Investigations of the structural, optoelectronic and band alignment properties of Cu2ZnSnS4 prepared by hot-injection method towards low-cost photovoltaic applications

Cu2ZnSnS4 is a promising, versatile and inexpensive quaternary semiconductor with suitable optoelectronic properties for solar energy conversion. In this work, we report the synthesis of CZTS nanocrystals (NCs) using low-cost homemade hot-injection method. Oleylamine was used as both the binder and stabilizer for the CZTS NCs during the growth process. Detailed investigation of the influence of sulphur concentration and reaction temperature on the structural, stoichiometric, morphological, and optoelectronic attributes of CZTS NCs was carried out. The XRD, Raman, and TEM measurements confirm the formation of phase-pure tetragonal kesterite CZTS NCs. The synthesized CZTS NCs exhibit particle sizes in the range of 15–30 nm and display strong optical absorption in the visible region. The nearly optimal chemical composition of the CZTS NCs was confirmed by energy dispersive X-ray spectroscopy. UV–Visible spectroscopy and electrochemical measurements predicts the band gap of the CZTS NCs in the range of 1.3–1.6 eV, which is very close to the optimum values for the fabrication of single junction solar cells. The estimated conduction band offset (CBO) and valence band offset (VBO) of the CZTS-3M/CdS heterostructure are predicted as 0.11 and 0.98 eV, respectively, whereas for CZTS-225 °C/CdS heterostructure, CBO and VBO are 0.10 and 1.0 eV, respectively. The small conduction band offset measured at the CZTS/CdS interface are encouraging characteristics for the carrier transport and the deeper understating of band alignment and interface properties provides a hopeful approach for designing higher efficiency and more efficient carrier separation in CZTS solar cells

Photoelectrochemical investigation on the cadmium sulfide (CdS) thin films prepared using spin coating technique

Photoelectrochemical cell technology is one of the simplest technologies, which converts light energy directly into electricity. The synthesis of cadmium sulfide (CdS) nanocrystals (NCs) was performed by the facile hot injection method. The NCs were characterized by different techniques such as XRD, Raman, UV-Vis, FESEM, and XPS. The XRD pattern confirms the phase pure hexagonal CdS NCs. The band gap of NCs calculated from the UV-Visible spectrum is at 2.40 eV, indicating good absorption in the visible spectrum. XPS analysis confirmed the presence of individual elements in CdS NCs. The CdS thin-films having different thicknesses were prepared on FTO substrates using the spin coating technique. Photoelectrochemical (PEC) investigation of CdS NCs thin-films photoelectrodes was performed by varying its thickness. The increase in the thickness of thin-films increased photocurrent density

Ternary Cu2SnS3: synthesis, structure, photoelectrochemical activity, and heterojunction band offset and alignment

Ternary Cu2SnS3 (CTS) is an attractive nontoxic and earth-abundant absorber material with suitable optoelectronic properties for cost-effective photoelectrochemical applications. Herein, we report the synthesis of high-quality CTS nanoparticles (NPs) using a low-cost facile hot injection route, which is a very simple and nontoxic synthesis method. The structural, morphological, optoelectronic, and photoelectrochemical (PEC) properties and heterojunction band alignment of the as-synthesized CTS NPs have been systematically characterized using various state-of-the-art experimental techniques and atomistic first-principles density functional theory (DFT) calculations. The phase-pure CTS NPs confirmed by X-ray diffraction (XRD) and Raman spectroscopy analyses have an optical band gap of 1.1 eV and exhibit a random distribution of uniform spherical particles with size of approximately 15–25 nm as determined from high-resolution transmission electron microscopy (HR-TEM) images. The CTS photocathode exhibits excellent photoelectrochemical properties with PCE of 0.55% (fill factor (FF) = 0.26 and open circuit voltage (Voc) = 0.54 V) and photocurrent density of −3.95 mA/cm2 under AM 1.5 illumination (100 mW/cm2). Additionally, the PEC activities of CdS and ZnS NPs are investigated as possible photoanodes to create a heterojunction with CTS to enhance the PEC activity. CdS is demonstrated to exhibit a higher current density than ZnS, indicating that it is a better photoanode material to form a heterojunction with CTS. Consistently, we predict a staggered type-II band alignment at the CTS/CdS interface with a small conduction band offset (CBO) of 0.08 eV compared to a straddling type-I band alignment at the CTS/ZnS interface with a CBO of 0.29 eV. The observed small CBO at the type-II band aligned CTS/CdS interface points to efficient charge carrier separation and transport across the interface, which are necessary to achieve enhanced PEC activity. The facile CTS synthesis, PEC measurements, and heterojunction band alignment results provide a promising approach for fabricating next-generation Cu-based light-absorbing materials for efficient photoelectrochemical applications

Solution-processed Cd-substituted CZTS nanocrystals for sensitized liquid junction solar cells

The Earth-abundant kesterite Cu2ZnSnS4 (CZTS) exhibits outstanding structural, optical, and electronic properties for a wide range of optoelectronic applications. However, the efficiency of CZTS thin-film solar cells is limited due to range of factors, including electronic disorder, secondary phases, and the presence of anti-site defects, which is key factor limiting the Voc. The complete substitution of Zn lattice sites in CZTS nanocrystals (NCs) with Cd atoms offers a promising approach to overcome several of these intrinsic limitations. Herein, we investigate the effects of substitution of Cd2+ into Zn2+ lattice sites in CZTS NCs through a facile solution-based method. The structural, morphological, optoelectronic, and power conversion efficiencies (PCEs) of the NCs synthesized have been systematically characterized using various experimental techniques, and the results are corroborated by first-principles density functional theory (DFT) calculations. The successful substitution of Zn by Cd is demonstrated to induce a structural transformation from the kesterite phase to the stannite phase, which results in the bandgap reducing from 1.51 eV (kesterite) to 1.1 eV (stannite), which is closer to the optimum bandgap value for outdoor photovoltaic applications. Furthermore, the PCE of the novel Cd-substituted liquid junction solar cell underwent a four-fold increase, reaching 1.1%. These results highlight the importance of substitutional doping strategies in optimizing existing CZTS-based materials to achieve improved device characteristics

Structural, optoelectronic, and photoelectrochemical investigation of CdSe NC's prepared by hot injection method

In this study, we report the synthesis and characterization of CdSe nanocrystals (NC's) by facile Hot injection (HI) method. The formation of CdSe NC's was confirmed by x-ray diffraction (XRD), Raman spectroscopy, and x-ray photoelectron spectroscopy (XPS). The optical properties were analyzed by UV-visible and photoluminescence (PL) spectroscopy shows an excitonic peak at 600 nm in UV-Vis spectra corresponds to the band gap of ~ 2 eV favorable for optoelectronic device applications. The Photoelectrochemical (PEC) performance of CdSe thin film prepared by spin coating demonstrates a rise of photocurrent density (Jsc = 0.081 µAcm-2) after illumination. The Mott-Schottky (MS) and electrochemical impedance spectroscopy (EIS) measurements were further carried out to understand intrinsic properties namely the type of conductivity, flat band potential, charge carrier density (ND), charge transfer resistance, and recombination lifetime. The n-type conductivity, the charge carrier density of ND = 1.292 x 1016 cm-2, and recombination lifetime of 32.4 µs suggest the ideal behavior of CdSe NC's for device quality photoelectrodes

Solution-processed Cd-substituted CZTS nanocrystals for sensitized liquid junction solar cells

The Earth-abundant kesterite Cu2ZnSnS4 (CZTS) exhibits outstanding structural, optical, and electronic properties for a wide range of optoelectronic applications. However, the efficiency of CZTS thin-film solar cells is limited due to a range of factors, including electronic disorder, secondary phases, and the presence of anti-site defects, which is a key factor limiting the Voc. The complete substitution of Zn lattice sites in CZTS nanocrystals (NCs) with Cd atoms offers a promising approach to overcome several of these intrinsic limitations. Herein, we investigate the effects of substituting Cd2+ into Zn2+ lattice sites in CZTS NCs through a facile solution-based method. The structural, morphological, optoelectronic, and power conversion efficiencies (PCEs) of the NCs synthesized have been systematically characterized using various experimental techniques, and the results are corroborated by first-principles density functional theory (DFT) calculations. The successful substitution of Zn by Cd is demonstrated to induce a structural transformation from the kesterite phase to the stannite phase, which results in the bandgap reduction from 1.51 eV (kesterite) to 1.1 eV (stannite), which is closer to the optimum bandgap value for outdoor photovoltaic applications. Furthermore, the PCE of the novel Cd-substituted liquid junction solar cell underwent a four-fold increase, reaching 1.1%. These results highlight the importance of substitutional doping strategies in optimizing existing CZTS-based materials to achieve improved device characteristics