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     

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     

等离子体活化硒对电沉积Cu-In-Ga金属预制层硒化的影响

使用等离子体活化硒源对电沉积制备的Cu-In-Ga金属预制层进行了硒化处理时, 发现等离子体功率对Cu(In_1-xGa_x)Se₂(CIGS)晶粒的生长有重要影响, 当等离子体功率为75 W时, 制备出单一Cu(In_0.7Ga_0.3)Se₂相的CIGS薄膜. 通过对不同衬底温度的等离子体活化硒源硒化的CIGS 薄膜进行了研究与分析, 并与普通硒化后的薄膜进行对比, 发现高活性硒在低温下会促进Ga-Se二元相的生成, 从而有利于Cu(In_0.7Ga_0.3)Se₂单相的生长. 对等离子体硒化后的CIGS薄膜进行了电池制备, 发现单相CIGS薄膜没有显著提高电池性能. 通过优化工艺, 所制备的CIGS电池效率达到了9.4%. 关键词： 0.7Ga_0.3)Se₂')" href="#">Cu(In_0.7Ga_0.3)Se₂ 电沉积 Cu-In-Ga金属预制层 等离子体活化硒     

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     

预制层溅射气压对CIGS薄膜结构及器件的影响

研究了金属预制层制备过程中溅射气压对Cu(In_1-xGa_x)Se₂(CIGS)薄膜及电池器件性能的影响.通过调节溅射气压改变预制层的结晶状态及疏松度与粗糙度,在合适的预制层结构下,活性硒化热处理过程中,可使Ga有效地掺入到薄膜中形成优质的CIGS固溶体.高溅射气压会使预制层过于致密,呈现非晶态趋势.经活性硒化热处理后,CIGS薄膜容易产生CIS与CGS"两相分离"现象,从而导致CIGS薄膜太阳电池的开路电压和填充因子降低,电池转换效率由10.03%降低到5.02%.     

电沉积Cu-In-Ga金属预制层的硒硫化研究

以H₂S气体作为硫源、固态蒸发硒蒸气作为硒源对电沉积Cu-In-Ga金属预制层进行硒硫化处理. 通过电沉积Cu-In-Ga金属预制层在不同衬底温度下硒化、硫化和硒硫化的对比实验,发现CuInS₂相和CuIn（S,Se）₂相优先生成,抑制了CuInSe₂相的生成,促使InSe相薄膜向内部扩散,减弱了薄膜两相分离现象. 采用先硒化后硒硫化处理工艺优化了Cu（In,Ga）（S,Se）₂薄膜的制备工艺,在250 ℃预硒化得到了开路电压为570 mV的太阳电池,在更高的预硒化温度得到了较大短路电流的太阳电池,最终优化得到了效率达到10.4%的电池器件. 关键词： 电化学沉积 Cu-In-Ga金属预制层 硒硫化处理 2薄膜')" href="#">Cu(In,Ga)(S,Se)₂薄膜     

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     

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.     

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(In1-xGax)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CuxSe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.     

太阳电池用Cu2ZnSnS4薄膜的反应溅射原位生长及表征

通过直流反应磁控溅射技术,原位生长制备了太阳电池用Cu₂ZnSnS₄(CZTS)薄膜.采用X射线能量色散谱仪、扫描电镜、X射线衍射仪、紫外可见分光光度计和霍尔效应测试系统对薄膜进行了表征.结果表明,原位生长的CZTS薄膜具有均质、致密和平整的形貌,且由贯穿整个薄膜厚度的柱状颗粒组成.不同基底温度下生长所得薄膜的Cu/(Zn+Sn) 值均约为1,而Zn/Sn值均大于1且随着基底温度升高而减小.所得薄膜在(112)方向上择优取向明显,且结构特征受基底温度和Cu/(Zn+Sn)的共同影响.所得薄膜均具有高达10⁴cm^-1的光吸收系数,其带隙宽度随着生长温度的增加而降低,并且在500℃时为(1.51±0.01)eV.薄膜的导电类型均为p型,且具有与器件级Cu(In,Ga)Se₂(CIGS)相当的载流子浓度. 关键词： 2ZnSnS₄')" href="#">Cu₂ZnSnS₄ 直流反应磁控溅射 原位生长 太阳电池     

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%.     

A comparative study of solution based CIGS thin film growth on different glass substrates

CuIn_xGa_1−xSe_yS_2−y (CIGS) thin films were synthesized on glass substrates by a paste coating of Cu, In, and Ga precursor solution with a three-step heat treatment process: oxidation, sulfurization, and selenization. In particular, morphological changes of CIGS films for each heat treatment step were investigated with respect to the kinds of glass substrates: bare, Mo-coated, and F-doped SnO₂ (FTO) soda-lime glasses. Very high quality CIGS film with large grains and low degree of porosity was obtained on the bare glass substrate. Similar morphology of CIGS film was also acquired on the Mo-coated glass except the formation of an undesired Mo oxide interfacial layer due to the partial oxidation of Mo layer during the first heat treatment under ambient conditions. On the other hand, CIGS film with much smaller grains and higher degree of porosity was gained when FTO glass was used as a substrate, resulting in slight solar to electricity conversion behavior (0.20%). Higher power conversion efficiency (1.32%) was attained by the device with the CIGS film grown on Mo-coated glass in spite of the presence of a Mo oxide impurity layer.     

氢退火的BZO前电极对非晶硅薄膜太阳能电池性能的影响

采用低压化学气相沉积方法在玻璃衬底上制备了B掺杂的ZnO（BZO）薄膜,通过氢退火对BZO进行处理,然后作为前电极进行了非晶硅薄膜太阳能电池的制备及性能研究。结果表明：在氢气气氛下退火后,BZO薄膜的载流子浓度基本无变化,但Hall迁移率显著提高,这使得BZO薄膜的导电能力提高;当采用厚度较小、透光率较高的BZO薄膜进行氢退火后作为前电极结构时,非晶硅薄膜太阳能电池的短路电流密度提高0.3~0.4 mA/cm²,电池的转化效率提高0.2%。实验结果可为通过优化前电极结构来提高非晶硅薄膜太阳能电池转化效率提供一种简易的方法。     

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.     

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.     

铜铟镓硒薄膜太阳能电池新型图形化透明前电极研究

为了优化铜铟镓硒薄膜太阳能电池的前电极,提高铜铟镓硒薄膜太阳能电池的效率,提出了一种可应用于铜铟镓硒薄膜太阳能电池的AZO/图案化Ag薄膜/AZO结构的前电极,中间层的Ag薄膜与电池顶层的金属栅线具有完全相同的图案和尺寸,并且位于金属栅线的正下方,这种新型结构可以提高电池前电极的电学性能,但对电池来说不会带来额外的光学损失。对比了新型前电极结构与几种传统前电极的电学和光学性能,并且制备了相应的电池进行了性能对比。实验结果表明,新型的前电极结构可以提高铜铟镓硒薄膜太阳能电池的短路电流,相对传统AZO电极,电池效率从13. 83%提高到14. 53%。本结构可以明显提高电池效率。     

Cu（In,Ga）Se2 Thin Films on Flexible Polyimide Sheet： Structural and Electrical Properties versus Composition

The structural and electrical properties of Cu（In,Ga）Se2 （CIGS） films grown on polyimide （PI） sheet using the three-stage co-evaporation process are investigated by x-ray diffraction spectra （XRD）, scanning electron microscopy （SEM）, Raman spectra, and Hall effect measurements, respectively. The results show that the properties of CIGS films on PI sheet are strongly dependent on the compositional ratio of Cu/（In＋Oa） （Cu/Ⅲ）. In contrast to the non-stoichiometric CIGS films, stoichiometric CIGS films show better structural and electrical properties, such as a relatively larger grain size, lower resistivity and higher carrier concentration. The flexible CIGS solar cells on PI sheet with the conversion efficiencies of 9.7% and 6.6% are demonstrated for the CIGS absorber layer with Cu/Ⅲ of 0.96 and 0.76, respectively （active area, 0.20cm^2）. The cell efficiency for Cu-poor CIGS films is limited by a relatively lower open circuit voltage and fill factor.     

Interface and bulk properties of Cu(In,Ga)Se2 solar cell with a cracker-ZnS buffer layer

Cu(In,Ga)Se₂ (CIGS) solar cells were fabricated by varying the film thickness of the cracker-ZnS (c-ZnS) buffer layer from 0 nm to 20 nm, and performance was found to depend on c-ZnS film thickness. The best cell efficiency of approximately 8% was obtained from the CIGS solar cell with an 8 nm thick-c-ZnS buffer layer. To investigate the primary factor to determine the cell performance, we utilized the impedance spectroscopy (IS) reflecting interface qualities, and capacitance-voltage (CV) profiling sensitive to bulk properties. In IS results, an equivalent circuit model including the resistance and capacitance was proposed to interpret cell performance, and carrier lifetime was obtained in connection with recombination probability at p-n junction. In CV profiling, the carrier concentration in the CIGS bulk, the depletion width, and the charge distribution related to the defect states along the depth direction were evaluated. The formation mechanism of c-ZnS buffer layer is suggested by measuring the chemical states, which is closely associated with the IS and CV results. The depletion width substantially increased at c-ZnS film thickness more than 15 nm due to the diffusion of Zn atoms toward CIGS layer, resulting in negative influence on cell performance. From this study, we demonstrated that IS and CV profiling are complementary analysis tools for interpretation of the solar cell operation concerning the interface and bulk properties.