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1.
Small ; 20(30): e2310584, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38470191

RESUMO

Renewable energy is crucial for sustainable future, and Cu2ZnSnS4 (CZTS) based solar cells shine as a beacon of hope. CZTS, composed of abundant, low-cost, and non-toxic elements, shares similarities with Cu(In,Ga)Se2 (CIGS). However, despite its promise and appealing properties for solar cells, CZTS-based solar cells faces performance challenges owing to inherent issues with CZTS material, and conventional substrate structure complexities. This review critically examines these roadblocks, explores ongoing efforts and breakthroughs, providing insight into the evolving landscape of CZTS-based solar cells research. Furthermore, as an optimistic turn in the field, the review first highlights the crucial need to transition to a superstrate structure for CZTS-based single junction devices, and summarizes the substantial progress made in this direction. Subsequently, dive into the discussion about the fascinating realm of CZTS-based tandem devices, providing an overview of the existing literature as well as outlining the possible potential strategies for enhancing the efficiency of such devices. Finally, the review provides a useful outlook that outlines the priorities for future research and suggesting where efforts should concentrate to shape the future of CZTS-based solar cells.

2.
Small ; 20(27): e2307807, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38342673

RESUMO

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%.

3.
Environ Res ; 258: 119371, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-38876420

RESUMO

Cu2ZnSnS4 (CZTS) was synthesized following hot injection method and the process was optimized by varying temperature conditions. Four samples at different temperatures viz., 200, 250, 300 and 350 °C were prepared and analyzed using different characterization techniques. Based on the correlation between XRD, Raman and XPS, we conclude that the formation of ZnS and SnS2 occurs at 350 °C but at 200 °C there is no breakdown of the complex as per XRD. According to Raman and XPS analysis, as the temperature rises, the bonds between the metals become weaker, which is visibly seen in Raman and XPS due to the minor peaks of copper sulfide. Scanning electron microscopic analysis confirmed nanometric particles which increase in size with temperature. The photocatalytic evaluation showed that CZTS synthesized at 200 °C performed efficiently in the removal of the two colorants, methylene blue and Rhodamine 6G, achieving 92.80% and 90.65%, respectively. The photocatalytic degradation efficiencies decreased at higher temperatures due to bigger sized CZTS particles as confirmed by SEM results. Computational simulations confirm that CZTS has a highly negative energy -25,764 Ry, confirming its structural stability and higher covalent than ionic character.


Assuntos
Cobre , Azul de Metileno , Rodaminas , Sulfetos , Rodaminas/química , Azul de Metileno/química , Sulfetos/química , Cobre/química , Catálise , Compostos de Estanho/química , Temperatura Alta , Poluentes Químicos da Água/química
4.
Environ Res ; 217: 114875, 2023 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-36435500

RESUMO

An exemplary vision to understand the fundamental role of metal-doped multi-components system such as Au/Ag doped CZTS (Cu2ZnSnS4) nanocrystals encourages the non-vacuum approach for the best performing photocatalyst. Hydrophilic nanoparticles (Au/Ag and CZTS) are allowed to amalgamate under NTP atmosphere, eradicating the prerequisite for high-end equipment. The potential of Au and Ag-doped CZTS nanoparticles was speculated using various optical and structural characterizations. The absorption range of CZTS nanoparticles lies in the visible range, while Au/Ag doping slightly red-shifts the absorption range, considered the desirable state for photocatalysis. The synthesized nanoparticles are highly monodispersed with ∼15-35 nm particle size for Ag, Au, and CZTS. Photocatalysis is a discernible scheme for treating wastewater containing dyes, textile effluents, chemicals, and heavy metals. Here, we strive to use these ex-situ synthesized nanomaterials as photocatalysts, where the real textile waste (collected from industrial outlets), dyes, and heavy metal (chromium (VI)) have been photo-reduced after scrutinizing the finest combination of Ag or Au doped CZTS. Au-CZTS shows superior catalytic activity with an efficiency of 99.7% with a rate constant of 0.2 min-1 (while Ag-CZTS shows 90% efficiency with a rate constant of 0.07 min-1); hence, used for real textile waste and heavy metal (Chromium VI) photo-reduction. The maximum efficiency achieved for textile-1, textile-2, and Cr (VI) reductions is 80%, 70%, and 97%, respectively. The nanocrystals are highly stable and recyclable, tested for 15 repeated cycles. These studies pave the way for developing cost-effective, environmentally-friendly, durable, and selective semiconductor-metal (Au/Ag) hybrid heterostructures as visible-light-driven photocatalysts for wastewater remediation.


Assuntos
Metais Pesados , Nanopartículas , Águas Residuárias , Nanopartículas/química , Corantes/química , Têxteis
5.
Small ; 17(31): e2100496, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-34173332

RESUMO

Copper-based chalcogenides have been considered as potential photocathode materials for photoelectrochemical (PEC) CO2 reduction due to their excellent photovoltaic performance and favorable conduction band alignment with the CO2 reduction potential. However, they suffer from low PEC efficiency due to the sluggish charge transfer kinetics and poor selectivity, resulting from random CO2 reduction reaction pathways. Herein, a facile heat treatment (HT) of a Cu2 ZnSnS4 (CZTS)/CdS photocathode is demonstrated to enable significant improvement in the photocurrent density (-0.75 mA cm-2 at -0.6 V vs RHE), tripling that of pristine CZTS, as a result of the enhanced charge transfer and promoted band alignment originating from the elemental inter-diffusion at the CZTS/CdS interface. In addition, rationally regulated CO2 reduction selectivity toward CO or alcohols can be obtained by tailoring the surficial sulfur vacancies by HT in different atmospheres (air and nitrogen). Sulfur vacancies replenished by O-doping is shown to favor CO adsorption and the CC coupling pathway, and thereby produce methanol and ethanol, whilst the CdS surface with more S vacancies promotes CO desorption capability with higher selectivity toward CO. The strategy in this work rationalizes the interface charge transfer optimization and surface vacancy engineering simultaneously, providing a new insight into PEC CO2 reduction photocathode design.

6.
Nano Lett ; 18(9): 5530-5537, 2018 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-30080050

RESUMO

Solution processing of polycrystalline compound semiconductor thin film using nanocrystals as a precursor is considered one of the most promising and economically viable routes for future large-area manufacturing. However, in polycrystalline compound semiconductor films such as Cu2ZnSnS4 (CZTS), grain size, and the respective grain boundaries play a key role in dictating the optoelectronic properties. Various strategies have been employed previously in tailoring the grain size and boundaries (such as ligand exchange) but most require postdeposition thermal annealing at high temperature in the presence of grain growth directing agents (selenium or sulfur vapor with/without Na, K, etc.) to enlarge the grains through sintering. Here, we show a different strategy of controlling grain size by tuning the kinetics of nucleation and the subsequent grain growth in CZTS nanocrystal thin films during a crystalline phase transition. We demonstrate that the activation energy for the phase transition can be varied by utilizing different shapes (spherical and nanorod) of nanocrystals with similar size, composition, and surface chemistry leading to different densities of nucleation sites and, thereby, different grain sizes in the films. Additionally, exchanging the native organic ligands for inorganic surface ligands changes the activation energy for the phase change and substantially changes the grain growth dynamics, while also compositionally modifying the resulting film. This combined approach of using nucleation and growth dynamics and surface chemistry enables us to tune the grain size of polycrystalline CZTS films and customize their electronic properties by compositional engineering.

7.
Front Chem ; 12: 1394191, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38882214

RESUMO

This review provides a comprehensive overview of the production and modification of CZTS nanoparticles (NPs) and their application in electrocatalysis for water splitting. Various aspects, including surface modification, heterostructure design with carbon nanostructured materials, and tunable electrocatalytic studies, are discussed. A key focus is the synthesis of small CZTS nanoparticles with tunable reactivity, emphasizing the sonochemical method's role in their formation. Despite CZTS's affordability, it often exhibits poor hydrogen evolution reaction (HER) behavior. Carbon materials like graphene, carbon nanotubes, and C60 are highlighted for their ability to enhance electrocatalytic activity due to their unique properties. The review also discusses the amine functionalization of graphene oxide/CZTS composites, which enhances overall water splitting performance. Doping with non-noble metals such as Fe, Co., and Ni is presented as an effective strategy to improve catalytic activity. Additionally, the synthesis of heterostructures consisting of CZTS nanoparticles attached to MoS2-reduced graphene oxide (rGO) hybrids is explored, showing enhanced HER activity compared to pure CZTS and MoS2. The growing demand for energy and the need for efficient renewable energy sources, particularly hydrogen generation, are driving research in this field. The review aims to demonstrate the potential of CZTS-based electrocatalysts for high-performance and cost-effective hydrogen generation with low environmental impact. Vacuum-based and non-vacuum-based methods for fabricating CZTS are discussed, with a focus on simplicity and efficiency. Future developments in CZTS-based electrocatalysts include enhancing activity and stability, improving charge transfer mechanisms, ensuring cost-effectiveness and scalability, increasing durability, integrating with renewable energy sources, and gaining deeper insight into reaction processes. Overall, CZTS-based electrocatalysts show great promise for sustainable hydrogen generation, with ongoing research focused on improving performance and advancing their practical applications.

8.
Adv Mater ; 36(3): e2307733, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37850716

RESUMO

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.

9.
Heliyon ; 10(3): e25354, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38333860

RESUMO

In this paper, we examine the impact of the precursor's mixing temperature and mixing protocol on the crystal structure and morphological and optical properties of Cu2ZnSnS4 (CZTS) thin films. Four samples of CZTS thin films were synthesized with the sol-gel spin coating technique by previously mixing precursors at (a) 150 °C and (b) room temperature (RT), either (i) all at once or (ii) through sequential adding the individual chemicals 30 min apart. SEM-EDX, XRD, Raman and Visible spectroscopy analysis showed that sample 150°C-ST (chemicals mixed at the same time at 150 °C) fulfilled all the theoretical stoichiometric criteria (poor in Cu, rich in Zn) for the high-quality CZTS absorbers. The larger grain size (850 nm) and crystallite size (73.96 nm), lower strain (0.49×10-3) and band gap Eg=1.44eV which is closest to the Shockley-Queisser limit for single junction solar cells (1.34 eV).

10.
ACS Appl Mater Interfaces ; 16(9): 11516-11527, 2024 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-38391145

RESUMO

High-quality Cu2(Zn,Fe,Cd)SnS4 (CZFCTS) thin films based on the parent CZTS were prepared by aerosol-assisted chemical vapor deposition (AACVD). Substitution of Zn by Fe and Cd significantly improved the electrical transport properties, and monophasic CZFCTS thin films exhibited a maximum power factor (PF) of ∼0.22 µW cm-1 K-2 at 575 K. The quality and performance of the CZFCTS thin films were further improved by postdeposition annealing. CZFCTS thin films annealed for 24 h showed a significantly enhanced maximum PF of ∼2.4 µW cm-1 K-2 at 575 K. This is higher than all reported values for single-phase quaternary sulfide (Cu2BSnS4, B = Mn, Fe, Co, Ni) thin films and even exceeds the PF for most polycrystalline bulk materials of these sulfides. Density functional theory (DFT) calculations were performed to understand the impact of Cd and Fe substitution on the electronic properties of CZTS. It was predicted that CZFCTS would have a smaller band gap than CZTS and a higher density of states (DoS) near the Fermi level. The thermal conductivity and thermoelectric figure of merit (zT) of the CZFCTS thin films have been evaluated, yielding an estimated maximum zT range of 0.18-0.69 at 550 K. The simple processing route and improved thermoelectric performance make CZFCTS thin films extremely promising for thermoelectric energy generation.

11.
Anal Chim Acta ; 1288: 342056, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-38220266

RESUMO

Bacterial infections, viral infections and autoimmune diseases pose a considerable threat to human health. Procalcitonin (PCT) has emerged as a biomarker for the detection of these diseases. To ensure accurate and reliable results, we propose a dual-mode approach that incorporates self-validation and self-correction mechanisms. Herein, we develop a dual-mode self-powered photoelectrochemical (PEC) and colorimetric sensor to determine PCT. The self-powered PEC sensor was constructed with a photoanode of spherical nanoflower-MoS2/Cu2ZnSnS4/Bi2S3 material and a photocathode of CuInS2 material. Ni4Cu2 bimetallic hollow nanospheres (BHNs) possess superoxide dismutase and catalase performance, which facilitate superoxide anion radical (·O2-) and H2O2 circulating generation, promoting the separation of photogenerated electrons and holes to amplify photocurrent signal. Thus Ni4Cu2 BHNs is used as a marker material for PEC sensor. Meanwhile, in colorimetric mode, Ni4Cu2 BHNs converts blue oxTMB to a colourless TMB for colorimetric detection of PCT. Based on this principle, dual-mode determination of PCT with high sensitivity is achieved. The dual-mode method not only demonstrates outstanding properties and practicability, but also presents an effective, highly efficient and reliable method for detecting PCT.


Assuntos
Técnicas Biossensoriais , Nanosferas , Humanos , Nanosferas/química , Pró-Calcitonina , Molibdênio/química , Peróxido de Hidrogênio , Colorimetria , Técnicas Eletroquímicas/métodos , Técnicas Biossensoriais/métodos , Limite de Detecção
12.
Nanomaterials (Basel) ; 13(20)2023 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-37887913

RESUMO

Massive emissions of carbon dioxide (CO2) have caused environmental issues like global warming, which needs to be addressed. Researchers have developed numerous methods to reduce CO2 emissions. Among these, photoelectrochemical (PEC) CO2 reduction is a promising method for mitigating CO2 emissions. Recently, Cu2ZnSnS4 (CZTS) has been recognized as good photocathode candidate in PEC systems for CO2 reduction due to its earth abundance and non-toxicity, as well as its favourable optical/electrical properties. The performance of PEC CO2 reduction can be evaluated based on its efficiency, selectivity, and stability, which are significantly influenced by the photocathode materials. As a result, researchers have applied various strategies to improve the performance of CZTS photocathodes, including band structure engineering and surface catalytic site engineering. This review provides an overview of advanced methods to enhance the PEC systems for CO2 reduction, focusing on CZTS.

13.
Nanomaterials (Basel) ; 13(3)2023 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-36770393

RESUMO

In Cu2ZnSnS4 (CZTS) solar cells, it is crucial to suppress the generation of and remove the SnS2 secondary phase to improve the solar cell characteristics, as the SnS2 secondary phase affects the barrier for carrier collection and diode characteristics of the device. In this study, the nano-metallic precursor was modified to effectively suppress the generation of the SnS2 secondary phase on the surface and simultaneously improve the uniformity and quality of the thin film. The CZTS bifacial solar cells prepared via the proposed method exhibited significantly improved junction-rectifying characteristics, as the efficiency was improved to 1.59%. The proposed method to figurremove SnS2 is effective, simple, and environmentally friendly.

14.
J Mol Graph Model ; 121: 108448, 2023 06.
Artigo em Inglês | MEDLINE | ID: mdl-36934620

RESUMO

Herein, we investigate different oxides layers: Zinc Oxide (ZnO), Nickel Oxide (NiO), Titanium Oxide (TiO2), and Copper Oxide (CuO), which are effective materials for Copper Zinc Tin Sulfide (CZTS) based solar cells due to their excellent electrical and optical properties. The different oxide films were prepared using spray pyrolysis as a low-cost technique. Then, the films were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and UV-Visible to examine different properties. The XRD pattern showed that the different oxides are polycrystalline. ZnO exhibits a hexagonal wurtzite structure, and NiO is cubic. For the TiO2, (101) and (004) peaks have been identified, corresponding to the tetragonal anatase phase. CuO showed diffraction peaks corresponding to the monoclinic structures. The SEM results revealed that the deposited films consist of crystals with low crystallinity for NiO and good crystallinity for the rest oxides. The band gap was calculated from the UV-visible measurement. We obtained 3.26 eV, 3.34 eV, 3.2 eV, and 1.7 eV for ZnO, NiO, TiO2, and CuO respectively. The performance of the CZTS-based solar cell was checked by using the simulator SCAPS. ZnO and TiO2 were used as window layers where CZTS efficiencies are 24.40% and 24.54%, respectively. These findings show that ZnO and TiO2 films can be produced by low-cost techniques such as spray pyrolysis to be used as windows and electron transport layers for CZTS-based solar cells.


Assuntos
Óxidos , Óxido de Zinco , Óxidos/química , Óxido de Zinco/química , Cobre/química , Zinco/química
15.
Chem Asian J ; : e202300813, 2023 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-37939281

RESUMO

A variety of unique compounds have been examined to accommodate the current demand for useful multi-functional nanomaterials, copper-based quaternary CZTS semiconductors are one of them. Due to their special characteristic features like non-toxicity, cheap, and abundance, they have been recommended in recent literature for various applications. Apart from individual CZTS, different hetero-structures have also been prepared with different compounds which is well discussed and elaborated in this article. Additionally, their preparation methods, properties, and application viability have also been discussed comprehensively. The application of CZTS such as photocatalytic dye degradation and hydrogen evolution reaction has been elaborated on in this article identifying their benefits and challenges to give readers a thorough visualization. Apart from that, challenges reported in studies, a few approaches are also mentioned to possibly counter them.

16.
Nanomaterials (Basel) ; 13(11)2023 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-37299634

RESUMO

A hydrothermal method was successfully employed to synthesize kesterite Cu2ZnSnS4 (CZTS) nanoparticles. X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and optical ultraviolet-visible (UV-vis) spectroscopy were used for characterization of structural, chemical, morphological, and optical properties. XRD results confirmed that a nanocrystalline CZTS phase corresponding to the kesterite structure was formed. Raman analysis confirmed the existence of single pure phase CZTS. XPS results revealed the oxidation states as Cu+, Zn2+, Sn4+, and S2-. FESEM and TEM micrograph images revealed the presence of nanoparticles with average sizes between 7 nm to 60 nm. The synthesized CZTS nanoparticles bandgap was found to be 1.5 eV which is optimal for solar photocatalytic degradation applications. The properties as a semiconductor material were evaluated through the Mott-Schottky analysis. The photocatalytic activity of CZTS has been investigated through photodegradation of Congo red azo dye solution under solar simulation light irradiation, proving to be an excellent photo-catalyst for CR where 90.2% degradation could be achieved in just 60 min. Furthermore, the prepared CZTS was reusable and can be repeatedly used to remove Congo red dye from aqueous solutions.

17.
Environ Sci Pollut Res Int ; 30(33): 79774-79788, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36997778

RESUMO

Colloidal route synthesis of quaternary compound CZTS (Cu2ZnSnS4) has been anticipated with an inimitable combination of coordinating ligands and solvents using the hot injection technique. CZTS is recognized as one of the worthiest materials for photo-voltaic/catalytic applications due to its exclusive properties (viz., non-toxic, economical, direct bandgap, high absorbance coefficient, etc.). This paper demonstrates the formation of crystalline, single-phased, monodispersed, and electrically passivated CZTS nanoparticles using a distinctive combination of ligands viz. oleic acid (OA)-trioctylphosphine (TOP) and butylamine (BA)-trioctylphosphine (TOP). Detailed optical, structural, and electrochemical studies were done for all CZTS nanoparticles, and the most efficient composition was found using ligands butylamine and TOP. CZTS nanocrystals were rendered hydrophilic via surface-ligand engineering, which was used for photocatalysis studies of organic pollutants. Malachite green (MG) and rhodamine 6G (Rh) for water remediation have great commercial prospects. The unique selling proposition of this work is the rapid synthesis time (~ 45 min) of colloidal CZTS nanocrystals, cost-effective ligand-exchange process, and negligible material wastage (~ 200 µl per 10 ml of pollutant) during photocatalytic experiments.


Assuntos
Poluentes Ambientais , Nanopartículas , Água , Butilaminas , Ligantes , Solventes
18.
Environ Sci Pollut Res Int ; 30(44): 98671-98681, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-36287362

RESUMO

Using zinc tellurium (ZnTe) as the buffer layer in the Cu2ZnSnS4 (CZTS)-based solar cells showed an improvement in overall efficiency. ZnTe is investigated as an alternative to replace the conventional toxic Cd-contained buffer layers. It may also reduce the overall cost of these cells as both layers (ZnTe and CZTS) have eco-friendly and earth-abundant constituents. The sol-gel spin coating method is used for the deposition of CZTS thin films on the corning glass substrates. The X-ray diffraction studies showed the peaks corresponding to (112), (200), (220), and (312) planes which confirmed the formation of the essential kesterite phase. The optical band gap of the deposited films was found at around 1.45 eV by the UV-visible-NIR spectrophotometer. The optimum thickness of the absorber layer (CZTS) and buffer layer (ZnTe) was investigated based on the performance of the ZnO:Al/ZnO/ZnTe/CZTS/Mo cell structure by using the AMPS-1D simulation tool. In contrast, the tool was molded by the experimentally investigated data for the constituent materials of the cell structure. The solar cells' efficiency was increased by 23.47% at 2500 nm and 50 nm thickness of the CZTS and ZnTe layers, respectively. In addition, it was analyzed and found that the current density value showed an improvement with operating temperature as it is one of the requirements in the high solar radiation areas where the temperature even rises more than 50 °C in the summer.


Assuntos
Energia Solar , Óxido de Zinco , Telúrio , Zinco , Simulação por Computador
19.
ACS Nano ; 17(16): 15742-15750, 2023 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-37578321

RESUMO

Conducting atomic force microscopy has been performed for a fundamental understanding of the mechanism responsible for the lower power conversion efficiency (PCE) of Cu2ZnSnS4 (CZTS) solar cells than that of CuIn1-xGaxSe2 (CIGS) solar cells. The difference in efficiency is partly attributed to the distinctly different band alignment between the grain boundaries (GBs) and grain interior (GI) for the two materials. While CIGS shows type-II band alignment, CZTS was discovered to demonstrate type-I band alignment with the conduction band shifting downward while the valence band shifting upward at the GBs. The type-I band alignment in CZTS leads to both electron and hole trapping, enhancing their recombination, and lowers the PEC. Band engineering was realized by moderate oxidative annealing of CZTS. The preferential GB oxidation changes the band alignment into inverse type-I (i.e., the conduction band upward bending and valence band downward bending at GBs). The blocking of carrier recombination at GBs leads to 30% enhancement in PCE. Our work reveals the critical role that band alignment between the grain boundary and interior plays in polycrystalline thin film solar cells and suggests band alignment engineering as a practical approach to enhance PCE. Furthermore, conducting AFM has been shown to be a powerful tool for qualitative and semiquantitative characterization of band alignment in polycrystalline films.

20.
ACS Appl Mater Interfaces ; 15(20): 24978-24988, 2023 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-37162157

RESUMO

Quaternary chalcogenide copper zinc tin sulfide (CZTS) nanoparticles are used to make the p-type absorber layer in CZTS solar cells, which are considered more benign alternatives to those based on cadmium telluride (CdTe) and less expensive than copper indium gallium selenide. CZTS has an ideal band gap and a high absorption coefficient for solar radiation, making the nanoparticles an attractive option for photovoltaic cells. In this work, we explore the toxicity of CZTS nanoparticles using an environmentally relevant bacterial model Shewanella oneidensis MR-1. This study also focuses on understanding the stability of CZTS-based thin films and their direct interaction with bacterial cells. Bacterial cell viability, stability of nanoparticles and thin films, as well as mechanisms of toxicity were evaluated using various analytical tools. The CZTS nanoparticle suspensions show significant acute toxic effects on bacterial cells, but long-term (72 h) exposure of bacterial cells to CZTS-based thin films (made from nanoparticles) do not exhibit similar detrimental impacts on bacterial viability. This result is compelling because it suggests that CZTS nanomaterials will have minimal unintended toxicity as long as they are incorporated into a stable film structure.

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