Cu2ZnSnS4 thin film solar cells by fast coevaporation

Solar cells based on kesterite‐type Cu₂ZnSnS₄ (CZTS) were fabricated on molybdenum coated soda lime glass by evaporation using ZnS, Sn, Cu, and S sources. The coevaporation process was performed at a nominal substrate temperature of 550°C and at a sulfur partial pressure of 2–3 × 10⁻³ Pa leading to polycrystalline CZTS thin films with promising electronic properties. The CZTS absorber layers were grown copper‐rich, requiring a KCN etch step to remove excess copper sulfide. The compositional ratios as determined by energy‐dispersive X‐ray spectroscopy (EDX) after the KCN etch are Cu/(Zn + Sn): 1.0 and Zn/Sn: 1.0. A solar cell with an efficiency of 4.1% and an open‐circuit voltage of 541 mV was obtained. Copyright © 2010 John Wiley & Sons, Ltd.     

Defects properties and vacancy diffusion in Cu2MgSnS4

Cu₂Mg_SnS₄(CZTS)is a promising photovoltaic absorber material,however,efficiency is largely hindered by potential fluctuation and a band tailing problem due to the abundance of defect complexes and low formation energy of an intrinsic Cu_Zndefect.Alternatives to CZTS by group I,II,or IV element replacement to circumvent this challenge has grown research in-terest.In this work,using a hybrid(HSE06)functional,we demonstrated the qualitative similarity of defect thermodynamics and electronic properties in Cu₂Mg_SnS₄(CMTS)to CZTS.We show Sn_Mgto be abundant when in Sn-and Cu-rich condition,which can be detrimental,while defect properties are largely similar to CZTS in Sn-and Cu-poor.Under Sn-and Cu-poor chemic-al potential,there is a general increase in formation energy in most defects except Sn_Mg,Cu_Mgremains as the main contribu-tion to p-type carriers,and Sn_Mgmay be detrimental because of a deep defect level in the mid gap and the possibility of form-ing defect complex Sn_Mg+Mg_Sn.Vacancy diffusion is studied using generalized gradient approximation,and we find similar va-cancy diffusion properties for Cu vacancy and lower diffusion barrier for Mg vacancy,which may reduce possible Cu-Mg dis-order in CMTS.These findings further confirm the feasibility of CMTS as an alternative absorber material to CZTS and suggest the possibility for tuning defect properties of CZTS,which is crucial for high photovoltaic performance.     

Impact of alloying duration of an electrodeposited Cu/Sn/Zn metallic stack on properties of Cu2ZnSnS4 absorbers for thin‐film solar cells

The impacts of preheating of an electrodeposited Cu/Sn/Zn (CTZ) stack precursor on structural changes of the CTZ precursor and the impact on structural and electric properties of the finally obtained Cu₂ZnSnS₄ (CZTS) films are discussed in detail. We found that preheating for relatively long durations improved the qualities of CZTS films: these films were composed of large grains and had compact and flat surface morphologies. The best solar cell with efficiency of 8.1% was obtained on the basis of a CZTS film derived from the CTZ precursor preheated for 200 min. The external quantum efficiency response of the cell indicated efficient utilization of photons with relatively long wavelength regions because of its good structural and electronic properties. On the other hand, a short circuit current density–temperature property of one of the best cells in this study suggested that the CZTS film had deep acceptor levels and/or an appreciable energy barrier to the Mo back contact. Moreover, an open circuit voltage–temperature property of the corresponding device showed activation energy of 1.18 eV, indicating preferential occurrence of CdS–CZTS interface recombination. Copyright © 2015 John Wiley & Sons, Ltd.     

Cu2ZnSnS4 films grown in one-step process by spray pyrolysis with improved properties

This work reports results of a study carried out to improve the optical, electrical and microstructural properties of Cu₂ZnSnS₄ (CZTS) films grown by spray pyrolysis in a one-step process using a precursor solution prepared dissolving thiourea and salts of Cu, Sn and Zn in a solvent constituted by a mixture of dimethyl sulfoxide (DMSO) and acetone. The improvement of the properties of the CZTS films was achieved through a parameters study performed by using an experimental design 2³ face centered central composite design (FCCCD). The study revealed that substrate temperature (T_s), carrier gas pressure (P_g), spray pulse time (t_sp) as well as their interaction are the parameters that most critically affect the above mentioned properties. Special emphasis was done on studying the influence of these parameters on the micro structural properties of the CZTS films using the XRD peak broadening method and Williamson-Hall equations, assuming the models UDM (uniform deformation model), USDM (uniform stress deformation model) and UDEDM (uniform deformation energy density model). Further, information regarding the influence of preparation conditions on the formation of structural defects was achieved through Urbach energy measurements.     

Rapid annealing of reactively sputtered precursors for Cu2ZnSnS4 solar cells

Cu₂ZnSnS₄ (CZTS) is a promising thin‐film absorber material that presents some interesting challenges in fabrication when compared with Cu(In,Ga)Se₂. We introduce a two‐step process for fabrication of CZTS films, involving reactive sputtering of a Cu‐Zn‐Sn‐S precursor followed by rapid annealing. X‐ray diffraction and Raman measurements of the sputtered precursor suggest that it is in a disordered, metastable CZTS phase, similar to the high‐temperature cubic modification reported for CZTS. A few minutes of annealing at 550 °C are sufficient to produce crystalline CZTS films with grain sizes in the micrometer range. The first reported device using this approach has an AM1.5 efficiency of 4.6%, with J_sc and V_oc both appearing to be limited by interface recombination. Copyright © 2012 John Wiley & Sons, Ltd.     

Improving the photovoltaic performance of co‐evaporated Cu2ZnSnS4 thin‐film solar cells by incorporation of sodium from NaF layers

We have investigated the influence of sodium (Na) on the properties of co‐evaporated Cu₂ZnSnS₄ (CZTS) layer microstructures and solar cells. The photovoltaic performance and diode properties were improved by incorporating Na from NaF layers into the CZTS layers, while Na had a negligible effect on the microstructural properties of the layer. The best cell fabricated by using an optimal CZTS layer (Cu/(Zn + Sn) = 0.70, Zn/Sn = 1.8) yielded an active area efficiency of 5.23%. The analysis of device properties suggests that charge‐carrier recombination at CZTS/CdS interface is suppressed by intentional Na incorporation from NaF layers. Copyright © 2016 John Wiley & Sons, Ltd.     

Locating the electrical junctions in Cu(In,Ga)Se2 and Cu2ZnSnSe4 solar cells by scanning capacitance spectroscopy

We determined the electrical junction (EJ) locations in Cu(In,Ga)Se₂ (CIGS) and Cu₂ZnSnSe₄ (CZTS) solar cells with ~20‐nm accuracy by developing scanning capacitance spectroscopy (SCS) applicable to the thin‐film devices. Cross‐sectional sample preparation for the SCS measurement was developed by high‐energy ion milling at room temperature for polishing the cross section to make it flat, followed by low‐energy ion milling at liquid nitrogen temperature for removing the damaged layer and subsequent annealing for growing a native oxide layer. The SCS shows distinct p‐type, transitional, and n‐type spectra across the devices, and the spectral features change rapidly with location in the depletion region, which results in determining the EJ with ~20‐nm resolution. We found an n‐type CIGS in the region next to the CIGS/CdS interface; thus, the cell is a homojunction. The EJ is ~40 nm from the interface on the CIGS side. In contrast, such an n‐type CZTS was not found in the CZTS/CdS cells. The EJ is ~20 nm from the CZTS/CdS interface, which is consistent with asymmetrical carrier concentrations of the p‐CZTS and n‐CdS in a heterojunction cell. Our results of unambiguously determination of the junction locations contribute significantly to understanding the large open‐circuit voltage difference between CIGS and CZTS. Copyright © 2016 John Wiley & Sons, Ltd.     

射频磁控溅射法制备Cu_2ZnSnS_4薄膜

利用射频磁控溅射法在玻璃基片上制备了Cu2ZnSnS4(CZTS)薄膜,薄膜在室温下生长,再在Ar气氛中快速退火。通过X射线衍射、X射线电子能谱、原子力显微镜和吸收谱研究了退火温度对薄膜结构、组分、形貌和禁带宽度的影响。结果表明,所制备样品为Cu2ZnSnS4多晶薄膜,具有较强的沿(112)晶面择优取向生长的特点,薄膜组分均为富S贫Cu,样品表面形貌比较均匀。退火温度为350,400,450和500℃的薄膜样品的禁带宽度分别是1.49,1.53,1.51和1.46 eV。     

Optical and Electrical Properties of Cu2ZnSnS4 Film Prepared by Sulfurization Method

Cu₂ZnSnS₄ (CZTS) films were prepared by sulfurization of sputtered Zn/Sn/Cu multilayer thin films. Raman peaks at 251 cm^?1, 289 cm^?1, 336 cm^?1, and 362 cm^?1 were detected, and the optical band gap energy of the CZTS was estimated to be about 1.53 eV. Energy-dispersive spectrometry and x-ray photoelectron spectroscopy reveal that the composition ratio of prepared CZTS film is close to stoichiometric. Photoresponse current measurements show persistent photoconductivity effect, with decay constants τ and β of 5.04 and 0.269, respectively.     

Effects of different precursors on Cu2ZnSnS4 thin film solar cells prepared by sputtering method

In this study, the impacts of different precursors on Cu₂ZnSnS₄ thin film solar cells were investigated. The two kinds of precursors of (Cu+Sn)/Zn and (Cu+Sn)/ZnS were deposited on Mo-coated soda lime glasses by magnetron sputtering. Cu₂ZnSnS₄ (CZTS) films based on different precursors were fabricated by soft annealing and following two-step sulfurization in sulphur vapour. The crystal structure, phase purity, surface morphology, composition and optical properties of CZTS films from different precursors were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), energy dispersive spectrometry (EDS) and UV–vis–NIR spectroscopy, respectively. As a result, the CZTS thin films with smooth surface and uniform compositional ratio distribution were obtained from the precursors of (Cu+Sn)/ZnS. The best conversion efficiency of the fabricated CZTS film solar cell based on (Cu+Sn)/ZnS precursors was 3.36%.     

Cu2ZnSnS4 photovoltaic cell with improved efficiency fabricated by high‐temperature annealing after CdS buffer‐layer deposition

To improve the photovoltaic properties of Cu₂ZnSnS₄ (CZTS) cells, we investigated the effect of both the thickness of the deposited CdS layers and the post‐annealing temperature following CdS deposition on the photovoltaic properties of CZTS cells using a two‐layer CZTS structure. By depositing a thin CdS layer (40 nm) followed by high temperature annealing (603 K), we observed a remarkable increase in the short‐circuit current density because of the enhancement of the external quantum efficiency in the wavelength range of 400–800 nm. The best CZTS cell exhibited a conversion efficiency of 9.4% in the active area (9.1% in the designated area). In addition, we also fabricated a CZTS cell with open‐circuit voltage of 0.80 V by appropriately tuning the composition of the CZTS layers. Copyright © 2016 John Wiley & Sons, Ltd.     

基于纳米颗粒的铜锌锡硫硒薄膜制备

采用热注入法制备了Cu2ZnSnS4(CZTS)纳米颗粒,并形成高分散、稳定的"墨水",采用滴注方法形成CZTS前驱体薄膜。利用X射线衍射(XRD)、拉曼光谱(Raman)、透射电子显微镜(TEM)和紫外-可见光谱(UV-VIS)对CZTS纳米颗粒的晶体结构、表面形貌和带隙进行了表征。Raman数据显示合成的纳米颗粒为纯的CZTS,不存在ZnS和Cu2SnS3等杂相。傅里叶红外光谱(FTIR)和UV-VIS表明合成的CZTS纳米颗粒表面被油胺(OLA)包覆,并且其带隙为1.52 eV。对CZTS前驱体薄膜在硫化氢气氛和固态硒气氛中退火处理,得到铜锌锡硫硒(CZTSSe)薄膜。结果表明,经硫化氢处理后薄膜表面平整但CZTS晶粒并没长大,而经过固态硒处理后得到了结晶质量较好的CZTSSe薄膜。     

XPS analysis and characterization of thin films Cu2ZnSnS4 grown using a novel solution based route

A new technique to grow single phase Cu₂ZnSnS₄ (CZTS) thin films for solar cells applications using a chemical route is presented; this consist in sequential deposition of Cu₂SnS₃ (CTS) and ZnS thin films followed by annealing at 550 °C in nitrogen atmosphere, where the CTS compound is prepared in one step process by simultaneous precipitation of Cu₂S and SnS₂ performed by diffusion membranes assisted CBD (chemical bath deposition) technique and ZnS by conventional CBD technique.Measurements of X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM) were used to identify the phases present in the CTS and CZTS films as well as to study their structural and morphological properties. Further, the oxidation states and the chemical composition homogeneity in the volume were studied by X-ray photoelectron spectroscopy (XPS) analysis. Oxidation states and results regarding structural and morphological characterization of CZTS films prepared using the novel technique are compared with those results obtained from single phase CZTS films prepared by sequential evaporation of metallic precursors in presence of elemental sulfur. XRD and Raman spectroscopy studies were used to verify that the CZTS films prepared by the novel method do not present secondary phases.     

Effect of sputter deposited Zn precursor film thickness and annealing time on the properties of Cu2ZnSnS4 thin films deposited by sequential reactive sputtering of metal targets

Cu₂ZnSnS₄ (CZTS) is made of earth abundant elements and also have suitable optical properties for solar cell applications. But, in phase diagram, CZTS exists in a narrow range of temperature and composition. Therefore, optimizing the elemental composition and annealing time is very important for obtaining phase pure CZTS. In this study, the effects of elemental composition and short annealing time on the structural and optical properties of reactively sputtered CZTS thin films are reported. Thin films were deposited by reactive sputtering of Cu: Sn (60:40 wt%), Sn and Zn targets sequentially in the presence of H₂S at room temperature. Amount of Zn precursor was varied by changing the sputter time for Zn. The films were rapidly annealed in inert atmosphere for varying time. The band gap of sample changed with change in the composition as well as annealing time. Sample with higher Zn content showed better crystallinity. With increase in the annealing time the crystallinity of samples improved. Sample annealed for 12 min at 550 °C was phase pure. Obtaining good quality film even for very short anneal time is the novelty of reactive sputtering method as all the elements are already mixed and short annealing is required only for crystal growth. Through detailed experiments, the optimum composition and annealing time required for the growth of phase pure CZTS has been established.     

Effects of Na and MoS2 on Cu2ZnSnS4 thin‐film solar cell

Cu₂ZnSnS₄ (CZTS)‐based materials have a useful band gap and a high absorption coefficient; however, their power conversion efficiency is low compared with that of CdTe and Cu(In,Ga)Se₂‐based solar cells. Two of the factors that strongly affect CZTS solar cell characteristics are the MoS₂ layer and the presence of defects. In this study, Mo back‐contact layers were annealed to control MoS₂ layer formation and the Na content in the Mo layer before the absorber precursor layer was deposited. The increase in oxygen content in the Mo layer suppressed MoS₂ layer formation. In addition, the increase in Na diffusion during the initial stage of the absorber precursor deposition decreased the defect density in the absorber layer and in the absorber–buffer interface. These results were verified through measurements of the external quantum efficiency, the temperature dependence of the open‐circuit voltage (V_OC), and admittance spectra. The current densities (J_SC) and V_OC, as well as the power conversion efficiencies, improved as the annealing temperature of the Mo layer increased, which suggests that CZTS solar cell characteristics can be improved by suppressing MoS₂ layer formation and increasing Na content in the Mo layer before deposition of the absorber precursor layer. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrical and optical properties of Cu2ZnSnS4 grown by a thermal co-evaporation method and its diode application

Cu₂ZnSnS₄ (CZTS) is low cost and constitutes non-toxic materials abundant in the earth crust. Environment friendly solar cell absorber layers were fabricated by a thermal co-evaporation technique. Elemental composition of the film was stated by energy dispersive spectroscopy (EDS). Some optical and electrical properties such as absorption of light, absorption coefficient, optical band gap charge carrier density, sheet resistance and mobility were extracted. Optical band gap was found to be as 1.44 eV, besides, charge carrier density, resistivity and mobility were found as 2.14×10¹⁹ cm⁻³, 8.41×10⁻⁴ Ω cm and 3.45×10² cm² V⁻¹ s⁻¹, respectively. In this study Ag/CZTS/n-Si Schottky diode was fabricated and basic diode parameters including barrier height, ideality factor, and series resistance were concluded using current–voltage and capacitance–voltage measurements. Barrier height and ideality factor values were found from the measurements as 0.81 eV and 4.76, respectively, for Ag/CZTS/n-Si contact.     

Effective Ligand Engineering of the Cu2ZnSnS4 Nanocrystal Surface for Increasing Hole Transport Efficiency in Perovskite Solar Cells

Effective engineering of surface ligands in semiconductor nanocrystals can facilitate the electronic interaction between the individual nanocrystals, making them promising for low‐cost optoelectronic applications. Here, the use of high purity Cu₂ZnSnS₄ (CZTS) nanocrystals as the photoactive layer and hole‐transporting material is reported in low‐temperature solution‐processed solar cells. The high purity CZTS nanocrystals are prepared by engineering the surface ligands of CZTS nanocrystals, capped originally with the long‐chain organic ligand oleylamine. After ligand removal, CZTS nanocrystals show substantial improvement in photoconductivity and mobility, displaying also an appreciable photoresponse in a simple heterojunction solar cell architecture. More notably, CZTS nanocrystals exhibit excellent hole‐transporting properties as interface layer in perovskite solar cells, yielding power conversion efficiency (PCE) of 15.4% with excellent fill factor (FF) of 81%. These findings underscore the importance of removing undesired surface ligands in nanocrystalline optoelectronic devices, and demonstrate the great potential of CZTS nanocrystals as both active and passive material for the realization of low‐cost efficient solar cells.     

Effects of temperature-time profile on Cu2ZnSnS4 films and cells based on sulfur-contained precursors

Cu₂ZnSnS₄ (CZTS) films with high-quality are necessary to the high-performance CZTS solar cells. The influence of different temperature-time profiles during sulfurization on CZTS films were investigated by characterizing the compactness, roughness and grain size of CZTS films. With slowing the heating-rate during sulfurization process, the grain size of the film is becoming larger and larger, but the large grain size degrades the flatness of the CZTS films at the same time. The formation of films having the target composition (EDX) and phase purity (Raman) was attributed to the optimum choice of composition ration of the precursor and the thermal profile during sulfurization. The optical and electrical properties of corresponding CZTS films were detected by using UV–vis–INR Spectrophotometer and Hall measurement, respectively. Finally, the CZTS film solar cells were fabricated and the best cell demonstrated 3.91% efficiency. A high R_s is the main reason to inhibit the performance of the cells.     

Structural and electrical characterization of Cu2ZnSnS4 ingot material grown by melting method

In this work,a Cu2ZnSnS4 (CZTS) ingot is grown via a melting method,then cooled;the resulting molten stoichiomet-ric mixture is sealed off in a quartz ampoule under vacuum.The CZTS powder chemical composition analyses are determined us-ing energy dispersive spectroscopy,and revealing the slightly Cu-rich and Zn-poor character of the ingot.Powder X-ray diffrac-tion analysis reveals a crystalline structure with a kesterite phase formation,and a preferred orientation of (112) plane.The lat-tice constants of the a-and c-axes,calculated based on the XRD analyses,are a =5.40 (A) and c =10.84 (A).Based on Hall measure-ments at room temperature,we find that the crystal exhibits p-type conductivity,with a high concentration of 1018 cm-3,a res-istivity of 1.7 Ω cm,and a mobility of 10.69 cm2V-1s-1.Activation energies are estimated based on an Arrhenius plot of conductiv-ity versus 1/T,for a temperature range of 80-350 K,measuring 35 and 160 meV in low-and high-temperature regimes,respect-ively,which is attributed to complex defects (2Cuzn+Snzn) and antisite defects (Cuzn),respectively.The observed scattering mech-anisms are attributed to ionized impurities and acoustic phonons at low and high temperatures,respectively.The extracted band-gap is 1.37 eV.     

High‐efficiency Cu2ZnSn(S,Se)4 solar cells fabricated through a low‐cost solution process and a two‐step heat treatment

A method for fabricating high‐efficiency Cu₂ZnSn(S,Se)₄ (CZTSSe) solar cells is presented, and it is based on a non‐explosive, low‐cost, and simple solution process followed by a two‐step heat treatment. 2‐Methoxyethanol was used as a solvent, and Cu, Zn, Sn, chloride salts, and thiourea were used as solutes. A CZTSSe absorber was prepared by sulfurising and then selenising an as‐coated Cu₂ZnSnS₄ (CZTS) film. Sulfurisation in a sulfur vapour filled furnace for a long time (2 h) enhanced the crystallisation of the as‐coated CZTS film and improved the stability of the CZTS precursor, and selenisation promoted further grain growth to yield a void‐free CZTSSe film. Segregation of Cu and S at the grain boundaries, the absence of a fine‐grain bottom layer, and the large grain size of the CZTSSe absorber were the main factors that enhanced the grain‐to‐grain transport of carriers and consequently the short‐circuit current (J_sc ) and efficiency. The efficiency of the CZTS solar cell was 5.0%, which increased to 10.1% after selenisation. For the 10.1% CZTSSe solar cell, the external quantum efficiency was approximately 80%, the open‐circuit voltage was 450 mV, the short‐circuit current was 36.5 mA/cm², and the fill factor was 61.9%. Copyright © 2016 John Wiley & Sons, Ltd.