Structural and optical properties of CdS/Cu(In,Ga)Se<Subscript>2</Subscript> heterostructures irradiated by high-energy electrons*

Thin films of Cu(In, Ga)Se₂ (CIGS) with a Ga/(Ga + In) ratio of ~0.27 corresponding to the standard elemental composition for solar-energy transducers were grown on Mo-coated glass substrates by the Cu, In, Ga, and Se co-evaporation technique from different sources. Transmission (T), photoluminescence (PL), and photoluminescence excitation (PLE) spectra at 4.2 K were used to analyze electronic properties in the asgrown and electron-irradiated CIGS films. The band-gap energy (E_g) of the CIGS films measured using both transmission and PLE methods was found to be about 1.28 eV at 4.2 K. Two deep bands in the PL spectra of the irradiated CIGS films, P₁ at ~0.91 eV and P₂ at ~0.77 eV, have been detected. These bands are tentatively associated with copper atoms substituting indium (Cu_In) and indium vacancies V_In, respectively, as the simplest radiation-induced defects.     

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.     

Ga梯度分布对Cu(In,Ga)Se_2薄膜及太阳电池的影响

传统制备Cu(In,Ga)Se2(CIGS)手段之一是共蒸发三步法,工艺中通过Cu,In,Ga,Se 4种元素相互扩散、作用形成抛物线形的Ga梯度分布.本文通过调整Ga源温度制备了Ga梯度分布不同的CIGS薄膜及电池.利用多种测试方法,研究了Ga梯度分布不同对CIGS薄膜表面及背面结构性质及电性质的影响,计算分析了表面导带失调值及背面电场对电池性能的影响,从而获得了合适的Ga梯度分布,提高了电池光谱相应,获得了较好的电池性能参数.     

Chemical elaboration of well defined Cu(In,Ga)Se2 surfaces after aqueous oxidation etching

The present work is an attempt to prepare well defined surfaces of Cu(In,Ga)Se₂ (CIGS) thin films in order to answer to basic questions about the relationship between bulk and surface composition. The approach is to use an oxidative etch with an aqueous bromine solution, known to lead to specular surfaces. The CIGS surface is then analyzed by mechanical profilometry, SEM and XPS, allowing for determination of the surface roughness and the nature of surface species. After short time bromine etch, a Se⁰ film is formed on the CIGS surface which can be completely removed by KCN treatment, leaving a CIGS specular surface. An highlight result is that under specific conditions, the surface composition is close to the stoichiometry of the Cu(In,Ga)₃Se₅ copper deficient phase. This is the first time that such a study is conducted on technology relevant thin polycrystalline CIGS film. It is expected that the method described will help conducting experiments (e.g. Angle resolved XPS, SIMS, etc.) with an improved resolution.     

Influence of different precursor surface layers on Cu(In<Subscript>1-x</Subscript>Ga<Subscript>x</Subscript>)Se<Subscript>2</Subscript> thin film solar cells

The properties of Cu(In_1-xGa_x)Se₂ (CIGS) thin films obtained by selenization of the precursors with different surface layers have been studied, and photovoltaic devices based on the absorbers were measured and analyzed. The devices constructed by the absorbers obtained by selenization of the precursors with CuGa-rich surface layers are improved, compared with those with In-rich surface layers. Through XRD, SEM, SIMS, illuminated J–V, QE and Raman spectra measurements, it was found that the increased Ga contents within the surface region of films and the graded Ga distribution can be realized in the selenized thin films fabricated by the precursors with the CuGa-rich surface layer. Consequently, the performances of the photovoltaic devices based on these thin films are further improved. PACS 61.72.Ss; 87.64.Jt; 68.60.Bs; 81.15.Cd; 84.60.Jt     

Photovoltaic performance of flexible Cu(In,Ga)Se2 thin-film solar cells with varying Cr impurity barrier thickness

We report the effect of Cr impurity barrier on Cu(In,Ga)Se₂ (CIGS) thin-film solar cells prepared on flexible substrates. The Cr films with varying the thickness (t_Cr) were deposited on stainless steel substrates using direct-current magnetron sputtering. The solar cell performance was improved by increasing t_Cr since the diffusion of Fe impurities from the substrate to CIGS was suppressed. Although the elemental composition, grain size, and strain of CIGS film showed little change with varying Fe content, the fill factor and the short-circuit current density increased as decreasing Fe. The Fe increased the series resistance, shunt paths, and saturation current density. The reduction of Fe caused a steeper bandgap grading in CIGS which enhances current collection due to higher electric fields in bulk CIGS. CIGS solar cells with 1000 nm-thick Cr barrier showed the best conversion efficiency of 9.05%.     

Surface modification of CIGS film by annealing and its effect on the band structure and photovoltaic properties of CIGS solar cells

The composition of Cu(In,Ga)Se₂ (CIGS) films employed in CIGS solar cells is Cu deficient. There can be point defects, including Cu vacancies, Se vacancies, and metal anti-site defects. The surface composition and defects are not well controlled right after CIGS film fabrication with a three-stage co-evaporation process. This fabrication technique can result in a large variation in cell efficiency. In order to control the CIGS film in a reproducible way, we annealed the CIGS film in air, S, or Se. With this annealing procedure, the Cu content of the CIGS surface was significantly reduced and Ga content was strongly increased. An intrinsic CIGS layer with a lower valence-band maximum and a wider ban gap was formed at the surface. By annealing the CIGS film, the open-circuit voltage and fill factor were significantly improved, which indicates that the surface intrinsic layer acts as a hole-blocking layer so that the surface recombination rate is suppressed. In addition to CIGS film annealing, with subsequent annealing of the completed devices using rapid thermal annealing, the efficiency and reproducibility of CIGS solar cells were markedly improved.     

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.     

Nd:YAG laser ablation characteristics of thin CIGS solar cell films

This work reports that the ablation characteristics of thin CuIn_1?x Ga _x Se₂ (CIGS) solar cell film differ significantly with elemental composition and laser pulse energy. From in situ shadowgraphs measured during Nd:YAG laser (1,064 nm) irradiation of CIGS films and crater morphologies, it was found that strong surface evaporation is dominant for low Ga concentration films of which band gap is well below the photon energy. As the band gap of CIGS film becomes close to or over the laser photon energy due to increased Ga content, surface absorption diminishes and at low laser energy, laser heating of the film plays an important role. It is demonstrated that for the CIGS films with Ga/(Ga + In) ratio being approximately over 0.2, the laser irradiation leads to solid phase removal of the film due to thermomechanical fracture at low laser energy but to ablative evaporation at elevated energy.     

硒化前后电沉积贫铜和富铜的Cu(In1-xGax)Se2薄膜成分及结构的比较

采用电沉积法获得了接近化学计量比的贫铜和富铜的Cu（In_1-xGa_x）Se₂（CIGS）预置层,研究比较了两种预置层及其硒化处理后的成分和结构特性.得到了明确的实验证据证明,硒化后富铜薄膜中的Cu_xSe相会聚集凝结成结晶颗粒分散在表面.研究表明：在固态源硒化处理后,薄膜成分基本不变;当预置层中原子比Cu/（In+Ga）<11时,硒化后薄膜表面存在大量的裂纹;而当Cu/（In+Ga） >12时,可以消除裂纹的产生,形成等轴状小晶粒;富铜预置层硒化时蒸发沉积少量In,Ga和Se后,电池效率已达到68%;而贫铜预置层硒化后直接制备的电池效率大于2%,值得进一步深入研究. 关键词： 1-xGa_x）Se₂薄膜')" href="#">Cu（In_1-xGa_x）Se₂薄膜 电沉积 硒化处理 贫铜或富铜薄膜     

A new method of generating Ga slope in Cu(In,Ga)Se2 film by controlling Se content in a multi-stacked precursor

An appropriate Ga slope is required in Cu(In,Ga)Se₂ (CIGS) film to enhance the cell performance of CIGS thin-film solar cells. In the conventional three-stage-co-evaporation process, the Ga slope was obtained by controlling Ga/In flux during deposition process. However, in two-step process, where a precursor was deposited first and then annealed in a Se environment for mass production, the desirable Ga slope was not achievable with the Ga/In flux control. We observed that the Ga/(Ga + In) ratio was nearly flat in CIGS film for Se-rich precursor and the ratio was nearly zero at surface and very high on bottom side of CISG film for Se-deficient precursor. We were able to generate a CIGS film with a Ga non-zero Ga surface and desired slope in the bulk by devising a precursor with Se-rich layer on top and Se-deficient layer on bottom, resulting in the enhancement of Cell performance.     

Compositional investigation of potassium doped Cu(In,Ga)Se2 solar cells with efficiencies up to 20.8%

We report on the interaction between intentional potassium doping of thin film Cu(In,Ga)Se₂ (CIGS) solar cells, CIGS absorber composition, and device efficiency. Up to now high efficiency CIGS solar cells could not be produced with a gallium/(gallium + indium) ratio higher than 35%. The new doping process step does not only increase solar cell conversion efficiencies up to 20.8%, but also allows a shift in the CIGS absorber composition towards higher gallium content whilst maintaining this high efficiencies level. We find that the saturation of the open circuit voltages for higher gallium content that is normally observed can partially be overcome by the new doping procedure. This observation leads us to the conclusion that even on this high performance level CIGS solar cells still hold a potential for further development beyond the record values reported here. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemical Structure of Fe<Subscript>78</Subscript>B<Subscript>13</Subscript>Si<Subscript>9</Subscript> Alloy Surface Layers in the Solid and Liquid States

The chemical structure of Fe₇₈B₁₃Si₉ alloy in the solid and liquid states and local atomic environment are studied in situ by X-ray photoelectron spectroscopy (XPS). The chemical bonds between elements in the melt are analyzed during a temperature increase. Two temperature regions are identified. The liquid surface in the first temperature region is shown to contain clusters of Fe-Si and (Fe-O _x )-Si types. In the second one, clusters of Fe-B and (Fe-O _x )-B types dominate. It is impossible to determine the composition of the clusters definitively using XPS data only. A jump-like change in the composition of the surface layers of the melt is detected, which is interpreted as structural transformations within the liquid state.     

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.     

Local current–voltage behaviors of preferentially and randomly textured Cu(In,Ga)Se2 thin films investigated by conductive atomic force microscopy

Electrical transport properties on polycrystalline Cu(In,Ga)Se₂ (CIGS) (Ga/(In+Ga) ≈35%) thin films were examined by conductive atomic force microscopy. The CIGS thin films with a (112) preferential or random texture were deposited on Mo-coated glass substrates. Triangular pyramidal grain growths were observed in the CIGS thin films preferentially textured to the (112) planes. Current maps of the CIGS surface were acquired with a zero or non-zero external voltage bias. The contrast of the images on the grain boundaries and intragrains displayed the conduction path in the materials. Local current–voltage measurements were performed to evaluate the charge conduction properties of the CIGS thin films.     

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)     

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     

Site occupation of indium and jump frequencies of cadmium in FeGa<Subscript><Emphasis Type="Bold">3</Emphasis></Subscript>

Perturbed angular correlation (PAC) measurements using the In-111 probe were carried out on FeGa₃ as part of a broader investigation of indium site occupation and cadmium diffusion in intermetallic compounds. One PAC signal was observed with hyperfine parameters ω ₁= 513.8(1) Mrad/s and η= 0.939(2) at room temperature. By comparison with quadrupole frequencies observed in PAC measurements on isostructural RuIn₃, it was determined that indium occupies only the 8j site in the FeGa₃ structure, denoted Ga(2) below because two out of the three Ga sites have this point symmetry. PAC spectra at elevated temperature exhibited damping characteristic of electric field gradients (EFGs) that fluctuate as Cd probes jump among Ga(2) sites within the lifetime of the excited PAC level. A stochastic model for the EFG fluctuations based on four conceivable, single-step jump-pathways connecting one Ga(2) site to neighboring Ga(2) sites was developed and used to fit PAC spectra. The four pathways lead to two observable EFG reorientation rates, and these reorientation rates were found to be strongly dependent on EFG orientation. Calculations using density functional theory were used to reduce the number of unknowns in the model with respect to EFG orientation. This made it possible to determine with reasonable precision the total jump rate of Cd among Ga(2) sites that correspond to a change in mirror plane orientation of site-symmetry. This total jump rate was found to be thermally activated with an activation enthalpy of 1.8 ±0.1 eV.     

New class of holographic materials based on CdF<Subscript>2</Subscript> semiconductor crystals with bistable centers. I. Role of covalence in the formation of bistable centers

Calculations of the electronic structure of In, Ga, and Al impurity centers in a CdF₂ crystal in the cluster approximation using the method of scattered waves are made. The first two impurities form in additively colored crystals bistable centers having a ground two-electron (deep) state and a metastable hydrogen-like (shallow) state. A change in the nature of the chemical bond on doping a crystal with these impurities is traced, which consists in a considerable increase of its covalent component. A change for deep In and Ga centers is shown to be caused by the reconstruction of centers in their ground state, and a conclusion about the character of reconstruction is made. This conclusion agrees with recent calculations made for the center structure using the pseudopotential method. Conditions of formation of bistable centers in CdF 2 and their structure in different charge states are discussed.     

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