons for low performance in this study may be as below: (i) the presence of small grains with discontinuous growth and rough surface morphology of the CZTSe samples, (ii) defects, (iii) mismatched energy band alignment at interfaces, (iv) poor crystallinity as increasing the annealing temperature, (v) low or high carrier density, and (vi) formation of MoSe2 layer at the interface of CZTSe and Mo layers. The high series resistance of thick MoSe2 can restrict the ability of the Mo electrode to collect photogenerated hole carriers [15,55,56,57]. This could result in the formation of defective recombination centers, thereby hindering the transport and collection of photogenerated charge carriers and ultimately causing low-performance parameters in the fabricated photovoltaic devices. These findings are being subjected to further investigation in our laboratory to improve the performance of CZTSe-based photovoltaic devices. Figure 11b,c shows cross-sectional images of the photovoltaic devices of Se2 and Se1_Na, respectively.
The following strategies have been used in the literature for improving the efficiency of CZTSe cells: (i) Surface treatments or surface passivation: after sintering, the appearance of a high conducting phase, such as CuxSey on the surface of the CZTSe NPs absorber layer shows a detrimental impact. Therefore, surface treatment, such as KCN etching is necessary to remove those secondary phases. Further, the passivation of CZTSe is necessary. (ii) In order to promote the crystallization, a high-temperature annealing step can be employed, and hence annealing under sulfurization or selenization is essential to increase the grain growth. (iii) The formation of MoSe2 can be reduced by passivation at the back contact interface. (iv) The deposition and pre-heating conditions can be optimized for the evaporation of the solvent and/or additives since too high drying temperature and speed can cause initial cracks in the deposited films. (v) Carrier doping density can be further optimized. (vi) A Cu-deficient (Cu/(Zn + Sn)~0.8) and Zn-rich (Zn/Sn~1.2) compositions are important for highly efficient photovoltaic devices, and therefore, the elemental composition of CZTSe samples requires further optimization [42,57,58].

4. Conclusions

In this study, single-phase CZTSe thin films were deposited using a simple, reproducible, and cost-effective colloidal ink method, that is, a non-vacuum synthesis technique. The kesterite CZTSe nanoparticles and ink were prepared using a mechanochemical milling process. CZTSe thin films were deposited from the prepared nanoparticle inks via spin-coating using inexpensive and innocuous azeotropic solvents (ethanol and MEK) under ambient conditions. The influence of different annealing temperatures (500–550 °C) and sodium incorporation on the photovoltaic performance and material properties, such as surface morphology, chemical composition, phase purity, optical properties, and electrical properties, were evaluated. The outcomes of material analyses support the successful formation of CZTSe in the single phase. The CZTSe thin films possessed small porous grains with discontinuous growth, regardless of the annealing temperature. EDS analysis showed the substantial incorporation of chalcogen (Se) into the absorber films during annealing at different temperatures. All the obtained CZTSe samples showed p-type conductivity with an optical bandgap between 0.82–1.02 eV. The efficiencies of the photovoltaic device fabricated from Se2 and Se1_Na were 0.16% and 0.12%, respectively. This simple and effective fabrication approach provides a low-cost and controlled method to produce CZTSe samples without the use of hazardous and toxic gases, dangerous solvents, or complicated vacuum equipment.

Supplementary Materials

The following supporting information can be downloaded from: https://www.mdpi.com/article/10.3390/nano12091503/s1, Preparation of CZTSe nanopowder, ink, and sodium solution; CZTSe thin-film coating, annealing, and photovoltaic device fabrication; Figure S1: Green synthesis of CZTSe nanoparticle and ink formation via wet ball milling method; Characterization; Table S1: Structural parameter: crystalline (D), strain (ε), dislocation density (δ), and lattice constant (a = b and c) of the CZTSe thin film annealed at different temperatures; Table S2: Relative intensity ratio of CZTSe (112), (204) and (312) plane; Table S3: Raman scattering band position of CZTSe and other secondary phases; Figure S2: Surface and cross-section images and EDS spectra of the Se0 thin film; Figure S3: Surface and cross-section images and EDS spectra of the Se0_Na thin film with the sodium layer; Figure S4: Surface and cross-section images and EDS spectra of the Se3 thin film; Figure S5: Surface and cross-section images and EDS spectra of the Se3_Na thin film with the sodium layer; Table S4: Elemental composition of CZTSe without the sodium layer; Table S5: Elemental composition of CZTSe with the sodium layer. References [59,60,61,62] are cited in the Supplementary Materials.

Author Contributions

Conceptualization, M.S.; investigation, M.S. and V.R.M.R.; data curation, M.S. and V.R.M.R.; analysis and data processing, M.S. and V.R.M.R.; writing—original draft preparation, M.S., V.R.M.R. and B.P.; writing—review and editing, V.R.M.R., W.K.K., C.P. and P.S.; supervision, W.K.K., C.P. and P.S.; funding acquisition, W.K.K., P.S. and C.P. All authors have read and agreed to the published version of the manuscript.

Funding

P.S. (author) acknowledges the IITB-ISRO space technology cell at IIT Bombay for funding this research (project code: 15ISROC002). This research was supported by Priority Research Center Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (grant number 2014R1A6A1031189). C.P. acknowledges a KENTECH Research Grant (KRG2021-01-008).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors also acknowledge that the e-beam evaporator, DC/RF sputtering system, and Hall Measurements at Yeungnam University, Regional Innovation Center (RIC) for Solar Cell/Module, were employed for solar cell fabrication and characterization.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Wibowo, R.A. Powder-to-film approach for fabricating critical raw material-free kesterite Cu2ZnSn (S,Se)4 thin film photovoltaic: A review. Sol. Energy 2018, 176, 157–169. [Google Scholar] [CrossRef]
  2. Luckert, F.; Hamilton, D.I.; Yakushev, M.V.; Beattie, N.S.; Zoppi, G.; Moynihan, M.; Forbes, I.; Karotki, A.V.; Mudryi, A.V.; Grossberg, M.; et al. Optical properties of high quality Cu2ZnSnSe4 thin films. Appl. Phys. Lett. 2011, 99, 062104. [Google Scholar] [CrossRef] [Green Version]
  3. Lee, Y.S.; Gershon, T.; Gunawan, O.; Todorov, T.K.; Gokmen, T.; Virgus, Y.; Guha, S. Cu2ZnSnSe4 thin-film solar cells by thermal co-evaporation with 11.6% efficiency and improved minority carrier diffusion length. Adv. Energy Mater. 2015, 5, 1401372. [Google Scholar] [CrossRef]
  4. Li, X.; Zhuang, D.; Zhang, N.; Zhao, M.; Yu, X.; Liu, P.; Wei, Y.; Ren, G. Achieving 11.95% efficient Cu2ZnSnSe4 solar cells fabricated by sputtering a Cu–Zn–Sn–Se quaternary compound target with a selenization process. J. Mater. Chem. A 2019, 7, 9948–9957. [Google Scholar] [CrossRef]
  5. Brammertz, G.; Buffière, M.; Oueslati, S.; ElAnzeery, H.; Ben Messaoud, K.; Sahayaraj, S.; Köble, C.; Meuris, M.; Poortmans, J. Characterization of defects in 9.7% efficient Cu2ZnSnSe4-CdS-ZnO solar cells. Appl. Phys. Lett. 2013, 103, 163904. [Google Scholar] [CrossRef]
  6. Bag, S.; Gunawan, O.; Gokmen, T.; Zhu, Y.; Todorov, T.K.; Mitzi, D.B. Low band gap liquid-processed CZTSe solar cell with 10.1% efficiency. Energy Environ. Sci. 2012, 5, 7060–7065. [Google Scholar] [CrossRef]
  7. Jeon, J.O.; Lee, K.D.; Seul Oh, L.; Seo, S.W.; Lee, D.K.; Kim, H.; Jeong, J.H.; Ko, M.J.; Kim, B.; Son, H.J. Highly efficient copper–zinc–tin–selenide (CZTSe) solar cells by electrodeposition. ChemSusChem 2014, 7, 1073–1077. [Google Scholar] [CrossRef]
  8. Tiwari, K.J.; Ren, M.-Q.; Vajandar, S.K.; Osipowicz, T.; Subrahmanyam, A.; Malar, P. Mechanochemical bulk synthesis and e-beam growth of thin films of Sb2Se3 photovoltaic absorber. Sol. Energy 2018, 160, 56–63. [Google Scholar] [CrossRef]
  9. Tiwari, K.J.; Kumar, D.P.; Mallik, R.C.; Malar, P. Ball mill synthesis of bulk quaternary Cu2ZnSnSe4 and thermoelectric studies. J. Electron. Mater. 2017, 46, 30–39. [Google Scholar] [CrossRef]
  10. Rohini, M.; Reyes, P.; Velumani, S.; Latha, M.; Becerril-Juarez, I.; Asomoza, R. Parametric optimization of mechanochemical process for synthesis of Cu (In, Ga)0.5Se2 nanoparticles. Mater. Sci. Semicond. Process. 2015, 37, 151–158. [Google Scholar] [CrossRef]
  11. Goyal, D.; Goyal, C.; Ikeda, H.; Malar, P. Role of growth temperature in photovoltaic absorber CuSbSe2 deposition through e-beam evaporation. Mater. Sci. Semicond. Process. 2020, 108, 104874. [Google Scholar] [CrossRef]
  12. Shyju, T.; Anandhi, S.; Suriakarthick, R.; Gopalakrishnan, R.; Kuppusami, P. Mechanosynthesis, deposition and characterization of CZTS and CZTSe materials for solar cell applications. J. Solid State Chem. 2015, 227, 165–177. [Google Scholar] [CrossRef]
  13. Tiwari, K.J.; Mallik, R.C.; Malar, P. Raman studies of Ball mill synthesized bulk Cu2ZnSnSe4. In AIP Conference Proceedings; AIP Publishing LLC: Bhubaneswar, Odisha, India, 2017; Volume 1832, p. 060019. [Google Scholar]
  14. Goyal, D.; Malar, P. Dry mill route for synthesis of single phase bulk and e-beam growth of thin films of Cu2ZnSnSe4 for photovoltaic applications. J. Alloy. Compd. 2020, 846, 156464. [Google Scholar] [CrossRef]
  15. Liu, Y.; Xu, X.; Liu, K.; Liu, H. Synthesis of Cu2ZnSnSe4 thin-film solar cells from nanoparticles by a non-vacuum mechanical ball milling and rapid thermal processing. Micro Nano Lett. 2020, 15, 887–891. [Google Scholar] [CrossRef]
  16. Tampo, H.; Kim, S.; Nagai, T.; Shibata, H. Sodium incorporation effect on morphological and photovoltaic properties for Cu2ZnSnSe4 solar cells. Jpn. J. Appl. Phys. 2020, 59, SCCD06. [Google Scholar] [CrossRef] [Green Version]
  17. Kim, J.; Kim, G.Y.; Nguyen, T.T.T.; Yoon, S.; Kim, Y.K.; Lee, S.Y.; Kim, M.; Cho, D.H.; Chung, Y.D.; Lee, J.H.; et al. Sodium-assisted passivation of grain boundaries and defects in Cu2ZnSnSe4 thin films. Phys. Chem. Chem. Phys. 2020, 22, 7597–7605. [Google Scholar] [CrossRef]
  18. Rehan, M.; Cho, A.; Amare, A.M.; Kim, K.; Yun, J.H.; Cho, J.S.; Park, J.H.; Gwak, J.; Shin, D. Defect passivation in Cu2ZnSnSe4 thin-film solar cells by novel sodium doping. Sol. Energy Mater Sol. Cells 2021, 228, 111138. [Google Scholar] [CrossRef]
  19. Jackson, P.; Wuerz, R.; Hariskos, D.; Lotter, E.; Witte, W.; Powalla, M. Effects of heavy alkali elements in Cu (In, Ga)Se2 solar cells with efficiencies up to 22.6%. Phys. Status Solidi Rapid Res. Lett. 2016, 10, 583–586. [Google Scholar] [CrossRef] [Green Version]
  20. Lin, S.; Liu, W.; Zhang, Y.; Cheng, S.; Fan, Y.; Zhou, Z.; He, Q.; Zhang, Y.; Sun, Y. Adjustment of alkali element incorporations in Cu (In, Ga) Se2 thin films with wet chemistry Mo oxide as a hosting reservoir. Sol. Energy Mater Sol. Cells 2018, 174, 16–24. [Google Scholar] [CrossRef]
  21. Yoon, J.H.; Kim, J.H.; Kim, W.M.; Park, J.K.; Baik, Y.J.; Seong, T.Y.; Jeong, J.h. Electrical properties of CIGS/Mo junctions as a function of MoSe2 orientation and Na doping. Prog. Photovolt. Res. Appl. 2014, 22, 90–96. [Google Scholar] [CrossRef]
  22. Hsu, C.H.; Su, Y.S.; Wei, S.Y.; Chen, C.H.; Ho, W.H.; Chang, C.; Wu, Y.H.; Lin, C.J.; Lai, C.H. Na-induced efficiency boost for Se-deficient Cu (In, Ga) Se2 solar cells. Prog. Photovolt.: Res. Appl. 2015, 23, 1621–1629. [Google Scholar] [CrossRef]
  23. Sahu, M.; Reddy, V.R.M.; Kim, B.; Patro, B.; Park, C.; Kim, W.K.; Sharma, P. Fabrication of Cu2ZnSnS4 Light Absorber Using a Cost-Effective Mechanochemical Method for Photovoltaic Applications. Materials 2022, 15, 1708. [Google Scholar] [CrossRef] [PubMed]
  24. Kadlag, K.P.; Rao, M.J.; Nag, A. Ligand-free, colloidal, and luminescent metal sulfide nanocrystals. J. Phys. Chem. Lett. 2013, 4, 1676–1681. [Google Scholar] [CrossRef]
  25. Huang, T.J.; Yin, X.; Tang, C.; Qi, G.; Gong, H. A low-cost, ligand exchange-free strategy to synthesize large-grained Cu2ZnSnS4 thin-films without a fine-grain underlayer from nanocrystals. J. Mater. Chem. A 2015, 3, 17788–17796. [Google Scholar] [CrossRef]
  26. Nag, A.; Kovalenko, M.V.; Lee, J.-S.; Liu, W.; Spokoyny, B.; Talapin, D.V. Metal-free inorganic ligands for colloidal nanocrystals: S2–, HS–, Se2–, HSe–, Te2–, HTe–, TeS32–, OH–, and NH2– as surface ligands. J. Am. Chem. Soc. 2011, 133, 10612–10620. [Google Scholar] [CrossRef] [PubMed]
  27. Prajapat, R.; Sharma, Y. Morphological characterization and microstructural study of Cu2ZnSnSe4 thin films with compositional variation. Mater. Res. Express 2019, 6, 116459. [Google Scholar] [CrossRef]
  28. Islam, M.; Rahman, K.; Haque, F.; Akhtaruzzaman, M.; Alam, M.; Alothman, Z.; Sopian, K.; Amin, N. Properties of low temperature vacuum annealed CZTS thin films deposited on polymer substrate. Chalcogenide Lett. 2014, 11, 233–239. [Google Scholar]
  29. Singh, A.K.; Aggarwal, G.; Singh, R.K.; Klein, T.R.; Das, C.; Neergat, M.; Kavaipatti, B.; van Hest, M.F.M. Synthesis of CZTS/Se and Their Solid Solution from Electrodeposited Cu–Sn–Zn Metal Precursor: A Study of S and Se Replacement Reaction. ACS Appl. Energy Mater 2018, 1, 3351–3358. [Google Scholar] [CrossRef]
  30. Shin, B.; Zhu, Y.; Bojarczuk, N.A.; Jay Chey, S.; Guha, S. Control of an interfacial MoSe2 layer in Cu2ZnSnSe4 thin film solar cells: 8.9% power conversion efficiency with a TiN diffusion barrier. Appl. Phys. Lett. 2012, 101, 053903. [Google Scholar] [CrossRef]
  31. Pareek, D.; Balasubramaniam, K.; Sharma, P. Synthesis and characterization of bulk Cu2ZnSnX4 (X: S, Se) via thermodynamically supported mechano-chemical process. Mater. Charact. 2015, 103, 42–49. [Google Scholar] [CrossRef]
  32. Amiri, N.B.M.; Postnikov, A. Electronic structure and lattice dynamics in kesterite-type Cu2ZnSnSe4 from first-principles calculations. Phys. Rev. B 2010, 82, 205204. [Google Scholar] [CrossRef]
  33. Wang, W.; Shen, H.; Wong, L.H.; Su, Z.; Yao, H.; Li, Y. A 4.92% efficiency Cu2ZnSnS4 solar cell from nanoparticle ink and molecular solution. RSC Adv. 2016, 6, 54049–54053. [Google Scholar] [CrossRef]
  34. Rehan, M.; Jeon, H.; Cho, Y.; Cho, A.; Kim, K.; Cho, J.-S.; Yun, J.H.; Ahn, S.; Gwak, J.; Shin, D. Fabrication and characterization of Cu2ZnSnSe4 thin-film solar cells using a single-stage Co-evaporation method: Effects of film growth temperatures on device performances. Energies 2020, 13, 1316. [Google Scholar] [CrossRef] [Green Version]
  35. Molla, A.; Sahu, M.; Kumar, Y.; Hussain, S. Soft template mediated synthesis of Bi–In–Zn–S and its efficient visible-light-driven decomposition of methylene blue. RSC Adv. 2015, 5, 41941–41948. [Google Scholar] [CrossRef] [Green Version]
  36. Molla, A.; Sahu, M.; Hussain, S. Under dark and visible light: Fast degradation of methylene blue in the presence of Ag–In–Ni–S nanocomposites. J. Mater. Chem. A 2015, 3, 15616–15625. [Google Scholar] [CrossRef] [Green Version]
  37. Marcos, M.A.; Cabaleiro, D.; Guimarey, M.J.; Comuñas, M.J.; Fedele, L.; Fernández, J.; Lugo, L. PEG 400-based phase change materials nano-enhanced with functionalized graphene nanoplatelets. Nanomaterials 2018, 8, 16. [Google Scholar] [CrossRef] [Green Version]
  38. Liu, Y.; Gu, J.; Zhang, J.; Yu, F.; Wang, J.; Nie, N.; Li, W. LiFePO4 nanoparticles growth with preferential (010) face modulated by Tween-80. Rsc Adv. 2015, 5, 9745–9751. [Google Scholar] [CrossRef]
  39. Indubala, E.; Sarveshvaran, S.; Sudha, V.; Mamajiwala, A.Y.; Harinipriya, S. Secondary phases and temperature effect on the synthesis and sulfurization of CZTS. Sol. Energy 2018, 173, 215–224. [Google Scholar] [CrossRef]
  40. Kishore, R.S.; Pappenberger, A.; Dauphin, I.B.; Ross, A.; Buergi, B.; Staempfli, A.; Mahler, H.-C. Degradation of polysorbates 20 and 80: Studies on thermal autoxidation and hydrolysis. J. Pharm. Sci. 2011, 100, 721–731. [Google Scholar] [CrossRef]
  41. Pramono, E.; Utomo, S.; Wulandari, V.; Clegg, F. The effect of polyethylene glycol Mw 400 and 600 on stability of Shellac Waxfree. In J. Phys. Conf. Ser. IOP Publ. 2016, 7, 012054. [Google Scholar]
  42. Tang, D.; Wang, Q.; Liu, F.; Zhao, L.; Han, Z.; Sun, K.; Lai, Y.; Li, J.; Liu, Y. An alternative route towards low-cost Cu2ZnSnS4 thin film solar cells. Surf. Coat. Technol. 2013, 232, 53–59. [Google Scholar] [CrossRef] [Green Version]
  43. Chen, J.; Wang, F.; Yang, B.; Peng, X.; Chen, Q.; Zou, J.; Dou, X. Fabrication of Cu2ZnSnS4 thin films based on facile nanocrystals-printing approach with rapid thermal annealing (RTA) process. Coatings 2019, 9, 130. [Google Scholar] [CrossRef] [Green Version]
  44. Kaupmees, L.; Altosaar, M.; Volobujeva, O.; Raadik, T.; Grossberg, M.; Danilson, M.; Mellikov, E.; Barvinschi, P. Isothermal and two-temperature zone selenization of Mo layers. Adv. Mater. Sci. Eng. 2012, 2012, 345762. [Google Scholar] [CrossRef] [Green Version]
  45. Li, J.; Chen, G.; Xue, C.; Jin, X.; Liu, W.; Zhu, C. Cu2ZnSnS4− xSex solar cells fabricated with precursor stacked layer ZnS/Cu/SnS by a CBD method. Sol. Energy Mater Sol. Cells 2015, 137, 131–137. [Google Scholar] [CrossRef]
  46. Amal, M.I.; Kim, K.H. Crystallization of kesterite Cu2ZnSnS4 prepared by the sulfurization of sputtered Cu–Zn–Sn precursors. Thin Solid Film. 2013, 534, 144–148. [Google Scholar] [CrossRef]
  47. Jirage, S.; Pagare, P.; Garadkar, K.; Bhuse, V. Structural and morphological studies of chemically deposited nanocrystalline and nano-flower like Cu2ZnSnSe4 thin films. Mater. Today Proc. 2021, 45, 3950–3954. [Google Scholar] [CrossRef]
  48. Olgar, M.A.; Başol, B.; Atasoy, Y.; Tomakin, M.; Aygun, G.; Ozyuzer, L.; Bacaksız, E. Effect of heat treating metallic constituents on the properties of Cu2ZnSnSe4 thin films formed by a two-stage process. Thin Solid Film. 2017, 624, 167–174. [Google Scholar] [CrossRef]
  49. Ito, K.; Nakazawa, T. Electrical and optical properties of stannite-type quaternary semiconductor thin films. Jpn. J. Appl. Phys. 1988, 27, 2094. [Google Scholar] [CrossRef]
  50. Saragih, A.D.; Wubet, W.; Abdullah, H.; Abay, A.K.; Kuo, D.-H. Characterization of Ag-doped Cu2ZnSnSe4 bulks material and their application as thin film semiconductor in solar cells. Mater. Sci. Eng. B 2017, 225, 45–53. [Google Scholar] [CrossRef]
  51. Chen, D.; Zhao, Y.; Chen, Y.; Wang, B.; Wang, Y.; Zhou, J.; Liang, Z. Hot-injection synthesis of Cu-doped Cu2ZnSnSe4 nanocrystals to reach thermoelectric zT of 0.70 at 450 C. ACS Appl. Mater. Interfaces 2015, 7, 24403–24408. [Google Scholar] [CrossRef]
  52. Khadka, D.B.; Kim, S.; Kim, J. Ge-alloyed CZTSe thin film solar cell using molecular precursor adopting spray pyrolysis approach. RSC Adv. 2016, 6, 37621–37627. [Google Scholar] [CrossRef]
  53. Li, J.; Huang, Y.; Huang, J.; Liang, G.; Zhang, Y.; Rey, G.; Guo, F.; Su, Z.; Zhu, H.; Cai, L. Defect Control for 12.5% Efficiency Cu2ZnSnSe4 Kesterite Thin-Film Solar Cells by Engineering of Local Chemical Environment. Adv. Mater. 2020, 32, 2005268. [Google Scholar] [CrossRef] [PubMed]
  54. Bag, S.; Gunawan, O.; Gokmen, T.; Zhu, Y.; Mitzi, D.B. Hydrazine-processed Ge-substituted CZTSe solar cells. Chem. Mater. 2012, 24, 4588–4593. [Google Scholar] [CrossRef]
  55. Gu, E.; Yan, C.; Liu, F.; Liu, Y.; Su, Z.; Zhang, K.; Chen, Z.; Li, J.; Liu, Y. Cu2ZnSnS4 thin film solar cells from coated nanocrystals ink. J. Mater. Sci. Mater. 2015, 26, 1932–1939. [Google Scholar] [CrossRef]
  56. Agarwal, M.; Patel, P.; Vijayan, O. Electrical studies on (Mo/W)Se2 single crystals. I. Electrical resistivity. Phys. Status Solidi 1983, 78, 133–136. [Google Scholar] [CrossRef]
  57. Sahu, M.; Reddy, V.R.M.; Park, C.; Sharma, P. Review article on the lattice defect and interface loss mechanisms in kesterite materials and their impact on solar cell performance. Sol. Energy 2021, 230, 13–58. [Google Scholar] [CrossRef]
  58. Shi, C.; Shi, G.; Chen, Z.; Yang, P.; Yao, M. Deposition of Cu2ZnSnS4 thin films by vacuum thermal evaporation from single quaternary compound source. Mater. Lett. 2012, 73, 89–91. [Google Scholar] [CrossRef]
  59. Altosaar, M.; Raudoja, J.; Timmo, K.; Danilson, M.; Grossberg, M.; Krustok, J.; Mellikov, E. Cu2Zn1–xCdxSn(Se1–y Sy)4 solid solutions as absorber materials for solar cells. Phys. Status Solidi (A) 2008, 205, 167–170. [Google Scholar] [CrossRef]
  60. Redinger, A.; Hönes, K.; Fontané, X.; Izquierdo-Roca, V.; Saucedo, E.; Valle, N.; Pérez-Rodríguez, A.; Siebentritt, S. Detection of a ZnSe secondary phase in coevaporated Cu2ZnSnSe4 thin films. Appl. Phys.Lett. 2011, 98, 101907. [Google Scholar] [CrossRef]
  61. Kim, Y.; Choi, I.-H. High pressure Raman scattering of a co-evaporated Cu2SnSe3 thin film. Thin SolidFilm. 2018, 647, 9–12. [Google Scholar] [CrossRef]
  62. Chihi, A.; Bessais, B. Synthesis and characterization of Cu2SnSe3 thin films by electrodeposition route. Superlattices Microstruct. 2016, 97, 287–297. [Google Scholar] [CrossRef]
Nanomaterials 12 01503 g001 550
Figure 1. (a) Zeta potential and (b) DLS of CZTSe ink.
Figure 1. (a) Zeta potential and (b) DLS of CZTSe ink.
Nanomaterials 12 01503 g001
Nanomaterials 12 01503 g002 550
Figure 2. XRD pattern of CZTSe thin films (a) without and (b) with sodium layer.
Figure 2. XRD pattern of CZTSe thin films (a) without and (b) with sodium layer.
Nanomaterials 12 01503 g002
Nanomaterials 12 01503 g003 550
Figure 3. Raman Spectra of CZTSe thin films: (a) As-synthesized CZTSe NP, (b) as-deposited CZTSe thin film (Se0), (c) Se1 (annealed at 500 °C), (d) Se2 (annealed at 520 °C), and (e) Se3 (annealed at 550 °C).
Figure 3. Raman Spectra of CZTSe thin films: (a) As-synthesized CZTSe NP, (b) as-deposited CZTSe thin film (Se0), (c) Se1 (annealed at 500 °C), (d) Se2 (annealed at 520 °C), and (e) Se3 (annealed at 550 °C).
Nanomaterials 12 01503 g003
Nanomaterials 12 01503 g004 550
Figure 4. FT-IR spectra of (a) Tween-80 and PEG-400, and (b) CZTSe thin films.
Figure 4. FT-IR spectra of (a) Tween-80 and PEG-400, and (b) CZTSe thin films.
Nanomaterials 12 01503 g004
Nanomaterials 12 01503 g005 550
Figure 5. Surface and cross-section images and EDS spectra of Se1 thin film.
Figure 5. Surface and cross-section images and EDS spectra of Se1 thin film.
Nanomaterials 12 01503 g005
Nanomaterials 12 01503 g006 550
Figure 6. Surface and cross-section images and EDS spectra of Se2 thin film.
Figure 6. Surface and cross-section images and EDS spectra of Se2 thin film.
Nanomaterials 12 01503 g006
Nanomaterials 12 01503 g007 550
Figure 7. Surface and cross-section images and EDS spectra of Se1_Na thin film with sodium layer.
Figure 7. Surface and cross-section images and EDS spectra of Se1_Na thin film with sodium layer.
Nanomaterials 12 01503 g007
Nanomaterials 12 01503 g008 550
Figure 8. Surface and cross-section images and EDS spectra of Se2_Na thin film with sodium layer.
Figure 8. Surface and cross-section images and EDS spectra of Se2_Na thin film with sodium layer.
Nanomaterials 12 01503 g008
Nanomaterials 12 01503 g009 550
Figure 9. Bulk XRD patterns of CZTSe thin films (a) without and (b) with sodium layer.
Figure 9. Bulk XRD patterns of CZTSe thin films (a) without and (b) with sodium layer.
Nanomaterials 12 01503 g009
Nanomaterials 12 01503 g010 550
Figure 10. (a) Transmission spectra and (b) bandgap of CZTSe thin films.
Figure 10. (a) Transmission spectra and (b) bandgap of CZTSe thin films.
Nanomaterials 12 01503 g010
Nanomaterials 12 01503 g011 550
Figure 11. (a) J-V curve of CZTSe photovoltaic device under AM 1.5G illumination, and cross-section image of (b) Se2 and (c) Se1_Na photovoltaic devices.
Figure 11. (a) J-V curve of CZTSe photovoltaic device under AM 1.5G illumination, and cross-section image of (b) Se2 and (c) Se1_Na photovoltaic devices.
Nanomaterials 12 01503 g011
Table
Table 1. Elemental composition of CZTSe without and with sodium layer.
Table 1. Elemental composition of CZTSe without and with sodium layer.
Sl No.Sample NameCu/Zn + SnZn/SnSe/(Cu + Zn + Sn)
1Se01.051.070.86
2Se10.951.190.85
3Se21.071.020.89
4Se30.911.320.92
5Se0_Na1.120.821.03
6Se1_Na1.220.830.89
7Se2_Na1.170.780.92
8Se3_Na1.121.050.98
Table
Table 2. Electrical properties of CZTS thin films with and without Na layer.
Table 2. Electrical properties of CZTS thin films with and without Na layer.
Sl. No.Sample NameCarrier Conc. (cm−3)Mobility cm2/V·sResistivity
(Ω cm)
1Se02.10 × 10181.212.47
2Se11.07 × 10181.334.41
3Se21.05 × 10181.543.87
4Se31.80 × 10181.133.06
5Se0_Na1.13 × 10181.124.96
6Se1_Na2.04 × 10176.714.56
7Se2_Na6.14 × 10171.765.77
8Se3_Na1.61 × 10193.860.101
Table
Table 3. Photovoltaic properties of CZTSe thin films with and without sodium layer.
Table 3. Photovoltaic properties of CZTSe thin films with and without sodium layer.
Sl No.Sample NameVoc (mV)Jsc (mA/cm2)FF (%)η (%)
1SC-Se12921.3736.560.14
2SC-Se22661.6237.790.16
3SC-Se32930.8541.430.10
4SC-Se1_Na3350.8644.190.12
5SC-Se2_Na3000.7641.320.10
6SC-Se3_Na1821.6033.550.09
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Sahu, M.; Minnam Reddy, V.R.; Patro, B.; Park, C.; Kim, W.K.; Sharma, P. Synthesis and Characterization of Cu2ZnSnSe4 by Non-Vacuum Method for Photovoltaic Applications. Nanomaterials 2022, 12, 1503. https://doi.org/10.3390/nano12091503

AMA Style

Sahu M, Minnam Reddy VR, Patro B, Park C, Kim WK, Sharma P. Synthesis and Characterization of Cu2ZnSnSe4 by Non-Vacuum Method for Photovoltaic Applications. Nanomaterials. 2022; 12(9):1503. https://doi.org/10.3390/nano12091503

Chicago/Turabian Style

Sahu, Meenakshi, Vasudeva Reddy Minnam Reddy, Bharati Patro, Chinho Park, Woo Kyoung Kim, and Pratibha Sharma. 2022. "Synthesis and Characterization of Cu2ZnSnSe4 by Non-Vacuum Method for Photovoltaic Applications" Nanomaterials 12, no. 9: 1503. https://doi.org/10.3390/nano12091503

APA Style

Sahu, M., Minnam Reddy, V. R., Patro, B., Park, C., Kim, W. K., & Sharma, P. (2022). Synthesis and Characterization of Cu2ZnSnSe4 by Non-Vacuum Method for Photovoltaic Applications. Nanomaterials, 12(9), 1503. https://doi.org/10.3390/nano12091503

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop