Inkjet printed Cu(In,Ga)S<Subscript>2</Subscript> nanoparticles for low-cost solar cells

Cu(In,Ga)Se₂ (CIGSe) thin film solar cells were fabricated by direct inkjet printing of Cu(In,Ga)S₂ (CIGS) nanoparticles followed by rapid thermal annealing under selenium vapor. Inkjet printing is a low-cost, low-waste, and flexible patterning method which can be used for deposition of solution-based or nanoparticle-based CIGS films with high throughput. XRD and Raman spectra indicate that no secondary phase is formed in the as-deposited CIGS film since quaternary chalcopyrite nanoparticles are used as the base solution for printing. Besides, CIGSe films with various Cu/(In + Ga) ratios could be obtained by finely tuning the composition of CIGS nanoparticles contained in the ink, which was found to strongly influence the devices performance and film morphology. To date, this is the first successful fabrication of a solar device by inkjet printing of CIGS nanoparticles.     

A new simple route to grow Cu(In,Ga)Se2 thin films with large grains in the co-evaporation process

In the conventional three-stage co-evaporation process to grow Cu(In,Ga)Se₂ (CIGS) film, a large grain is achieved by the co-evaporation of Cu and Se on (In,Ga)₂Se₃ layer at 550 °C in the second stage and then a p-type is achieved by the co-evaporation of In, Ga, and Se in the third-stage. We reported a new process where a CIGS film with a large gain and p-type is achieved by evaporation of Cu only in the second stage at 400 °C and by the Se annealing in the third stage. In the new process, thermal budget was lowered and the third-stage co-evaporation process was eliminated. It was found that the CIGS gain size increased when the Cu/(In + Ga) ratio was above 0.7 and an addition thin CIGS layer appeared on the CIGS surface. The reaction path with Cu was described in the Cu-In-Se ternary phase diagram. The cell conversion efficiency increased from 9.6 to 15.4% as the Se annealing temperature increased from 400 to 550 °C in the third stage, mainly due to the increase of open-circuit voltage and fill factor. Our process demonstrated a new route to grow a CIGS film with a less thermal budget and simpler process in the co-evaporation process.     

低温超薄高效Cu(In,Ga)Se2太阳电池的实现

衬底温度保持恒定, 在Se气氛下按照一定的元素配比顺序蒸发Ga, In, Cu制备厚度约为0.7 μrm的Cu(In_0.7Ga_0.3)Se₂ (CIGS)薄膜. 利用X射线衍射仪分析薄膜的晶体结构及物相组成, 扫描电子显微镜表征薄膜形貌及结晶质量, 二次离子质谱仪测试薄膜内部元素分布, 拉曼散射谱 分析薄膜表面构成, 带积分球附件的分光光度计测量薄膜光学性能. 研究发现在Ga-In-Se预制层内, In主要通过晶界扩散引起Ga/(Ga+In)分布均匀化. 衬底温度高于450 ℃时, 薄膜呈现单一的Cu(In_0.7Ga_0.3)Se₂相; 低于400℃, 薄膜存在严重的Ga的两相分离现象, 且高含Ga相主要存在于薄膜的上下表面; 低于300 ℃, 薄膜结晶质量进一步恶化. 薄膜表层的高含Ga相Cu(In_0.5Ga_0.5)Se₂以小晶粒形式均匀分布于薄膜表面, 增加了薄膜的粗糙度, 在电池内形成陷光结构, 提高了超薄电池对光的吸收. 加上带隙值较小的低含Ga相的存在, 使电池短路电流密度得到较大改善. 衬底温度在550 ℃–350 ℃变化时, 短路电流密度J_SC是影响超薄电池转换效率的主要因素; 而衬底温度T_sub低于300 ℃时, 开路电压V_OC和填充因子FF降低已成为电池性能减退的主要原因. T_sub为350 ℃时制备的0.7 μm左右的超薄CIGS电池转换效率达到了10.3%. 关键词： 2薄膜')" href="#">Cu(In,Ga)Se₂薄膜 衬底温度 超薄 太阳电池     

Material and device properties of Cu(In,Ga)Se2 absorber films prepared by thermal reaction of InSe/Cu/GaSe alloys to elemental Se vapor

The aim of this work was to study the influence of selenization temperature on the morphological and structural properties of CuIn_1−xGa_xSe₂ (CIGS) polycrystalline thin films prepared by a two-step method. The compound and metallic precursors were deposited sequentially using GaSe, InSe and Cu sources by thermal evaporation. These identical InSe/Cu/GaSe precursors are then selenized with Se vapor in a vacuum system. All the CIGS films showed chalcopyrite structure and presence of secondary phases observed at low temperatures. High temperature treatment led to better crystalline and an increase in grain size. Solar cell devices are fabricated and J–V measurements performed under AM1.5 global solar spectra conditions at 25 °C are presented.     

Effect of post annealing on the characteristics of In2S3 buffer layer grown by chemical bath deposition on a CIGS substrate

In₂S₃ as an alternative Cd-free buffer in Cu(In,Ga)Se₂ (CIGS) solar cells was deposited on CIGS substrate by a chemical bath deposition and characterized after post annealing to optimize film properties for CIGS solar cells. A uniform and pinhole-free In₂S₃ film was deposited on a CIGS substrate by H₂O₂ treatment prior to chemical bath deposition. The In₂S₃ layer was an amorphous state due to the co-existence of In–S, In–O, and In–OH bonds. Annealing at 200 °C induced copper diffusion from CIGS into In₂S₃ layer and lowered the band gap from 3.3 to 1.9 eV, leading to phase change from amorphous state to crystalline state. The conduction band alignment at the In₂S₃/CIGS interface can be controlled by the post annealing. The shunt current through In₂S₃ film was prevented down to the thickness of 30 nm and a 1.15 eV shallow defect was eliminated by the annealing. The results indicated that post annealing in air is a critical to fabricate CIGS solar cells with a sub-30 nm CBD-In₂S₃ buffer layer.     

Growth mechanism of thermally processed Cu(In,Ga)S2 precursors for printed Cu(In,Ga)(S,Se)2 solar cells

We investigate a process used for the selenisation of particle‐based precursors to prepare low‐cost Cu(In,Ga)(S,Se)₂ (CIGS) solar cells. It is suitable for high throughput with a short optimum selenisation duration of 3–5 min and employs a rapid thermal annealing system with elemental selenium vapour. Homogeneous crack‐free Cu(In,Ga)S₂ precursor films of up to 1 µm are obtained via doctor blading. The high selenium vapour pressure in the selenisation reaction chamber results in the formation of a compact Cu(In,Ga)(S,Se)₂ layer on top of a carbon‐rich underlayer. In order to investigate the phase development in the film, the selenisation process was interrupted at different stages and the samples were monitored via XRD and surface‐sensitive Raman measurements. We find the formation of a polycrystalline Cu(In,Ga)Se₂ phase already after 1 s at the target temperature of 550 °C. Furthermore, the effect of initial precursor thickness on solar cell parameters is discussed. Complete solar cells are prepared by conventional methods, leading to conversion efficiencies well above 8%. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Post-annealing effect on the reactively sputter-grown CIGS thin films and its influence to solar cell performance

Using a reactive co-sputtering from Cu_0.6Ga_0.4 and Cu_0.4In_0.6 alloy targets, we prepared CuIn_1−xGa_xSe₂ (CIGS) thin films on Mo/soda-lime glass (SLG) in association with a thermal cracker for elemental atomic Se radicals. The film growth was performed at 500 °C for 90 min. To achieve the composition ratio of CIGS absorber layer, Cu_0.6Ga_0.4 target was set at RF power of 50 W, 60 W, 70 W, and 80 W while keeping at 100 W for Cu_0.4In_0.6 alloy target. Post-annealing was done for all the CIGS films at 550 °C for 30 min. The composition ratio of [Cu]/[In + Ga] and [Ga]/[In + Ga] was increased with RF power but showed no change after post-annealing. X-ray diffraction analysis revealed all the samples has grown dominantly in the [112] crystal orientation. We found the Cu_2−xSe and (InGa)_2−xSe₃ defect phase both at the surface and in the bulk, and developed with post-annealing. From the devices fabricated in the structure of grid/ITO/i-ZnO/CdS/CIGS/Mo/soda-lime glass (SLG), the external quantum efficiency (EQE) was observed to improve in the wavelength, λ ≥ 550 nm in the samples treated with annealing. In the current–voltage (J–V) measurements, the solar cell showed the best performance of FF = 54.1%, V_oc = 0.48 V, J_sc = 33.1 mA/cm² and η = 8.5% in the sample with [Cu]/[In + Ga] = 0.84 that improved largely from η = 4.6% for the solar cell with an as-grown CIGS films.     

Cu(In,Ga)Se2 thin film solar cells from nanoparticle precursors

A non-vacuum process for Cu(In,Ga)Se₂ (CIGS) thin film solar cells from nanoparticle precursors was described in this work. CIGS nanoparticle precursors was prepared by a low temperature colloidal route by reacting the starting materials (CuI, InI₃, GaI₃ and Na₂Se) in organic solvents, by which fine CIGS nanoparticles of about 15 nm in diameter were obtained. The nanoparticle precursors were then deposited onto Mo/glass substrate by the doctor blade technique. After heat treating the CIGS/Mo/glass layers in Se gas atmosphere, a complete solar cell structure was fabricated by depositing the other layers including CdS buffer layer, ZnO window layer and Al electrodes by conventional methods. The resultant solar cell showed a conversion efficiency of 0.5%.     

Extending absorption of near-infrared wavelength range for high efficiency CIGS solar cell via adjusting energy band

The efficient photon harvesting in near infrared wavelength range is still a challenging problem for high performance Cu(In_1-x, Ga_x)Se₂ (CIGS) solar cell. Herein, adjusting the energy band distribution of CIGS solar cell could provide significant academic guidance for devices with superior output electric power. To understand the role of each functional layer, the optimal 3000 nm CIGS absorber layer with 1.3 eV bandgap and 30 nm CdS buffer layer were firstly obtained via simulating the uniform band-gap structures. By introducing CIGS absorber layer with a double grading Ga/(Ga+In) profile, the power conversion efficiency of the double gradient band gap cell is superior to that of uniform band-gap cell through extending absorption of near-infrared wavelength range. Upon optimization, the best power conversion efficiency of CIGS with a double gradient band gap solar cell is improved significantly to 24.90%, among the best values reported in literatures, which is an 8.17% relative increase compared with that of the uniform band-gap cell. Our findings provide a theoretical guide toward the design of high performance solar cells and enrich the understandings of the energy band engineering for developing of novel semiconductor devices.     

Temperature dependent surface and spectral modifications of nano V<Subscript>2</Subscript>O<Subscript>5</Subscript> films

Nanocrystalline V₂O₅ films have been deposited on glass substrates at 300°C substrate temperature using thermal evaporation technique and were subjected to thermal annealing at different temperatures 350, 400, and 550°C. X-ray diffraction (XRD) spectra exhibit sharper and broader characteristic peaks respectively indicating the rearrangement of nanocrystallite phases with annealing temperatures. Other phases of vanadium oxides started emerging with the rise in annealing temperature and the sample converted completely to VO₂ (B) phase at 550°C annealing. FESEM images showed an increase in crystallite size with 350 and 400°C annealing temperatures followed by a decrease in crystallite size for the sample annealed at 550°C. Transmission spectra showed an initial redshift of the fundamental band edge with 350 and 400°C while a blue shift for the sample annealed at 550°C, which was in agreement with XRD and SEM results. The films exhibited smart window properties as well as nanorod growth at specific annealing temperatures. Apart from showing the PL and defect related peaks, PL studies also supported the observations made in the transmission spectra.     

Improvement in efficiency of solar cell by removing Cu2－xSe from CIGS film surface

CIGS thin films are deposited by sputtering and selenization. The synthesis of semiconducting polycrystalline thin films and characteristics of devices based on the CIGS absorbing layers are investigated. Their microstructures are characterized by x-ray diffraction and Raman spectroscopy. The results reveal that there exist metallic Cu_2-xSe compounds in CIGS film surfaces and the compounds are thought to be responsible for the degradation of the open circuit voltage of solar cells. The optimization of selenization temperature profile and copper content in the precursor surfaces is studied, concluding that the conversion efficiency may be improved by removing metallic Cu_2-xSe compounds from the surfaces of CIGS thin films.     

Solid-state synthesis in Ni/Fe/MgO(001) epitaxial thin films

Solid-state synthesis in Ni/Fe/MgO(001) bilayer epitaxial thin films has been studied experimentally. The phase sequence Fe/Ni→(～350°C)Ni₃Fe→(～400°C)NiFe→(～ 550°C)γ_par is formed as the annealing temperature increases. The crystal structure in the invar region consists of epitaxially intergrown single-crystal blocks consisting of the paramagnetic γ_par and ferromagnetic NiFe phases, which satisfy the orientation relationship [100](001)NiFe ∥ [100](001) γ_par. It has been shown that the nucleation temperatures of the Ni₃Fe, NiFe, and γ_par phases coincide with the temperatures of solid-state transformations in the Ni-Fe system.     

Improved growth of solution‐deposited thin films on polycrystalline Cu(In,Ga)Se2

CdS and Zn(O,S) grown by chemical bath deposition (CBD) are well established buffer materials for Cu(In,Ga)Se₂ (CIGS) solar cells. As recently reported, a non‐contiguous coverage of CBD buffers on CIGS grains with {112} surfaces can be detected, which was explained in terms of low surface energies of the {112} facets, leading to deteriorated wetting of the chemical solution on the CIGS surface. In the present contribution, we report on the effect of air annealing of CIGS thin films prior to the CBD of CdS and Zn(O,S) layers. In contrast to the growth on the as‐grown CIGS layers, these buffer lay‐ ers grow densely on the annealed CIGS layer, even on grains with {112} surfaces. We explain the different growth behavior by increased surface energies of CIGS grains due to the annealing step, i.e., due to oxidation of the CIGS surface. Reference solar cells were processed and completed by i‐ZnO/ZnO:Al layers for CdS and by (Zn,Mg)O/ZnO:Al for Zn(O,S) buffers. For solar cells with both, CdS and Zn(O,S) buffers, air‐annealed CIGS films with improved buffer coverage resulted in higher power‐conversion efficiencies, as compared with the devices containing as‐grown CIGS layers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Improved quantitative analysis of Cu(In,Ga)Se2 thin films using MCs+-SIMS depth profiling

The chalcopyrite semiconductor, Cu(InGa)Se₂ (CIGS), is popular as an absorber material for incorporation in high-efficiency photovoltaic devices because it has an appropriate band gap and a high absorption coefficient. To improve the efficiency of solar cells, many research groups have studied the quantitative characterization of the CIGS absorber layers. In this study, a compositional analysis of a CIGS thin film was performed by depth profiling in secondary ion mass spectrometry (SIMS) with MCs⁺ (where M denotes an element from the CIGS sample) cluster ion detection, and the relative sensitivity factor of the cluster ion was calculated. The emission of MCs⁺ ions from CIGS absorber elements, such as Cu, In, Ga, and Se, under Cs⁺ ion bombardment was investigated using time-of-flight SIMS (TOF-SIMS) and magnetic sector SIMS. The detection of MCs⁺ ions suppressed the matrix effects of varying concentrations of constituent elements of the CIGS thin films. The atomic concentrations of the CIGS absorber layers from the MCs⁺-SIMS exhibited more accurate quantification compared to those of elemental SIMS and agreed with those of inductively coupled plasma atomic emission spectrometry. Both TOF-SIMS and magnetic sector SIMS depth profiles showed a similar MCs⁺ distribution for the CIGS thin films.     

Thickness study of Al:ZnO film for application as a window layer in Cu(In1−xGax)Se2 thin film solar cell

Structural, electrical and optical properties of Al doped ZnO (Al:ZnO) thin film of various thicknesses, grown by radio-frequency magnetron sputtering system were studied in relation to the application as a window layer in Cu(In_1−xGa_x)Se₂ (CIGS) thin film solar cell. It was found that the electrical and structural properties of Al:ZnO film improved with increasing its thickness, however, the optical properties degraded. The short circuit current density, J_sc of the fabricated CIGS based solar cells was significantly influenced by the variation of the Al:ZnO window layer thickness. Best efficiency was obtained when CIGS solar cell was fabricated with electrically and optically optimized Al:ZnO window layer.     

Influence of deposition pressure and power on characteristics of RF-Sputtered Mo films and investigation of sodium diffusion in the films

Mo films deposited by DC sputtering are widely used as back contact in CIGS and CZTS based thin film solar cells. However, there have been only a few studies on the deposition of Mo films by RF sputtering method. In this context, Mo films on SLG substrates were prepared as a function of deposition pressure and power by using RF magnetron sputtering method to contribute to this shortcoming. Mo films were deposited at 250 °C substrate temperature by using 20, 15, 10 mTorr Ar pressures at 120 W RF power and 10 mTorr Ar pressure at 100 W RF power. Structural, morphological and reflectivity properties of RF-sputtered Mo films were clarified by XRD, AFM, FE-SEM and UV–Vis measurements. In addition, due to sodium incorporation from SLG substrate to the absorber layer through Mo back contact layer is so essential in terms of improving the conversion efficiency values of CIGS and CZTS thin film solar cell devices, the effects of Na diffusion in the films were analyzed with SIMS depth profile. The electrical properties of the films such as mobility, carrier density and resistivity were determined by Hall Effect measurements. It was found that Mo films prepared at 120 W, 10 mtorr and 250 °C substrate temperature and then annealed at 500 °C for 30 min, had resistivity as low as 10⁻⁵ Ω cm, as well as higher amount of Na incorporation than other films.     

Structural and optical characterization of Bi4Ti3O12 thin films prepared by metallorganic solution deposition technique

Single phase and nanosized microstructure Bi₄Ti₃O₁₂ thin films were prepared on fused quartz substrate by metallorganic solution deposition technique using titanium butoxide and bismuth nitrate at relatively low annealing temperature. The structural properties were characterized by XRD and AFM, which revealed that the crystallite sizes and crystallite cluster sizes of Bi₄Ti₃O₁₂ were increased with the increase of the annealing temperature and about 8.65–18.3 nm by XRD study and 60–110 nm by AFM study, respectively. The refractive index and extinction coefficient of the films were calculated by Manifacier method from the spectral transmission measurement. They were increased with the increase of the annealing temperature and decreased with the increase of wavelength. The band gaps of the films were about 2.96, 2.88 and 2.80 eV for 450, 550 and 650°C annealing temperatures, respectively.     

Cu(In,Ga)Se2 薄膜在共蒸发"三步法"中的相变过程

CIGS薄膜的结晶相是制备高质量薄膜的关键问题. 本文采用共蒸发"三步法"工艺沉积Gu(In, Ga)Se₂ (CIGS) 薄膜, 通过X射线衍射仪 (XRD) 和X射线荧光光谱仪 (XRF)、扫描电镜 (SEM) 结合的方法详细研究了"三步法"工艺的相变过程, 并制备出转换效率超过15% 的 CIGS 薄膜太阳电池. 关键词： CIGS薄膜 共蒸发三步法 相变过程     

Investigations on the sulphur incorporation in sputtered Cu,In multilayer precursors

High quality CuInS₂ layers have been grown using a two step process. Multiple Cu, In bilayers were deposited by RF magnetron sputtering on Mo-coated glass substrates followed by sulphurisation using elemental sulphur in a closed graphite box at different temperatures up to 550°C. The layers were characterised to study their structure and composition using XRD, SEM and EDAX. More sulphur was incorporated at lower annealing temperatures with sulphur content higher than 50 at.%, while the Cu/In ratio ranges between 0.9 to 1.1. As the annealing temperature increases beyond 400°C, the composition of sulphur decreases to 46 at.% with an incorporation of Mo in the layers. The secondary phases observed at different annealing temperatures were identified and reported. Polycrystalline, single phase and densely packed CuInS₂ layers with (1 1 2) preferred orientation were obtained for annealing temperatures of about 350°C.     

Evolution of phase purity and texture on annealing of BiFeO3 thin film prepared by sol-gel technique

We report preparation of phase pure BiFeO₃ thin films on glass, ITO and Si(100) substrates through chemical route using spin coating technique. Sol-gel process was adopted to prepare the films using bismuth nitrate and iron nitrate as precursors. X-Ray diffraction and Raman spectroscopy studies revealed amorphous nature of the as deposited films. Rhombohedral crystalline phase of BiFeO₃ evolved on annealing the films at 500°C, but with Bi₂Fe₄O₉ and Bi₂₄Fe₂O₃₉ as impurity phases. Increasing the annealing temperature to 550°C caused a drastic reduction of the impurity phases and at 600°C, the films were phase-pure BiFeO₃. Micro Raman spectra showed features consistent with the reported characteristic peaks of BiFeO₃ crystalline phase for films annealed at 500 and 550°C. Crystallite size obtained from X-ray diffraction line width analysis are within 30 to 40 nm. Atomic force microscopy (AFM) however showed grain size of ∼192 nm, indicating polycrystalline nature of the grains.