Structural and electrical properties of co-evaporated In,Garich CIGS thin films

The CIGS thin trims are prepared by co-evaporation of elemental In, Ga and Se on the substrates of Mo-coated glasses at 400℃ followed by co-evaporation of elemental Cu and Se at 550℃. We study the structural and electrical properties using XRD, XRF and Hall effect measurements. In general, Cu（In,Ga）sSes phase exists when Cu/（In＋Ga） ratio is from 0.17 to 0.27, Cu（In,Ga）3Se5 phase exists for Cu/（In＋Ga） ratio between 0.27 and 0.41, Cu2（in,Ga）4Se7 and Cu（In,Ga）2Se3.5 phases exist for Cu/0n＋Ga） ratio between 0.41 and 0.61, and OVC（or ODC） and CuIn0.7Ga0.3Se2 phases exist when Cu/（In＋Ga） ratio is from 0.61 to 0.88. With the increase of Cu/（In＋Ga） ratio, the carrier concentrations of the films gradually increase, but the electrical resistivity gradually decreases.     

CIGS薄膜(InGa)2Se3-富Cu-富In(Ga)的演变

采用三步共蒸发工艺顺序沉积铜铟镓硒(CuInGaSe2,CIGS)薄膜.薄膜的厚度、组份、晶相结构分别由台阶仪、X射线荧光光谱仪(XRF)和X射线衍射仪(XRD)来表征.在(In,Ga)2Se3预制层-富Cu相的演变过程中,依次发生以下相变:Cu(In,Ga)5Se8、Cu(In,Ga)3Se5、Cu2(In,Ga)4Se7(或Cu(In,Ga)2Se3.5)、Cu(In,Ga)Se2(液相CuxSe).在富Cu相-富In(Ga)相的演变过程中,依次发生以下相变:Cu(In,Ga)Se2(液相CuxSe)、Cu2(In,Ga)4Se7(或Cu(In,Ga)2Se3.5)、Cu(In,Ga)3Se5、Cu(In,Ga)5Se8.对这两个演变过程中薄膜的生长机理和结构特性进行了讨论.     

铜含量变化对Cu(In,Ga)Se2薄膜微结构的影响

报道了不同的铜含量(Cu/(Ga+In)=0.748~0.982)对Cu(In,Ga)Se2 (CIGS)薄膜微结构的影响.文章中的CIGS薄膜采用磁控溅射金属预置层后硒化的方法制备, 其X射线衍射谱(XRD)中一系列黄铜矿结构CIGS(CH-CIGS)相的衍射峰确认了CH-CIGS相的存在.对CIGS薄膜拉曼光谱的分析表明, 随着铜含量的上升, CIGS薄膜经历了CH-CIGS和有序缺陷化合物(OVC)混合相、CH-CIGS单相、CH-CIGS和CuxSe混合相三种状态.进一步的分析显示, CIGS薄膜拉曼峰的半高宽随铜含量变化, 并在Cu/(Ga+In)=0.9附近时达到最小值, 这说明此时CIGS薄膜具有更好的结晶度和更少的无序性.此外还得到了CIGS薄膜拉曼峰半高宽与铜含量的经验关系公式.这些研究表明拉曼光谱能比XRD更加灵敏地探测CIGS薄膜的微结构, 可望作为一种无损和快速测量方法, 用于对CIGS薄膜晶相和铜含量的初步估计.     

Polycrystalline GaSb thin films grown by co-evaporation

We report optical and electrical properties of polycrystalline GaSb thin films which were successfully grown by co-evaporation on soda-lime glass substrates. The thin films have preferential orientation of the (111)direction. SEM results indicate that the average grain size of GaSb thin film is 500 nm with the substrate temperature of 560 ℃. The average reflectance of GaSb thin film is about 30% and the absorption coefficient is of the order of 104 cm-1. The optical bandgap of GaSb thin film is 0.726 eV. The hole concentration shows a clear increasing trend as the Ga-evaporation-temperature/Sb-evaporation-temperature (TGa/TSb) ratio increases. When the Ga crucible temperature is 810 ℃ and the antinomy crucible temperature is 415 ℃, the hole concentration of polycrystalline GaSb is 2 x 1017 cm-3 and the hole mobility is 130 cm2/(V-s). These results suggest that polycrystalline GaSb thin film is a good candidate for the use as a cheap material in TPV cells.     

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.     

Time‐resolved investigation of Cu(In,Ga)Se2 growth and Ga gradient formation during fast selenisation of metallic precursors

Ga segregation at the backside of Cu(In,Ga)Se₂ solar cell absorbers is a commonly observed phenomenon for a large variety of sequential fabrication processes. Here, we investigate the correlation between Se incorporation, phase formation and Ga segregation during fast selenisation of Cu–In–Ga precursor films in elemental selenium vapour. Se incorporation and phase formation are analysed by real‐time synchrotron‐based X‐ray diffraction and fluorescence analysis. Correlations between phase formation and depth distributions are gained by interrupting the process at several points and by subsequent ex situ cross‐sectional electron microscopy and Raman spectroscopy. The presented results reveal that the main share of Se incorporation takes place within a few seconds during formation of In–Se at the top part of the film, accompanied by outdiffusion of In out of a ternary Cu–In–Ga phase. Surprisingly, CuInSe₂ starts to form at the surface on top of the In–Se layer, leading to an intermediate double graded Cu depth distribution. The remaining Ga‐rich metal phase at the back is finally selenised by indiffusion of Se. On the basis of a proposed growth model, we discuss possible strategies and limitations for the avoidance of Ga segregation during fast selenisation of metallic precursors. Solar cells made from samples selenised with a total annealing time of 6.5 min reached conversion efficiencies of up to 14.2 % (total area, without anti‐reflective coating). The evolution of the Cu(In,Ga)Se₂ diffraction signals reveals that the minimum process time for high‐quality Cu(In,Ga)Se₂ absorbers is limited by cation ordering rather than Se incorporation. Copyright © 2014 John Wiley & Sons, Ltd.     

Reactive Sputtering Process for CuIn1‐xGaxSe2 Thin Film Solar Cells

CuIn_1‐xGa_xSe₂ (CIGS) thin films are grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker is used to deliver reactive Se molecules. The Cu and (In_0.7Ga_0.3)₂Se₃ targets are simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on film composition are investigated. The Cu/(In+Ga) composition ratio increases as the Se flux increases at a plasma power of less than 30 W for the Cu target. The (112) crystal orientation becomes dominant, and crystal grain size is larger with Se flux. The power conversion efficiency of a solar cell fabricated using an 800‐nm CIGS film is 8.5%.     

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.     

掺Na制备柔性聚酰亚胺衬底CIGS薄膜太阳电池

研究了Na掺入对低温沉积柔性聚酰亚胺(PI)衬底Cu(In,Ga)Se2(CIGS)薄膜的结构和电学特性影响。研究结果表明:Na元素的掺入使Ga元素的扩散受到了阻滞,但对CIGS薄膜晶粒尺寸没有明显的影响,少量的Na可提高CIGS薄膜的载流子浓度和降低电阻率;Na的掺入可明显提高CIGS薄膜太阳电池的器件特性,通过优化掺Na工艺,制备的柔性PI衬底—CIGS薄膜太阳电池的最高转换效率达到10.4%。     

Solar Cells Based on CuInSe2 and Related Compounds: Material and Device Properties and Processing

This paper summarizes recent material and device results obtained at the Institute of Physical Electronics at Stuttgart University (IPE). Properties of the material system Cu(In, Ga)(S, Se)₂ were analysed and wherever possible a correlation between the material properties and the device characteristics is made. Different high-vacuum techniques of absorber preparation are presented and compared. The formation of different alloys of the family Cu(In, Ga)(S, Se)₂ is possible for the co-evaporation and at least one of the sequential evaporation techniques. The model for Cu-rich growth of CuInSe₂ known from the co-evaporation process can also be used for the Cu-rich growth in the sequential evaporation processes. The surface composition of slightly (In, Ga)-rich bulk compositions is always determined to be the defect chalcopyrite Cu(In, Ga)₃Se₅. Solar cells prepared with different processes and therefore different morphologies yielded similar device performance. An exponential decay of the density of states from the valence and conduction bands was obtained. Improved cell performance is achieved using absorber layers with higher carrier concentrations. The carrier concentration can be increased by using Na-containing substrates or by utilizing a new Cd-free buffer layer. Device efficiencies in the range of 15% were achieved using the Cd-free buffer layer.     

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.     

Nanoscale insight into the p‐n junction of alkali‐incorporated Cu(In,Ga)Se2 solar cells

The effects of alkali diffusion and post‐deposition treatment in three‐stage processed Cu(In,Ga)Se₂ solar cells are examined by using atom probe tomography and electrical property measurements. Cells, for which the substrate was treated at 650°C to induce alkali diffusion from the substrate prior to absorber deposition, exhibited high open‐circuit voltage (758 mV) and efficiency (18.2%) and also exhibited a 50 to 100‐nm‐thick ordered vacancy compound layer at the metallurgical junction. Surprisingly, these high‐temperature samples exhibited higher concentrations of K at the junction (1.8 at.%) than post‐deposition treatment samples (0.4 at.%). A model that uses Ga/(Ga + In) and Cu/(Ga + In) profiles to predict bandgaps (±17.9 meV) of 22 Cu(In,Ga)Se₂ solar cells reported in literature was discussed and ultimately used to predict band properties at the nanoscale by using atom probe tomography data. The high‐temperature samples exhibited a greater drop in the valence band maximum (200 meV) due to a lower Cu/(Ga + In) ratio than the post‐deposition treatment samples. There was an anticorrelation of K concentrations and Cu/(Ga + In) ratios for all samples, regardless of processing conditions. Changes in elemental profiles at the active junctions correlate well with the electrical behaviour of these devices. Copyright © 2017 John Wiley & Sons, Ltd.     

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.     

Texture and morphology variations in (In,Ga)2Se3 and Cu(In,Ga)Se2 thin films grown with various Se source conditions

Texture and morphology variations in co‐evaporated (In,Ga)₂Se₃ and Cu(In,Ga)Se₂ (CIGS) films grown with various Se source conditions during growth were studied. The Se species of simply evaporated, large molecular Se (E‐Se, low‐sticking coefficient), and RF‐plasma cracked atomic Se (R‐Se, high sticking coefficient) were used in the present work. (In,Ga)₂Se₃ precursor films, which were prepared during the first stage of CIGS film growth by the three‐stage process, showed systematic variations in texture and Na distribution profile with varying evaporative Se (E‐Se) flux. The properties of CIGS films and solar cells also showed systematic variations, and the open‐circuit voltage (V_oc) and fill factor were found to be especially sensitive to the E‐Se flux. R‐Se grown (In,Ga)₂Se₃ precursor films featured granular morphology with strong (105) and (301) peaks in the diffraction pattern, and the texture was very similar to an E‐Se grown film fabricated with a Se to group III metal (In + Ga) flux ratio (P_{[Se]/[In + Ga]}) of about 6, although the nominal P_{[Se]/[In + Ga]} used for an R‐Se source was very small and less than 0.5. The R‐Se grown CIGS films displayed, however, highly dense surfaces and larger grain sizes than E‐Se grown CIGS films. The controllability of film morphology and the Na diffusion profile in (In,Ga)₂Se₃ and CIGS films with various Se source conditions are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Research on structure of Cu2ZnSn(S, Se)4 thin films with high Sn-related phases

Cu2ZnSn(S, Se)4 (CZTSSe) thin films were deposited on flexible substrates by three evaporation processes at high temperature. The chemical compositions, microstructures and crystal phases of the CZTSSe thin films were respectively characterized by inductively coupled plasma optical emission spectrometer (ICP-OES), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman scattering spectrum. The results show that the single-step evaporation method at high temperature yields CZTSSe thin films with nearly pure phase and high Sn-related phases. The elemental ratios of Cu/(Zn+Sn)=1.00 and Zn/Sn=1.03 are close to the characteristics of stoichiometric CZTSSe. There is the smooth and uniform crystalline at the surface and large grain size at the cross section for the films, and no other phases exist in the film by XRD and Raman shift measurement. The films are no more with the Sn-related phase deficiency.     

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.     

Adjusting the Ga grading during fast atmospheric processing of Cu(In,Ga)Se2 solar cell absorber layers using elemental selenium vapor

We study the sequential fabrication of Cu(In,Ga)Se₂ (CIGSe) absorber layers by using an atmospheric pressure selenization with a process duration of only a few minutes and the utilization of elemental selenium vapor from independent Se sources. This technology could proof to be an industrially relevant technology for the fabrication of thin‐film solar cells. Controlling the amount of Se provided during the selenization of metal precursors is shown to be an effective measure to adjust the Ga in‐depth distribution. A reduced Se supply for CIGSe formation leads to a more homogeneous Ga distribution within the absorber. The underlying growth dynamics is investigated by interrupting the selenization at different times. At first, CIGSe formation occurs in accordance with previously suggested growth paths and Ga segregates at the Mo back contact. Between 520 and 580 °C, the growth dynamics differs distinctly, and In and Ga distribute far more uniformly within the absorber depth. We also studied the impact of the precursor architecture. The best performing precursor in terms of efficiency of the respective solar cells was a multilayer with 22 In/CuGa/In triple layers. Simple bilayers stacks lead to films of higher roughness and correlated shunting. By optimizing the precursor architecture and the Ga in‐depth distribution in the CIGSe layer, a conversion efficiency of up to 15.5% (active area) could be achieved. To our knowledge, this is the highest reported efficiency for sulfur free CIGSe‐based solar cells utilizing fast (few minutes) atmospheric processes and elemental Se vapor. Copyright © 2017 John Wiley & Sons, Ltd.     

Dynamic radiative properties of the Cu(In,Ga)Se2 layer during the co‐evaporation process

A study of the wavelength‐integrated emissivity has been performed on the optical stack Cu_xSe/Cu(In,Ga)Se₂/Mo. The wavelength interval used in the study was 2–20 µm, which covers 95% of the radiated heat from a black body heated to 500°C. Substrate temperatures around 500°C are commonly used in production of Cu(In,Ga)Se₂ thin films for solar cells. The integrated emissivity was obtained from directional reflectivity measurements of experimental samples with different thicknesses of the Cu_xSe layers. It was subsequently compared to the emissivity from numerical simulations based on newly obtained values of the refractive index values for Cu(In,Ga)Se₂ and Cu_xSe at these wavelengths. Good agreement was found between the measured and simulated values. At a Cu(In,Ga)Se₂ thickness of 1.8 µm and a Mo thickness of 400 nm, a maximum in the integrated emissivity was found for a Cu_xSe thickness of 30 nm. The results are valuable input into understanding the dynamics of the change in emissivity between Cu‐rich Cu(In,Ga)Se₂ with segregated Cu_xSe and Cu‐poor single phase Cu(In,Ga)Se₂ at temperatures around 500°C. In co‐evaporation of Cu(In,Ga)Se₂, this emissivity change is often monitored and used as a process control (end‐point detection). Copyright © 2010 John Wiley & Sons, Ltd.     

Non‐destructive optical analysis of band gap profile,crystalline phase,and grain size for Cu(In,Ga)Se2 solar cells deposited by 1‐stage, 2‐stage,and 3‐stage co‐evaporation

Cu(In,Ga)Se₂ (CIGS) thin films co‐evaporated by 1‐stage, 2‐stage, and 3‐stage processes have been studied by spectroscopic ellipsometry (SE). The disappearance of a Cu_2‐xSe optical signature, detected by real time SE during multistage CIGS, has enabled precise endpoint control. Band gap energies determined by SE as depth averages show little process variation for fixed [Ga]/([In] + [Ga]) atomic ratio, whereas their broadening parameters decrease with increasing number of stages, identifying successive grain size enhancements. Refined SE analysis has revealed band gap profiling only for 3‐stage CIGS. Solar cells incorporating these absorbers have yielded increased efficiencies in correlation with phase control, grain size, and band gap profiling. Copyright © 2013 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.