电沉积Cu(In,Ga)Se_2预置层硫化退火制备Cu(In,Ga)(Se,S)_2薄膜及表征

在550℃下的H2S气氛中退火处理电沉积制备的Cu(In,Ga)Se2(CIGS)预置层,制备了太阳电池光吸收层Cu(In,Ga)(Se,S)2(CIGSS)薄膜.采用X射线能量色散谱、俄歇电子能谱、扫描电镜、X射线衍射和拉曼光谱对退火前后的薄膜进行表征.结果表明,H2S气氛下退火能够实现薄膜中O的去除和S的掺入,同时使得各元素的纵向分布更加均匀并可消除Cu-Se微相.此外,H2S退火还可改善薄膜的结晶性能,并使S和Ga进入黄铜矿结构,薄膜晶格参数变小.     

Cu元素对Cu(In,Ga)Se_2薄膜及太阳电池的影响

Cu元素成分对Cu(In,Ga)Se2(简称CIGS)薄膜材料的电学性质及其电池器件性能有很重要的影响.本文利用蒸发法制备了贫Cu和富Cu的CIGS吸收层(0.7Cu/(Ga+In)1.15)及相应的电池器件.扫描电镜和Hall测试发现,富Cu材料的结构特性(晶粒大、结晶状态好)和电学特性(电阻率低、迁移率高等)优于贫Cu材料,而性能测试表明贫Cu器件的效率优于富Cu器件.变温性能测试分析表明,贫Cu器件的主要复合路径是体复合,激活能与CIGS禁带宽度相当;富Cu器件的主要复合路径是界面复合,其激活能远小于CIGS禁带宽度,这大大降低了开路电压Voc,从而降低了电池效率.最后利用蒸发三步法制备了体材料稍富Cu表面贫Cu的CIGS吸收层,降低了短路电流和开路电压的损失,获得了超过15%的电池效率.     

Efficiency enhancement of Cu(In,Ga)Se2 thin‐film solar cells by a post‐deposition treatment with potassium fluoride

Alkali‐free Cu(In,Ga)Se₂(CIGS) absorbers grown on Mo‐coated alumina (Al₂O₃) substrates were doped with potassium (K) after CIGS growth by a potassium fluoride (KF) post‐deposition treatment (PDT). The addition of K to the absorber leads to a strong increase in cell efficiency from 10.0% for the K‐free cell to 14.2% for the K‐doped cell, mainly driven by an increase in the open‐circuit voltage V_oc and the fill factor FF, and to an increase in the net charge carrier density. Hence K doping by KF‐PDT is comparable to doping with Na.

     

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     

Optoelectrical improvement of ultra‐thin Cu(In,Ga)Se2 solar cells through microstructured MgF2 and Al2O3 back contact passivation layer

Decreasing the absorber layer thickness of thin‐film solar cells can be an effective solution for cost reduction of photovoltaic electricity generation. Unfortunately, this reduction leads to detrimental effects such as incomplete photon absorption and increased charge carrier recombination at the rear electrode. To tackle these losses in ultra‐thin 0.5 µm Cu(In,Ga)Se₂ (CIGS) solar cells, we developed different passivation structures made of MgF₂ and Al₂O₃ at the molybdenum–CIGS interface, leading to localized back contacts. The influence of the distance between those contacts on the cell performance was studied by varying the periodicity of the applied 1D patterns from 6 μm to 30 μm. Thus, an increase in performance was measured for microstructured layers with a periodicity of up to 12 µm. More precisely, a MgF₂ layer yielded an increase in power conversion efficiency (PCE) of up to 9%_rel compared to an unpassivated cell design, and a passivation layer comprising Al₂O₃ led to up to a 5%_rel increase in PCE. The gains were primarily attributed to an increased reflectivity of the back contact, while the formation of a negative backside field in the case of Al₂O₃ might have contributed to this increase by preventing electrons from recombining at the backside interface. Our findings indicate a high lateral conductivity for holes inside the multicrystalline CIGS compound over few tens of micrometres, which allows an independent design of future back contacts and light‐trapping schemes.

False‐colour scanning electron microscopy cross‐section picture of a passivated solar cell, with the front contact layers coloured in green, the 0.5 µm CIGS absorber in dark red, the MgF₂ passivation layer in blue, and the Mo back contact in grey.     

Stage2沉积速率对低温生长CIGS薄膜特性及器件的影响

研究了三步法第二步沉积速率对低温生长Cu(In,Ga)Se₂薄膜结构、 电学特性和器件特性的影响. 通过改变第二步沉积速率发现, 提高沉积速率可以显著促进薄膜晶粒生长, 提高晶粒紧凑程度降低晶界复合, 同时有效改善两相分离现象, 提高电池的开路电压和短路电流, 有助于Cu(In,Ga)Se₂电池光电转换效率的提高. 但同时研究表明, 随着第二步沉积速率的增加, 会促进暂态Cu_2-xSe晶粒的生长, 引起Cu(In,Ga)Se₂薄膜表面粗糙度增大, 并阻碍Na向Cu(In,Ga)Se₂薄膜表面的扩散, 造成施主缺陷钝化效应降低, 薄膜载流子浓度下降和电阻率升高, 且过高的沉积速率会引起电池内部复合增加并产生分流路径, 造成开路电压下降进而引起电池效率恶化. 最终, 通过最佳化第二步沉积速率, 在衬底温度为420℃时, 得到最高转换效率为11.24%的Cu(In,Ga)Se₂薄膜太阳电池.     

Compositional and electrical properties of line and planar defects in Cu(In,Ga)Se2 thin films for solar cells – a review

The present review gives an overview of the various reports on properties of line and planar defects in Cu(In,Ga)(S,Se)₂ thin films for high‐efficiency solar cells. We report results from various analysis techniques applied to characterize these defects at different length scales, which allow for drawing a consistent picture on structural and electronic defect properties. A key finding is atomic reconstruction detected at line and planar defects, which may be one mechanism to reduce excess charge densities and to relax deep‐defect states from midgap to shallow energy levels. On the other hand, nonradiative Shockley–Read–Hall recombination is still enhanced with respect to defect‐free grain interiors, which is correlated with substantial reduction of luminescence intensities. Comparison of the microscopic electrical properties of planar defects in Cu(In,Ga)(S,Se)₂ thin films with two‐dimensional device simulations suggest that these defects are one origin of the reduced open‐circuit voltage of the photovoltaic devices. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

不同成分比例CIGS薄膜及太阳电池的快速退火

研究了110~180 ℃(2 min)下的快速热退火对Cu(In,Ga)Se2(CIGS)薄膜特性及CIGS太阳电池性能的影响.结果表明:对于不同成分比例的CIGS(正常、富Cu、高Ga)电池来说,150 ℃,2 min的快速退火最利于电池性能及二极管特性的增加.其中,退火对富Cu电池的开路电压Voc改善最大,这是因为快速热退火对消除部分CIGS薄膜中的CuSex有积极作用,从薄膜的电阻率有少量提高,器件的短路电流Jsc有少量下降可以得到验证;而对于高Ga电池来说,填充因子FF的改善最大,这是因为高Ga样品的缺陷较多,退火会消除薄膜内部的部分缺陷,从而薄膜的迁移率及Jsc都有所提高,使得FF有较大的增加.     

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)     

Performance improvement of CdS/Cu（In,Ga）Se2 solar cells after rapid thermal annealing

In this paper, we investigated the effect of rapid thermal annealing (RTA) on solar cell performance. An opto-electric conversion efficiency of 11.75% (Voc=0.64 V, Jsc = 25.88mA/cm2 , FF=72.08%) was obtained under AM 1.5G when the cell was annealed at 300℃ for 30s. The annealed solar cell showed an average absolute efficiency 1.5% higher than that of the as-deposited one. For the microstructure analysis and the physical phase confirmation, X-ray diffraction (XRD), Raman spectra, front surface reflection (FSR), internal quantum efficiency (IQE), and X-ray photoelectron spectroscopy (XPS) were respectively applied to distinguish the causes inducing the efficiency variation. All experimental results implied that the RTA eliminated recombination centers at the p-n junction, reduced the surface optical losses, enhanced the blue response of the CdS buffer layer, and improved the ohmic contact between Mo and Cu(In, Ga)Se2 (CIGS) layers. This leaded to the improved performance of CIGS solar cell.     

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.     

Real‐time analysis of the microstructural evolution and optical properties of Cu(In,Ga)Se2 thin films as a function of Cu content

Thin films of Cu(In,Ga)Se₂ with various copper contents were deposited by co‐evaporation onto thermally oxidized silicon substrates. Characterization by real‐time spectroscopic ellipsometry reveals clear similarities among the samples, as well as key variations with Cu content. Although all films exhibit a Volmer–Weber nucleation and similar fundamental critical point energies in the analysis of optical properties, Cu‐rich films exhibit enhanced coalescence, smoother surfaces, larger grain sizes, as well as a sub‐bandgap absorption which is absent in Cu‐poor films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

The effect of Na on the electronic properties of Cu(In,Ga)Se2 thin films: A local‐probe study

We investigated the effect of Na incorporation on the electronic properties of polycrystalline CuIn_0.7Ga_0.3Se₂ thin films using scanning tunneling microscopy and spectroscopy. The tunneling spectra indicate a reduced in‐gap density of states at grain boundaries and reveal a downward band‐bending in Na‐rich grain boundaries with respect to the adjacent grains, in agreement with our conductive atomic force microscopy data. It thus appears that Na passivates deep‐level defects at grain boundaries and induces a downward band‐bending there. Moreover, we provide evidence that Na passivates mainly Cu vacancy related defects. We suggest that the grain‐boundary passivation, which reduces the recombination rate of photogenerated carriers, is at least of major importance in the well known Na‐induced improvement in the efficiency of the corresponding solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Radiation-induced defects in thin Cu(In,Ga)Se<Subscript>2</Subscript> films on exposure to high-energy electron irradiation

At 4.2 K, the photoluminescence spectra of Cu(In,Ga)Se₂ films irradiated by electrons with an energy of 5 MeV displayed the 0.93-and 0.79-eV bands that owe their origin to the radiative recombination of nonequilibrium charge carriers on radiation-induced defects. The position of the energy levels of the defects is determined and their nature is discussed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 805–808, November–December, 2005.     

衬底对Cu(In,Ga)Se2薄膜织构的影响

分别在苏打石灰玻璃、Mo箔、无择优取向的Mo薄膜以及(110)择优取向的Mo薄膜四种不同衬底上，采用共蒸发工艺沉积约2 μm厚的Cu(In,Ga)Se₂薄膜，用X射线衍射仪测量薄膜的织构，研究衬底对Cu(In,Ga)Se₂薄膜织构的影响.在以上四种衬底上沉积的Cu(In,Ga)Se₂薄膜的(112)衍射峰强度依次逐渐减弱，(220/204)衍射峰从无到有且强度逐渐增强.在苏打石灰玻璃和Mo箔衬底上的Cu(In,Ga)Se_{2关键词： 择优取向 Cu(In 2}薄膜')" href="#">Ga)Se₂薄膜 太阳电池