Passivating Grain Boundaries via Graphene Additive for Efficient Kesterite Solar Cells.

Grain boundaries (GBs)-triggered severe non-radiative recombination is recently recognized as the main culprits for carrier loss in polycrystalline kesterite photovoltaic devices. Accordingly, further optimization of kesterite-based thin film solar cells critically depends on passivating the grain interfaces of polycrystalline Cu2 ZnSn(S,Se)4 (CZTSSe) thin films. Herein, 2D material of graphene is first chosen as a passivator to improve the detrimental GBs. By adding graphene dispersion to the CZTSSe precursor solution, single-layer graphene is successfully introduced into the GBs of CZTSSe absorber. Due to the high carrier mobility and electrical conductivity of graphene, GBs in the CZTSSe films are transforming into electrically benign and do not act as high recombination sites for carrier. Consequently, benefitting from the significant passivation effect of GBs, the use of 0.05 wt% graphene additives increases the efficiency of CZTSSe solar cells from 10.40% to 12.90%, one of the highest for this type of cells. These results demonstrate a new route to further increase kesterite-based solar cell efficiency by additive engineering.

An ITO-Free Kesterite Solar Cell.

Photovoltaic thin film solar cells based on kesterite Cu2 ZnSn(S, Se)4 (CZTSSe) have reached 13.8% sunlight-to-electricity conversion efficiency. However, this efficiency is still far from the Shockley-Queisser radiative limit and is hindered by the significant deficit in open circuit voltage (VOC ). The presence of high-density interface states between the absorber layer and buffer or window layer leads to the recombination of photogenerated carriers, thereby reducing effective carrier collection. To tackle this issue, a new window structure ZnO/AgNW/ZnO/AgNW (ZAZA) comprising layers of ZnO and silver nanowires (AgNWs) is proposed. This structure offers a simple and low-damage processing method, resulting in improved optoelectronic properties and junction quality. The ZAZA-based devices exhibit enhanced VOC due to the higher built-in voltage (Vbi ) and reduced interface recombination compared to the usual indium tin oxide (ITO) based structures. Additionally, improved carrier collection is demonstrated as a result of the shortened collection paths and the more uniform carrier lifetime distribution. These advances enable the fabrication of the first ITO-free CZTSSe solar cells with over 10% efficiency without an anti-reflective coating.

Regulating Hetero-Nucleation Enabling Over 14% Efficient Kesterite Solar Cells.

Developing well-crystallized light-absorbing layers remains a formidable challenge in the progression of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. A critical aspect of optimizing CZTSSe lies in accurately governing the high-temperature selenization reaction. This process is intricate and demanding, with underlying mechanisms requiring further comprehension. This study introduces a precursor microstructure-guided hetero-nucleation regulation strategy for high-quality CZTSSe absorbers and well-performing solar cells. The alcoholysis of 2-methoxyethanol (MOE) and the generation of high gas-producing micelles by adding hydrogen chloride (HCl) as a proton additive into the precursor solution are successfully suppressed. This tailored modification of solution components reduces the emission of volatiles during baking, yielding a compact and dense precursor microstructure. The reduced-roughness surface nurtures the formation of larger CZTSSe nuclei, accelerating the ensuing Ostwald ripening process. Ultimately, CZTSSe absorbers with enhanced crystallinity and diminished defects are fabricated, attaining an impressive 14.01% active-area power conversion efficiency. The findings elucidate the influence of precursor microstructure on the selenization reaction process, paving a route for fabricating high-quality kesterite CZTSSe films and high-efficiency solar cells.

11.88% Efficient Flexible Ag-Free CZTSSe Solar Cell: Spontaneously Tailoring the Alkali Metal Level.

Alkali metal is the requirement for highly efficient Cu2ZnSn(S, Se)4 (CZTSSe) solar cells, thus it is crucial to additionally incorporate alkali metal into the absorber layer for flexible solar cells. However, the efficiency of flexible CZTSSe devices reported to date, based on the conventional alkali incorporation strategies, still lags behind those made on rigid substrates. One of the main issues is the inability to control the alkali content and distribution in the absorber layer. Here, a facile alkaline incorporation approach is proposed, effectively regulating the content and distribution of alkali metals in the film. Such a method can spontaneously tailor the alkali metal content to a proper level, thus leading to the suppression of non-radiative recombination and a better carrier transport through the enhanced film quality and the optimized band binding structure. Finally, a champion flexible CZTSSe solar cell with an efficiency of 11.88% is achieved, the highest reported efficiency for a CZTSSe solar cell without noble Ag doping. This study affords an innovative spontaneous alkali-doping design for the preparation of high-performance flexible CZTSSe solar cells and provides a deeper insight into the extent of alkali metal doping.

The Multiple Roles of Na Ions in Highly Efficient CZTSSe Solar Cells.

Sodium (Na) doping is a well-established technique employed in chalcopyrite and kesterite solar cells. While various improvements can be achieved in crystalline quality, electrical properties, or defect passivation of the absorber materials by incorporating Na, a comprehensive demonstration of the desired Na distribution in CZTSSe is still lacking. Herein, a straightforward Na doping approach by dissolving NaCl into the CZTS precursor solution is proposed. It is demonstrated that a favorable Na ion distribution should comprise a precisely controlled Na+ concentration at the front surface and an enhanced distribution within the bottom region of the absorber layer. These findings demonstrated that Na ions play several positive roles within the device, leading to an overall power conversion efficiency of 12.51%.

Introducing Bi2S3 Interlayer to Synergistically Modify Mo Back Contact and Regulate Bulk Defects in Kesterite Solar Cells.

A suitable interlayer between the Mo back electrode and kesterite absorber layer has been proven to have a positive effect on limiting the bulk defects of the absorber by the constitute diffusion. Here, a thin Bi2S3 layer is used as the back-interface intermediate layer for the first time, this innovative approach allows for simultaneous modification of the back contact and reduction of bulk defects, resulting in improving the power conversion efficiency of the kesterite device from 9.66% to 11.8%. The evaporated Bi2O3 thin films turn into the Bi2S3 interlayers after sintering the Cu2ZnSnS4 precursor thin films. The Bi2S3 interlayer can inhibit the decomposition reaction of back contact and suppress the formation of the secondary phases. It can also optimize the Fermi level offset and promote the separation of the photoinduced carriers, resulting from its characteristic of high work function. Besides, a small part of the Bi element can diffuse into Cu2ZnSn(S, Se)4 film and induce the crystal growth and restrain Zn-related defects, which is attributed to forming the low melting-point liquid BiSex phase during the high-temperature selenization process. The conclusions highlight the bifunction of the thin Bi2S3 intermediate layer, which can provide a new approach to improve the photoelectric conversion efficiency of kesterite solar cells.

Oxygen Aspects in the High-Pressure and High-Temperature Sintering of Semiconductor Kesterite Cu2ZnSnS4 Nanopowders Prepared by a Mechanochemically-Assisted Synthesis Method.

We explore the important aspects of adventitious oxygen presence in nanopowders, as well as in the high-pressure and high-temperature-sintered nanoceramics of semiconductor kesterite Cu2ZnSnS4. The initial nanopowders were prepared via the mechanochemical synthesis route from two precursor systems, i.e., (i) a mixture of the constituent elements (Cu, Zn, Sn, and S), (ii) a mixture of the respective metal sulfides (Cu2S, ZnS, and SnS), and sulfur (S). They were made in each system in the form of both the raw powder of non-semiconducting cubic zincblende-type prekesterite and, after thermal treatment at 500 °C, of semiconductor tetragonal kesterite. Upon characterization, the nanopowders were subjected to high-pressure (7.7 GPa) and high-temperature (500 °C) sintering that afforded mechanically stable black pellets. Both the nanopowders and pellets were extensively characterized, employing such determinations as powder XRD, UV-Vis/FT-IR/Raman spectroscopies, solid-state 65Cu/119Sn NMR, TGA/DTA/MS, directly analyzed oxygen (O) and hydrogen (H) contents, BET specific surface area, helium density, and Vicker's hardness (when applicable). The major findings are the unexpectedly high oxygen contents in the starting nanopowders, which are further revealed in the sintered pellets as crystalline SnO2. Additionally, the pressure-temperature-time conditions of the HP-HT sintering of the nanopowders are shown (in the relevant cases) to result in the conversion of the tetragonal kesterite into cubic zincblende polytype upon decompression.

10.3% Efficient Green Cd-Free Cu2 ZnSnS4 Solar Cells Enabled by Liquid-Phase Promoted Grain Growth.

Small grain size and near-horizontal grain boundaries are known to be detrimental to the carrier collection efficiency and device performance of pure-sulfide Cu2 ZnSnS4 (CZTS) solar cells. However, forming large grains spanning the absorber layer while maintaining high electronic quality is challenging particularly for pure sulfide CZTS. Herein, a liquid-phase-assisted grain growth (LGG) model that enables the formation of large grains spanning across the CZTS absorber without compromising the electronic quality is demonstrated. By introducing a Ge-alloyed CZTS nanoparticle layer at the bottom of the sputtered precursor, a Cu-rich and Sn-rich liquid phase forms at the high temperature sulfurization stage, which can effectively remove the detrimental near-horizontal grain boundaries and promote grain growth, thus greatly improving the carrier collection efficiency and reducing nonradiative recombination. The remaining liquid phase layer at the rear interface shows a high work function, acting as an effective hole transport layer. The modified morphology greatly increases the short-circuit current density and fill factor, enabling 10.3% efficient green Cd-free CZTS devices. This work unlocks a grain growth mechanism, advancing the morphology control of sulfide-based kesterite solar cells.

Ab Initio Study of Carrier Mobility, Thermodynamic and Thermoelectric Properties of Kesterite Cu2ZnGeS4.

The kesterite Cu2ZnGeS4 (CZGS) has recently gained significant interest in the scientific community. In this work, we investigated the thermodynamic and thermoelectric properties of CZGS by employing the first-principals calculation in association with the quasi-harmonic approximation, Boltzmann transport theory, deformation potential theory, and slack model. We obtained a bandgap of 2.05 eV and high carrier mobility. We found that CZGS exhibits adequate thermoelectric properties as a promising material for thermoelectric applications. The calculated Seebeck coefficient at room temperature is 149 µV·K-1. We also determined the thermal and electrical conductivity, the power factor, and the figure of merit. In addition, the thermodynamic properties such as Debye temperature, entropy, and constant volume heat capacity are estimated. According to our results, it is concluded that the Slack model fails to provide correct values for lattice thermal conductivity in this material.

Application of artificial neural network and global optimization techniques for high throughput modeling of the crystal structure of stannites and kesterites.

This study aims to apply artificial neural networks for the prediction of the lattice parameters of materials with stannite- and kesterite-type structure, and to compare the results of predictions with that obtained in the calculations exploiting the density functional theory. Crystallographic data for 49 compounds with stannite-type structure and for four compounds with the kesterite-type structure are found and, based on it, crystal structures are calculated using the density functional theory (DFT) method in a two-step relaxation procedure for all compounds. An multilayer Perceptron is constructed, which then is trained on gathered crystallographic data. Values predicted by a neural network (lattice parameters) are compared with experimental data and with results of DFT calculations. Moreover, a global optimization method (the Uspex code) is used to find potentially novel crystal structures for investigated chemical compositions. The results are discussed in the term of advantages and disadvantages of each method.

Nanoscale surface potential variation correlates with local S/Se ratio in solution-processed CZTSSe solar cells.

Thin film solar cells made from Cu, Zn, Sn, and S/Se can be processed from solution to yield high-performing kesterite (CZTS or CZTSSe) photovoltaics. We present a microstructural study of solution-deposited CZTSSe films prepared by nanocrystal-based ink approaches using scanning probe microscopy (SPM) and scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). We correlate scanning Kelvin probe microscopy (SKPM) maps of local surface potential with SEM/EDS images of the exact same regions of the film, allowing us to relate observed variations in surface potential to local variations in stoichiometry. Specifically, we find a correlation between surface potential and the S/(S + Se) composition ratio. In particular, we find that regions with high S/(S + Se) ratios are often associated with regions of more negative surface potential and thus higher work function. The change in work function is larger than the expected change in the valence band position with these small changes in sulfur, and thus the data suggest an increase in acceptor-like defects with increasing sulfur. These findings provide new experimental insight into the microscopic relationships between composition, structure, and electronic properties in these promising photovoltaic materials.

Thermogravimetric/Thermal-Mass Spectroscopy Insight into Oxidation Propensity of Various Mechanochemically Made Kesterite Cu2ZnSnS4 Nanopowders.

Thermogravimetry coupled with thermal analysis and quadrupole mass spectroscopy TGA/DTA-QMS were primarily used to assess the oxidation susceptibility of a pool of nanocrystalline powders of the semiconductor kesterite Cu2ZnSnS4 for prospective photovoltaic applications, which were prepared via the mechanochemically assisted synthesis route from two different precursor systems. Each system, as confirmed by XRD patterns, yielded first the cubic polytype of kesterite with defunct semiconductor properties, which, after thermal annealing at 500 °C under neutral gas atmosphere, was converted to the tetragonal semiconductor polytype. The TGA/DTA-QMS determinations up to 1000 °C were carried out under a neutral argon Ar atmosphere and under a dry, oxygen-containing gas mixture of O2:Ar = 1:4 (vol.). The mass spectroscopy data confirmed that under each of the gas atmospheres, a distinctly different, multistep evolution of such oxygen-bearing gaseous compounds as sulfur oxides SO2/SO3, carbon dioxide CO2, and water vapor H2O was taking place. The TGA/DTA changes in correlation with the nature of evolving gases helped in the elucidation of the plausible chemistry linked to kesterite oxidation, both in the stage of nanopowder synthesis/storage at ambient air conditions and during forced oxidation up to 1000 °C in the dry, oxygen-containing gas mixture.

Cd-Free Pure Sulfide Kesterite Cu2 ZnSnS4 Solar Cell with Over 800 mV Open-Circuit Voltage Enabled by Phase Evolution Intervention.

The Cd-free Cu2 ZnSnS4 (CZTS) solar cell is an ideal candidate for producing low-cost clean energy through green materials owing to its inherent environmental friendliness and earth abundance. Nevertheless, sulfide CZTS has long suffered from severe open-circuit voltage (VOC ) deficits, limiting the full exploitation of performance potential and further progress. Here, an effective strategy is proposed to alleviate the nonradiative VOC loss by manipulating the phase evolution during the critical kesterite phase formation stage. With a Ge cap layer on the precursor, premature CZTS grain formation is suppressed at low temperatures, leading to fewer nucleation centers at the initial crystallization stage. Consequently, the CZTS grain formation and crystallization are deferred to high temperatures, resulting in enhanced grain interior quality and less unfavorable grain boundaries in the final film. As a result, a champion efficiency of 10.7% for Cd-free CZTS solar cells with remarkably high VOC beyond 800 mV (63.2% Schockley-Queisser limit) is realized, indicating that nonradiative recombination is effectively inhibited. This strategy may advance other compound semiconductors seeking high-quality crystallization.

Disorder induced band gap lowering in kesterite type Cu2ZnSnSe4and Ag2ZnSnSe4: a first-principles and special quasirandom structures investigation.

Quaternary chalcogenides, i.e. Cu2ZnSnS4, crystallising in the kesterite crystal structure have already been demonstrated as potential building blocks of thin film solar cells, containing only abundant elements and exhibiting power conversion efficiencies of about 14.9% so far. However, due to the potential presence of several structurally similar polymorphs, the unequivocal identification of their ground state crystal structures required the application of more elaborate neutron diffraction experiments. One particular complication arose from the later identified Cu-Zn disorder, present in virtually all thin film samples. Subsequently, it has been shown experimentally that this unavoidable Cu-Zn disorder leads to a band gap lowering in the respective samples. Additional theoretical investigations, mostly based on Monte-Carlo methods, tried to understand the atomistic origin of this disorder induced band gap lowering. Here, we present theoretical results from first-principles calculations based on density functional theory for the disorder induced band gap lowering in kesterite Cu2ZnSnSe4and Ag2ZnSnSe4, where the Cu-Zn and Ag-Zn disorder is modelled via a supercell approach and special quasirandom structures. Results of subsequent analyses of structural, electronic, and optical properties are discussed with respect to available experimental results, and will provide additional insight and knowledge towards the atomistic origin of the observed disorder induced band gap lowering in kesterite type materials.

Facile Tailor on the Surface of Mo Foil Toward High-Efficient Flexible CZTSSe Solar Cells.

Flexible Cu2ZnSn(S,Se)4 (CZTSSe) solar cells is attracting much attention because of their enormous application prospects. However, current flexible CZTSSe solar cells with Mo foil as substrate still suffer from severe back interface problems due to the complexity of substrate surfaces. Herein, a facile approach to tailor the surface of the flexible substrate and modify the back interface between CZTSSe and Mo foil is proposed. The study discloses that a simple polishing can not only improve the wettability of the precursor solution on the substrate unexpectedly and thus improve the quality of the CZTSSe film, but also increase the mechanical stability of the absorber layer grown on Mo foil. The subsequent UV-ozone treatment helps to form a favorite MoO3 layer for efficient CZTSSe devices. Surprisingly, the quasi-ohmic contact is formed between CZTSSe/Mo foil by such combined treatments and thus promoting the carrier collection. Consequently, the efficiency of the flexible CZTSSe solar cell is significantly improved from 4.94% to 10.32% without anti-reflection layer. The bending durability of the cell fabricated on the treated Mo foil is increased greatly. This work discloses that back contact interface is very important for the carrier collection and thus the highly efficient flexible thin film solar cells.

Synergistic Crystallization Modulation and Defects Passivation in Kesterite via Anion-Coordinate Precursor Engineering for Efficient Solar Cells.

It has been validated that enhancing crystallinity and passivating the deep-level defect are critical for improving the device performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Coordination chemistry interactions within the Cu-Zn-Sn-S precursor solution play a crucial role in the management of structural defects and the crystallization kinetics of CZTSSe thin films. Therefore, regulating the coordination environment of anion and cation in the precursor solution to control the formation process of precursor films is a major challenge at present. Herein, a synergetic crystallization modulation and defect passivation method is developed using P2S5 as an additive in the CZTS precursor solution to optimize the coordination structure and improve the crystallization process. The alignment of theoretical assessments with experimental observations confirms the ability of the P2S5 molecule to coordinate with the metal cation sites of CZTS precursor films, especially more liable to the Zn2+, effectively passivating the Zn-related defects, thereby significantly reducing the defect density in CZTSSe absorbers. As a result, the device with a power conversion efficiency of 14.36% has been achieved. This work provides an unprecedented strategy for fabricating high-quality thin films by anion-coordinate regulation and a novel route for realizing efficient CZTSSe solar cells.

Modifying Surface Termination by Bidentate Chelating Strategy Enables 13.77% Efficient Kesterite Solar Cells.

Surfaces display discontinuities in the kesterite-based polycrystalline films can produce large defect densities, including strained and dangling bonds. These physical defects tend to introduce electronic defects and surface states, which can greatly promote nonradiative recombination of electron-hole pairs and damage device performance. Here, an effective chelation strategy is reported to suppress these harmful physical defects related to unterminated Cu, Zn, and Sn sites by modifying the surface of Cu2ZnSn(S,Se)4 (CZTSSe) films with sodium diethyldithiocarbamate (NaDDTC). The conjoint theoretical calculations and experimental results reveal that the NaDDTC molecules can be coordinate to surface metal sites of CZTSSe films via robust bidentate chelating interactions, effectively reducing surface undercoordinated defects and passivating the electron trap states. Consequently, the solar cell efficiency of the NaDDTC-treated device is increased to as high as 13.77% under 100 mW cm-2 illumination, with significant improvement in fill factor and open-circuit voltage. This surface chelation strategy provides strong surface termination and defect passivation for further development and application of kesterite-based photovoltaics.

Unveiling the Role of Ge in CZTSSe Solar Cells by Advanced Micro-To-Atom Scale Characterizations.

Kesterite is an earth-abundant energy material with high predicted power conversion efficiency, making it a sustainable and promising option for photovoltaics. However, a large open circuit voltage Voc deficit due to non-radiative recombination at intrinsic defects remains a major hurdle, limiting device performance. Incorporating Ge into the kesterite structure emerges as an effective approach for enhancing performance by manipulating defects and morphology. Herein, how different amounts of Ge affect the kesterite growth pathways through the combination of advanced microscopy characterization techniques are systematically investigated. The results demonstrate the significance of incorporating Ge during the selenization process of the CZTSSe thin film. At high temperature, the Ge incorporation effectively delays the selenization process due to the formation of a ZnSe layer on top of the metal alloys through decomposition of the Cu-Zn alloy and formation of Cu-Sn alloy, subsequently forming of Cu-Sn-Se phase. Such an effect is compounded by more Ge incorporation that further postpones kesterite formation. Furthermore, introducing Ge mitigates detrimental "horizontal" grain boundaries by increasing the grain size on upper layer. The Ge incorporation strategy discussed in this study holds great promise for improving device performance and grain quality in CZTSSe and other polycrystalline chalcogenide solar cells.

In Situ Vanadium Modification Induced a Back Interfacial Field Passivation Effect toward Efficient Kesterite Solar Cells beyond 11% Efficiency.

Realization of a high-quality back electrode interface (BEI) with suppressed recombination is crucial for Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. To achieve this goal, the construction of a traditional chemical passivation effect has been widely adopted and investigated. However, there is currently a lack of reports concerning the construction of a field passivation effect (FPE) for the BEI. Herein, considering the characteristic of the negligible difference in ionic radius between Mo (0.65 Å) and V (0.64 Å) as well as the presence of one less valence electron compared to Mo, vanadium (V) was employed and in situ incorporated into the MoSe2 interfacial layer during the deposition of the Mo:V electrode and selenization process. This allowed for the establishment of a desirable in situ VI-FPE interface with p-MoSe2:V/p-CZTSSe at the BEI. The p-type characteristic in MoSe2:V is attributed to the presence of the VMo acceptor; notably, the Fermi energy level of MoSe2:V has shifted downward by 0.62 eV compared to MoSe2, thereby facilitating the formation of an optimized band alignment between MoSe2:V and the absorber. Consequently, the photovoltaic parameters of the cell-FPE have experienced a significant increase due to the enhanced carrier transportation efficiency compared to cell-ref, resulting in a remarkable improvement in efficiency from 8.28 to 11.11%.

Interferon gamma (IFN-γ)-sensitive TB aptasensor based on novel chitosan-indium nano-kesterite (χtCITS)-labeled DNA aptamer hairpin technology.

There has been increasing interest in the use of biosensors for diagnosis of infectious diseases such as tuberculosis (TB) due to their simplicity, affordability, and potential for point-of-care application. The incorporation of aptamer molecules and nanomaterials in biosensor fabrication explores the advantages of high-binding affinity and low immunogenicity of aptamers as well as the high surface-to-volume ratio of nanomaterials, for increased aptasensor performance. In this work, we employed a novel microwave-synthesized copper indium tin sulfide (CITS) substituted-kesterite nanomaterial, together with a natural biopolymer (chitosan), for signal amplification and increased loading of aptamer molecules. Study of the optical properties of CITS nanomaterials showed strong absorption in the UV region characteristic of kesterite semiconductor nanomaterials. X-ray diffraction analysis confirmed the presence of the kesterite phase with average crystallite size of 6.188 nm. Fabrication of interferon-gamma (IFN-γ) TB aptasensor with a chitosan-CITS nanocomposite (χtCITS) increased the aptasensor's electrochemical properties by 77.5 % and improved aptamer loading by 73.7 %. The aptasensor showed excellent sensitivity to IFN-γ concentrations with limit of detection of 6885 fg/mL (405 fM) and linear range of 850-17000 fg/mL (50 - 1000 fM). The aptasensor also exhibited excellent storage and electrochemical stability, with good selectivity towards IFN-γ and possible real sample application.