共蒸发三步法制备CIGS薄膜的性质

采用PID温度控制器控制共蒸发设备中蒸发源及衬底加热的温度,以三步法工艺制备CIGS(Cu(In,Ga)Se2)薄膜,通过恒功率加热衬底测试温度的变化,可实现在线组分监测,得到CIGS薄膜的组成重现性很好.CIGS薄膜的表面光洁,粗糙度多数小于10nm.但是组成相同的CIGS薄膜,其结晶择优取向可能不同,主要有(112)和(220)/(204)两种;其结晶形貌也有很大的不同,晶粒粗大且成柱状的薄膜电池效率高,虽然从Cu/(In Ga)＜1的组成可以认为CIGS薄膜为贫Cu结构,但Hall测试多数CIGS薄膜呈p型,少数呈n型.     

Influence of growth temperature and thickness on the orientation of Cu(In,Ga)Se2 film

Cu(In,Ga)Se2(CIGS) films are deposited on the Na-free glass substrate using three-stage co-evaporation process,and the effects of thickness and growth temperature on the orientation of CIGS film are investigated by X-ray diffraction(XRD) and scanning electron microscopy(SEM).When the growth of CIGS film does not experience the Cu-rich process,the increase of the growth temperature at the second stage(Ts2) promotes the(112) orientation of CIGS film,and weakens the(220) orientation.Nevertheless,when the growth of CIGS film experiences Cu-rich process,the increase of Ts2 significantly promotes the(220) orientation.In addition,with the thickness of CIGS film decreasing,the extent of(In,Ga)2Se3(IGS) precursor orientation does not change except for the intensity of Bragg peak,yet the(220) orientation of following CIGS film is hindered,which suggests that(112) plane preferentially grows at the initial growth of CIGS film.     

Modification of deposition process for Cu(In, Ga)Se2 thin film solar cells on polyimide substrate at low temperature

We fabricate polycrystalline Cu(In, Ga)Se₂ (CIGS) film solar cells on polyimide (PI) substrate at temperature of 450 °C with single-stage process, and obtain a poor crystallization of CIGS films with several secondary phases in it. For improving it further, the two-stage process is adopted instead of the single-stage one. An extra Cu-rich CIGS layer with the thickness from 100 nm to 200 nm is grown on the substrate, and then another Cu-poor CIGS film with thickness of 1.5–2.0 μm is deposited on it. With the modification of the evaporation process, the grain size of absorber layer is increased, and the additional secondary phases almost disappear. Accordingly, the overall device performance is improved, and the conversion efficiency is enhanced by about 20%.     

CIGS Thin Films for Cd-Free Solar Cells by One-Step Sputtering Process

Cu(In_1?x Ga _x )Se₂ (CIGS) thin films were deposited by a one-step radio frequency (RF) magnetron sputtering process using a quaternary CIGS target. The influence of substrate temperature on the composition, structure, and optical properties of the CIGS films was investigated. All the CIGS films exhibited the chalcopyrite structure with a preferential orientation along the (112) direction. The CIGS film deposited at 623 K showed significant improvement in film crystallinity and surface morphology compared to films deposited at 523 and 573 K. To simplify the manufacturing procedure of solar cells and avoid the use of the toxic element Cd, the properties of ZnS films prepared by RF sputtering were also investigated. The results revealed that the sputtered ZnS film exhibits good lattice matching with the sputtered CIGS film with significantly lower optical absorption loss. Finally, all-sputtered Cd-free CIGS-based heterojunction solar cells with the structure SLG/Mo/CIGS/ZnS/AZO/Al grids were fabricated without post-selenization. Furthermore, the results demonstrated the feasibility of using a full sputtering process for the fabrication of Cd-free CIGS-based solar cell.     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Preferred orientation of Cu(In,Ga)Se2 thin film deposited on stainless steel substrate

The influences of process parameters and Fe diffusing into Cu(In,Ga)Se₂ (CIGS) films on the orientation of CIGS absorbers grown on the stainless steel (SS) foils are investigated. The structural properties, morphology, and elemental profiles are characterized using X‐ray diffraction, scanning electron microscopy, and second ion mass spectroscopy, respectively. The orientation of CIGS thin films on the SS substrates strongly depends on the texture of the (In,Ga)₂Se₃ precursor, determined by the substrate temperature at the first stage (Ts1) and the flux ratio of Se to (In + Ga). Among these factors, Ts1 is the prerequisite to achieve [300]‐oriented IGS layer, which will yield [200]‐oriented CIGS thin film in the later process. The results indicate that through the comparison of CIGS thin films on the Mo/SS substrates and on the Mo/ZnO/SS substrates and combined with simply calculation, Fe diffusing into the CIGS layer will hinder the growth of the CIGS grains along [112] orientation. The grazing‐incidence X‐ray diffraction results suggest that the surface of the [220]‐textured CIGS thin film on the SS substrate still has [220] predominance, whereas the surface texture of the [220]‐texture CIGS thin film on the Mo/soda‐lime glass substrate became [112] predominant, which is due to the different compensation ability between Fe and Na elements. Finally, the relations between the device parameters and the degrees of the preferred orientation of CIGS absorbers are investigated. Copyright © 2012 John Wiley & Sons, Ltd.     

Preparation of CuInxGa1−xSe2 solar cells by electron beam evaporation of powdered evaporants

Cu(In,Ga)Se₂ (CIGS) thin films were deposited by electron beam evaporation of ball-milled powders containing various amounts of gallium. The effects of the gallium concentration in the Cu(In,Ga)Se₂ on the structure, surface morphology and optical properties of the films were investigated using X-ray diffraction, energy-dispersive X-ray analysis, atomic force microscopy and optical spectroscopy. All of the films, which were deposited at 450 °C, were polycrystalline and exhibited a chalcopyrite structure with a (112) preferred orientation. The optical constants of the films were calculated. The grain size, the roughness and the band gap increased with increasing amounts of gallium in the films. A glass/TCO/CdS/CIGS/Au solar cell with 12.87% efficiency was prepared directly from the powdered material.     

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。     

周期顺序蒸发工艺生长的Cu(In,Ga)Se_2薄膜结构

采用新颖的周期顺序蒸发和真空硒化退火工艺生长出p型CuIn0 7Ga0 3 Se2 薄膜.通过XPS谱、Raman谱、XRD谱分析了预生长层以及硒化后的CuIn0 7Ga0 3 Se2 薄膜,对四元化合物Cu(In ,Ga)Se2 的Raman谱进行了讨论,并观察到Ga对A1模式峰位的移动影响,同时发现薄膜倾向于沿(112 )晶面生长,薄膜贫Cu会加剧(2 2 0 ) / (2 0 4)表面自发分解成{ 112 }小晶面.研究表明,薄膜具有良好的电学特性和结构特性.     

新型CIGS阻挡层多横向界面Mo的特性及对器件性能的影响

采用磁控溅射方法,在不锈钢箔上制备多横向界 面Mo(M-Mo,multi-transverse interface Mo)和单横向界面Mo(S-Mo)薄 膜,并利用共蒸发三步法分别在M-Mo和S-Mo薄膜上制备Cu(In,Ga)Se₂(CIGS)薄膜及 器件。通过二次离子质谱仪(SIMS)、X射线衍射仪(XRD)和扫描电子显微镜(SEM)研究了不同 结构的Mo薄膜对CIGS影响。通过I-V测试,表征M-Mo和S -Mo作为背电极的CIGS电池电学性能。XRD结果显示,M-Mo和S-Mo 薄膜均以(110)为择优取向。SEM结果显示,M-Mo薄膜相对 于S-Mo,薄膜晶粒 较小,粗糙度较大。J-V测试结果显示,M-Mo薄膜作为背 电极的电池的开路电压Voc、短路电流J sc和填充因子(FF)均有所提高。     

Impacts of surface sulfurization on Cu(In1−x,Gax)Se2 thin‐film solar cells

In this work, the impacts of surface sulfurization of high‐quality Cu(In_1−x,Ga_x)Se₂ (CIGS) thin films deposited by three‐stage process on the film properties and the cell performance were investigated. The CIGS thin films were sulfurized at 550 °C for 30 min using H₂S gas. The X‐ray photoelectron spectroscopy analysis revealed that sulfur atoms diffused into the CIGS surface layer and that the valence band minimum was lowered by the film sulfurization. The open circuit voltage (V_oc) drastically increased from 0.590 to 0.674 V as a result of the sulfurization process. Temperature‐dependent current–voltage and capacitance–frequency measurements also revealed that interface recombination was drastically decreased by the lowering of the defect's activation energy level at the vicinity of the buffer/CIGS interface after the sulfurization. Copyright © 2014 John Wiley & Sons, Ltd.     

Research on structural characteristics of large-scale CdS thin films deposited by CBD under low ammonia condition

Cadmium sulfide (CdS) buffer layers with the scale of 10 cm×10 cm are deposited by chemical bath deposition (CBD) with different temperatures and thiourea concentrations under low ammonia condition. There are obvious hexagonal phases and cubic phases in CdS thin films under the conditions of low temperature and high thiourea concentration. The main reason is that the heterogeneous reaction is dominant for homogeneous reaction. At low temperature, CdS thin films with good uniformity and high transmittance are deposited by adjusting the thiourea concentration, and there is almost no precipitation in reaction solution. In addition, the low temperature is desired in assembly line. The transmittance and the band gap of CdS thin films are above 80% and about 2.4 eV, respectively. These films are suitable for the buffer layers of large-scale Cu(In,Ga)Se2 (CIGS) solar cells.     

Fabrication of Cu(In,Ga)Se2 thin films by sputtering from a single quaternary chalcogenide target

Single‐layered Cu‐In‐Ga‐Se precursors were fabricated by one‐step sputtering of a single quaternary Cu(In,Ga)Se₂ (CIGS) chalcogenide target at room temperature, followed by post selenization using Se vapor obtained from elemental Se pellets. The morphological and structural properties of both as‐deposited and selenized films were characterized by X‐ray diffraction (XRD), Raman spectroscope and scanning electron microscope (SEM). The precursor films exhibited a chalcopyrite structure with a preferential orientation in the (112) direction. The post‐selenization process at high‐temperature significantly improved the quality of the chalcopyrite CIGS. The CIGS layers after post‐selenization were used to fabricate solar cells. The solar cell had an open‐circuit voltage Voc of 0.422 V, a short‐circuit current density J = 24.75 mA, a fill factor of 53.29%, and an efficiency of 7.95%. Copyright © 2010 John Wiley & Sons, Ltd.     

Properties of the Mo Back Contact for the Formation of a Thin-Film Photovoltaic Absorber

A Taguchi experimental design was used to find which deposition parameter has the most dominant effect on the electrical resistivity of molybdenum (Mo) films. Based on the most important parameter, the Mo films were further characterized by structural, electrical, and adhesive methods. Then, a copper indium gallium selenide (CIGS) thin film was fabricated by a two-stage process on the obtained Mo layer. The results show that working pressure had a dominant effect on electrical resistivity. The Mo films deposited at 1 mTorr and 2 mTorr exhibited compressive strain and dense polycrystalline microstructure, whereas those deposited at 3 mTorr and 4 mTorr exhibited tensile strain and an elongated grain with open boundaries. A Mo film with open porous structure, tensile strain, and lower resistivity was suitable for the formation of CIGS films. After selenization at 560°C, a single-phase chalcopyrite CIGS film with a layer of MoSe₂ at the Mo/CIGS interface was obtained.     

Growth of Cu(In,Ga)Se2 thin films by a novel single‐stage route based on pulsed electron deposition

We report a novel route for growing Cu(In,Ga)Se₂ (CIGS) thin films, based upon the Pulsed Electron Deposition (PED) technique. Unlike other well‐known deposition techniques, PED process allows the stoichiometric deposition of CIGS layers in a single stage, without requiring any further treatments for Cu/(In + Ga) ratio adjustment nor selenization. The structural properties of polycrystalline CIGS films strongly depend on the growth temperature, whereas post‐deposition annealing enhances the grain size and the <112> out‐of‐plane preferred orientation of the chalcopyrite structure, without affecting the film composition. Preliminary measurements of the performances of solar cells based on these films confirm the great potentiality of PED‐grown CIGS as absorber layers. Copyright © 2011 John Wiley & Sons, Ltd.     

Na‐induced efficiency boost for Se‐deficient Cu(In,Ga)Se2 solar cells

Among different process routes for Cu(In,Ga)Se₂ (CIGS) solar cells, sufficient Se supply is commonly required to obtain high‐quality CIGS films. However, supplying extra Se increases the cost and the complexity. In this work, we demonstrate that extra Na incorporation can substantially increase efficiency of Se‐deficient CIGS solar cells, fabricated by sputtering from a quaternary CIGS target without extra Se supply, from 1.5% to 11.0%. The Se‐deficient CIGS device without extra NaF reveals a roll‐over I–V curve at room temperature as well as significantly reduced J_sc and fill factor at low temperatures. The electrical characteristics of Se‐deficient CIGS films are well explained and modeled by the low p‐type doping due to high density of compensating donors and the presence of deep defects possibly originating from the anti‐bonding levels of Se vacancies. The significant improvement after extra Na incorporation is attributable to the Na‐induced passivation of Se vacancies and the increased p‐type doping. Our result suggests that extra Na addition can effectively compensate the Se deficiency in CIGS films, which provides a valuable tuning knob for compositional tolerance of absorbers, especially for the Se‐deficient CIGS films. We believe that our findings can shine light on the development of novel CIGS processes, distinct from previous ones fabricated in Se‐rich atmosphere. Copyright © 2015 John Wiley & Sons, Ltd.     

Fabrication and characterization of thin-film Cu (In,Ga) Se2 solar cells on a PET plastic substrate using screen printing

Chalcopyrite copper indium gallium diselenide (CIGS) ink was prepared by dissolving copper, indium, gallium acetylacetonate and Se powder in oleylamine using the hot injection methods. CIGS films were deposited on a PET plastic substrate by a screen-printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. X-ray diffraction patterns reveal that the films exhibit a chalcopyrite-type structure. The crystalline grain sizes of the films decrease with increasing Ga content. AFM data shows that the root mean square (RMS) surface roughness of the CIGS film decreases with increasing Ga content. The effects of the Ga content in the CIGS absorber layer on the optical properties of the corresponding thin films and solar cells were studied. The band-gap energies of the CIGS thin films increased with an increasing Ga/(In+Ga) ratio. The short-circuit current (I_SC) of the solar cell decreased linearly with the Ga/(In+Ga) ratio, while the open-circuit voltage (V_OC) increased with this ratio. The solar cell exhibited its highest efficiency of 4.122% at a Ga/(In+Ga) ratio of 0.3.     

Fabrication of CIGS Films by Electrodeposition Method for Photovoltaic Cells

Cu(InGa)Se₂ (CIGS) thin films were fabricated by electrochemical deposition in a single bath containing Cu, In, Ga, and Se ions. The electrolyte was prepared by dissolving CuCl₂, InCl₃, GaCl₃, H₂SeO₃, and LiCl in deionized water. The potentiostatic deposition process was achieved by applying a voltage ranging from ?0.5?V to ?0.8?V versus Ag/AgCl. The effects of different chemical bath concentrations on the film composition and morphology were investigated. Stoichiometric CIGS film composition could be achieved by controlling the chemical compositions of the bath and the voltage. Gelatin was added to the solution to improve the surface and microstructures of the CIGS film. The as-deposited films were annealed at 500°C in Ar atmosphere for crystallization. The structural, morphological, and compositional properties of the CIGS thin films before and after annealing were examined by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. This study showed that the composition of the CIGS films is dependent on the bath concentration, whereas the applied potential had relatively less effect on the CIGS film composition. In addition, the use of gelatin helped in the fabrication of crack-free CIGS thin films with greatly improved surface morphology.     

The structural evolution of Cu(In,Ga)Se2 thin film and device performance prepared through a three-stage process

Cu(In,Ga)Se₂ (CIGS) absorber layer is grown on Mo-coated soda-lime glass (SLG) substrates using co-evaporation deposition technique. The growth characteristics of the CIGS films deposited through a three-stage process are examined by interrupting the deposition along the reaction pathway. In the three-stage process, the absorber layer undergoes several phase transformations with Cu content. The γ-(In,Ga)₂Se₃ layer is formed first and is then converted to α-Cu(In,Ga)Se₂ via β-Cu(In,Ga)₃Se₅. When α-Cu(In,Ga)Se₂ stoichiometry is reached, Cu_2−xSe segregation at the surface and at grain boundaries begins to occur. The Cu_2−xSe improved the densification and grain growth of the absorber layer. Then, as the absorber layer reverts to substoichiometric composition, the Cu_2−xSe phase disappears and the depleted server Cu near the surface instead. This paper reports several types of defects found in absorber layers that act as non-radiative recombination centers, such as impurity phases (Cu_2−xSe and Cu(In,Ga)₃Se₅), deep point defects (In_Cu), grain boundaries, and voids. The highest efficiency at 10.97% was achieved when the bulk [Cu]/([In]+[Ga]) ratio was 0.98 at the third stage of the process. This result is attributed to the low-concentration deep-level defects that act as recombination centers and to the denser structure with larger grain size.     

Effect of Se flux on CuIn1‐xGaxSe2 film in reactive sputtering process

CuIn_1‐xGa_xSe₂ (CIGS) thin films were grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker was used to deliver reactive Se molecules. The Cu_0·6 Ga_0·4 and Cu_0·4In_0·6 targets were simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on CIGS film deposition were investigated. The CIGS film growth rate decreased, and the surface roughness of a film increased as the Se flux increased. The [112] crystal orientation was dominant, and metallic crystal phases such as Cu₉Ga₄ and Cu₁₆In₉ in a film were disappearing with increasing Se flux. A solar cell fabricated using a 900‐nm CIGS film showed the power conversion efficiency of 8·6%, the highest value found in a sub‐micron thick CIGS solar cell related to a reactive sputtering process with metallic targets. Copyright © 2011 John Wiley & Sons, Ltd.