退火温度对铜铟镓硒薄膜电学性能的影响

使用磁控溅射铜铟镓硒(CuIn1-xGaxSe2,CIGS)四元陶瓷靶材制备沉积态预制膜,在240-550℃对预制膜进行退火处理,着重研究了退火温度对薄膜电学性能(载流子浓度及迁移率)的影响。结果表明:退火温度低于270℃时薄膜中存在CuSe低电阻相,CIGS薄膜的载流子浓度在1017-1019cm-3,迁移率在0.1 cm2·V-1·s-1左右,不适于作为太阳电池的吸收层;当退火温度高于410℃时薄膜中不存在CuSe相,薄膜具有10 cm2·V-1·s-1左右的较高迁移率,载流子浓度在1014-1017cm-3;退火温度高于410℃时,随着退火温度的升高薄膜晶粒长大,结晶性增强,此时薄膜内部缺陷减少,载流子浓度升高;对于用作太阳电池吸收层的CIGS,从载流子浓度及迁移率的角度评判,合适的退火温度区间为450-550℃。     

硒源温度对CIGS薄膜结构和形貌的影响

采用中频交流磁控溅射方法，在Mo层上沉积了CuInGa（CIG）预制膜，采用固态硒化法制备获得了Cu（In1-xGax）Se2（CIGS）吸收层薄膜，考察了硒源温度对CIGS薄膜结构和形貌的影响。采用SEM和EDS观察和分析了薄膜的表面形貌和成分，采用XRD表征了薄膜的组织结构。结果表明，在不同的硒源温度下制备的CIGS薄膜，均为黄铜矿相结构，薄膜具有（112）面的择优取向。当硒源温度为575℃、580℃和585℃时，CIGS薄膜表面结构疏松，多孔隙；当硒源温度为590℃、595℃和600℃时，CIGS薄膜结构致密，表面平整。当硒源温度为600℃时，Cu、In和Ga原子含量处于制备弱P型CIGS吸收层薄膜的理想范围。     

前驱膜叠层及硒化升温方式对铜铟镓硒薄膜性能的影响

以钠钙玻璃为衬底,利用两靶磁控溅射的方法,选择不同的叠层方式制备铜铟镓前驱膜.然后将前驱膜放入特制的真空炉中选择不同的升温方式进行硒化退火,得到四元化合物铜铟镓硒半导体纳米薄膜,对薄膜进行各项表征.分析了前驱膜叠层及硒化升温方式对铜铟镓硒(CIGS)薄膜性能的影响,证明In/CuGa/In多层前驱膜先在250℃恒温20min加热,再升温至560℃硒化温度30min,能制备出较高质量黄铜矿结构的多晶薄膜,适合做CIGS太阳能电池吸收层材料.     

非晶CIGS前驱膜无硒退火的相变历程

采用一步射频磁控溅射法在室温获得了CIGS薄膜,研究了不同的真空无硒退火温度(150～350℃)对CIGS薄膜相变历程的影响。薄膜相变历程中的结构和性能采用XRD、SEM、EDS、紫外-可见光吸收和四探针等测试手段进行测试表征。结果表明,室温下制备的CIGS薄膜为非晶态,随退火温度升高发生非晶CIGS→CuSe→CIGS的相变。150℃退火形成的CuSe薄膜的电阻率最低,光透过性能最差。退火温度超过200℃便生成CIGS相,CIGS相的结晶质量随退火温度升高而改善,薄膜的电阻率和光透过率也随退火温度的提高而增加。     

铜铟镓硒薄膜的真空制备工艺及靶材研究现状

阐述了两种真空法制备铜铟镓硒(CIGS)薄膜的工艺原理和工艺过程,比较和分析了两工艺的优缺点;介绍了溅射靶材的熔融铸造法和粉末冶金法,列举了靶材制备中所需的温度、压强、保温时间等参数。最后分析认为,用均匀细小的黄铜矿相CIGS粉末压制烧结成四元靶材,经溅射成膜后退火处理,可制备出优异的CIGS薄膜,具有更广阔的应用前景。     

氮气流量对CIGS薄膜结构和形貌的影响

采用中频交流磁控溅射方法,在Mo层上沉积了CuInGa(CIG)预制膜.以N2为载气,采用固态硒化法制备获得了Cu(In1-xGax)Se2(CIGS)吸收层薄膜,考察了N2流量对CIGS薄膜结构和形貌的影响.采用SEM和EDS观察和分析了薄膜的表面形貌和成分,采用XRD表征了薄膜的组织结构.结果表明,在不同的N2流量下制备的CIGS薄膜,均具有单一的黄铜矿相结构,薄膜具有(112)面的择优取向.当Ar流量为0.40m3/h时,薄膜表面结构致密,晶粒大小均匀,并且Cu、In、Ga原子含量,处于制备弱p型CIGS薄膜的理想范围.     

不同靶材制备ZrW_2O_8薄膜的对比研究

分别采用摩尔比n(WO3):n(ZrO2)=2.8:1复合陶瓷靶材、纯ZrW208陶瓷靶材以及WO3和ZrO2双靶,以射频磁控溅射法在石英基片上沉积制备ZrW2O8薄膜.利用x射线衍射仪(XRD)、扫描电子显微镜(SEM)研究了退火温度对采用不同靶材沉积制备薄膜的相组成和表面形貌的影响;用划痕仪、表面粗糙轮廓仪测量薄膜与基片之间的结合力和薄膜厚度.试验结果表明:采用不同靶材磁控溅射制备的薄膜均为非晶态,经过不同温度退火后,不同靶材制备的薄膜的相组成和表面形貌有所不同,但在高温1200℃热处理3 min后均得到立方相ZrW2O8薄膜,其中采用WO3和ZrO2双靶交替磁控溅射制备的立方相ZrW2O8薄膜纯度最高,致密度好,且薄膜与基片之间结合力良好.     

退火对反应磁控溅射制备ITO薄膜性能影响

采用铟锡合金靶 (铟 锡 ,90 - 10 ) ,通过直流反应磁控溅射在玻璃基片上制备出ITO薄膜 ,并在大气环境下高温退火处理。研究了退火温度对薄膜结构、光学和电学性能的影响。研究表明 ,随着退火温度升高薄膜的电学特性得到很大提高     

RF磁控溅射法制备ZnO薄膜的XRD分析

采用RF磁控溅射法，在玻璃村底上制备多晶ZnO薄膜，并对所制备的ZnO薄膜在空气气氛中进行了不同温度（350～600℃）的退火处理和600℃时N2气氛中的退火处理。利用X射线衍射分析了溅射参数如溅射功率、溅射氧分压、衬底温度以及退火处理对ZnO薄膜结晶性能的影响。结果表明，合适的衬底温度和退火处理能够提高ZnO薄膜的结晶质量。     

预置层退火温度对CIGS薄膜晶体结构与光学性质的影响

在众多有关CIGS薄膜的制备实验条件中,温度是影响薄膜生长的重要因素之一。实验利用三步共蒸法在常温下沉积CIGS薄膜,而后对每一步制得的预制膜真空退火处理,系统研究了预置层退火温度对CIGS薄膜的晶体结构、表面形貌及光学性质的影响。研究表明,三步共蒸法中预置层退火温度应严格控制在350℃左右,有利于制备出单一黄铜相结构的CIGS薄膜,近红外波段光学反射率低至2%以下。     

脉冲激光沉积溅射工艺对CIGS薄膜成分和结构的影响

采用脉冲激光沉积溅射法在玻璃衬底上制备Cu-In-Ga预制膜,后经硒化、退火处理,得到CIGS薄膜。采用X射线衍射仪表征了薄膜的晶体结构,采用扫描电子显微镜和能量散射谱观察和分析了薄膜的表面形貌和元素成分,采用光电子能谱分析了薄膜表面的化学价态。结果表明,预制膜采用玻璃/In/Cu-Ga的叠层顺序且溅射脉冲数为In靶60000,Cu-Ga靶50000的溅射方式,可制备出沿(112)晶向择优生长的CIGS薄膜。     

Effect of Reaction Temperature and Time on the Structural Properties of Cu（In,Ga）Se2 Thin Films Deposited by Sequential Elemental Layer Technique

Thin films of copper indium gallium selenide Cu（In,Ga）Se2 （CIGS） were prepared by sequential elemental layer deposition in vacuum at room temperature. The as-deposited films were heated in vacuum for compound formation, and were studied at temperature as high as 1250℃ for the first time. These films were concurrently studied for their structural properties by X-ray diffraction （XRD） technique. The XRD analyses include phase transition studies, grain size variation and microstrain measurements with the reaction temperature and time.It has been observed that there are three distinct regions of variation in all these parameters. These regions belong to three temperature regimes： 〈450℃, 450-950℃, and 〉950℃. It is also seen that the compound formation starts at 250℃, with ternary phases appearing at 350℃ or above. Whereas, there is another phase shift at 950℃ without any preference to the quaternary compound.     

靶功率对溅射沉积CIGS薄膜的结构与光学性能的影响

采用单靶磁控溅射方法分别在玻璃和镀有Mo背电极的Soda-lime玻璃衬底上沉积Cu(In0.7Ga0.3)Se2(CIGS)薄膜。研究了靶功率变化对CIGS薄膜的晶体结构、表面形貌和光学性能的影响。采用XRD表征薄膜的组织结构,SEM和EDS观察和分析薄膜的表面形貌和成分,紫外-可见光分光光度计测试薄膜的透过率光谱。结果表明,在不同功率下制备的CIGS薄膜均具有(112)面择优取向。当溅射功率为300W时,CIGS薄膜的表面形貌最平整,结晶最均匀,n(Cu):n(In):n(Ga):n(Se)=30.00:15.01:3.97:51.03组分符合高效吸收层的要求。溅射沉积的CIGS薄膜对可见光的平均透过率低于2%,光学带隙约为1.4eV。     

Non-toxic selenization using thermal annealing for CuGa/In bi-layer precursors deposited by sputtering

Cu(In_xGa_1?x)Se₂ (CIGS) thin films were produced using a two-step sputtering process consisting of precursor formation and selenization. In the first stage, we prepared Cu_0.75Ga_0.25/In bi-layer precursors by direct current sputtering on Mo/soda-lime glass substrates. In the second stage, the stacked precursors were selenized using non-toxic Se pellets in a graphite box in which the temperature was controlled at 475–680 °C during rapid thermal annealing. We investigated the effect of thermal annealing temperature on Ga distribution and the crystallinity of the Cu(In_xGa_1?x)Se₂ films. Thermal annealing significantly affected the distribution of Ga atoms. At low temperatures, segregation of Ga atoms into the CIGS/Mo interface and an absence of Ga content on the surface were observed. In addition, a phase-separated CuInSe₂/CuGaSe₂ structure and incomplete selenization phases were observed. At high temperatures, CIGS films were formed with the proper distribution of Ga content.     

One-step RF magnetron sputtering method for preparing Cu(In,Ga)Se<Subscript>2</Subscript> solar cells

Cu(In, Ga)Se₂ (CIGS) solar cell is one of the most promising thin film solar cells. However the marketization of the CIGS solar cells is hindered by the uncertainty of the element ratios. Traditional sputtering with post selenization is one of the most widespread methods to produce the CIGS solar cells. Nevertheless, the post selenization process is the most difficult part of this technique, which could lead to element mismatch and heterogeneous. To simplify the preparing process, Cu(In, Ga)Se₂ (CIGS) solar cells were prepared without post-selenization process by RF sputtering CIGS target with abundant Se element. We focus on the effect of working pressure, substrate temperature and sputtering power on the properties of CIGS solar cells. When CIGS thin film was deposited at 580 °C, 0.8 Pa working pressure and 160 W sputtering power, the solar cell showed the highest power conversion efficiency (PCE) of 5.77%, which is only 0.64% lower than that of the solar cell prepared by traditional sputtering with post selenization method, and the two kinds of solar cells have same structure without MgF₂ antireflection layer, but the one-step sputtering method could greatly simplify the manufacture process of the CIGS solar cells. Our work makes clear that element Se would run off almost half during the sputtering process. And the element atomic ratios and the photovoltaic properties could be controlled by changing the sputtering parameters.     

基底温度对四元叠层硒化法制备铜铟镓硒(CIGS)薄膜的影响

利用四元叠层硒化法制备了铜铟镓硒(缩写为CIGS)薄膜,重点分析了在叠层法制备CIGS薄膜过程中,基底温度对CIGS薄膜的晶体结构,表面形貌以及各种元素沿深度分布的影响.实验结果表明,在叠层法制备CIGS薄膜时,发现在550℃的基底温度时,不经过退火便可以生成CIGS晶体,表面Ga的含量处于比较合适的范围.而基底温度为500℃,450℃时,只能生成铜铟硒(CIS)晶体,Ga元素表面的含量较少,主要分布在薄膜底部.     

硒化温度对CIGS/Mo界面微观结构和化学成分的影响

采用磁控溅射和硒化热处理的方法在钠钙玻璃上沉积了一系列铜铟镓硒(CIGS)薄膜。利用X射线衍射(XRD)、高分辨透射电子显微术(HR-TEM)、高角环形暗场相(HAADF)和X射线能量散射光谱(EDS)元素面扫描分析等表征手段,研究了铜铟镓硒/钼(CIGS/Mo)界面特性随硒化温度的变化规律。结果表明,400℃硒化的薄膜中CIGS与Mo层之间界面清晰;当硒化温度为500℃时,CIGS/Mo界面上出现MoSe_2薄层和富Na的二次相纳米颗粒;当硒化温度升至600℃时,MoSe_2层增厚,同时富Na二次相纳米颗粒连接形成不平整的条带,CIGS/Mo界面演变为CIGS/富Na的二次相/MoSe_2/Mo多层结构。此外,MoSe_2的取向对富Na二次相的形成有一定的影响。     

Effect of stacking type in precursors on composition, morphology and electrical properties of the CIGS films

The copper-indium-gallium (CIG) metallic precursors with different stacking type (A: CuGa/CuIn/CuGa/glass and B: CuInGa/CuIn/CuInGa/glass) were prepared onto glass substrates by magnetron sputtering method. In order to prepare Cu(In_1?xGa_x)Se₂ (CIGS) thin films, the CIG precursors were then selenized with solid Se powder using a three-step reaction temperature profile. The influence of stacking type in precursors on structure, composition, morphology and electrical properties of the CIGS films is investigated by X-ray diffraction, energy dispersive spectrometer, scanning electron microscope and Hall effect measurement. The results reveal that the stacking type of the precursor has a strong influence on composition, morphology and properties of the CIGS thin films. The atomic ratios of Cu/(In+Ga)/Se of the CIGS films A and B are 1.61:1:2.11 and 1.39:1:2.04, respectively. The better quality CIGS thin films can be obtained through selenization of metallic precursor of CuInGa/CuIn/CuInGa/glass. The CIGS films are p-type semiconductor material. The hole concentration, resistivity and hole mobility of the CIGS thin films is 2.51 × 10¹⁷ cm^?3, 3.11 × 10⁴ Ω cm and 19.8 cm² V^?1 s^?1, respectively.     

Adjustment of the selenium amount during ion beam sputtering deposition of CIS thin films

CuInSe₂ (CIS) films were prepared by ion beam sputtering depositing Cu, In and Se layers sequentially on BK7 glass substrates and annealing the 3-layer film in the same vacuum chamber. The adjustment of the Se amount in the film was achieved by controlling the sputtering time of the Se target. X-ray diffraction pattern shows CIS films have chalcopyrite structure and preferential (112) orientation when the sputtering of the Se layer is between 60 and 180 min. It also can be seen that the most intense and narrow peak indicates the highest crystallinity for the sample with sputtering Se of 60 min, which is in agreement with the Raman measurement. The content of Cu, In and Se in the film deviates from 1, 1 and 2 with increasing the sputtering time of the Se target. Direct band gap energy between 0.96 and 1.05 eV, depending on the Se amount, and a high absorption coefficient of 10⁵ cm⁻¹ are found. The measured film resistivities vary from 0.01 to 0.05 Ω cm. Thus, the structural, optical and electrical characteristics of the CIS thin films were dependent on the Se amount during the fabrication of films and after fitting the sputtering time of Se, an optimization of the properties and a saving of Se consumption were achieved.     

In-situ fabrication and performance optimization of CIGS thin film deposited by ion-beam sputtering without post-selenization

Cu(In, Ga)Se₂ thin films were fabricated by an in situ fabrication process of ion beam sputtering deposition without post-selenization. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy and four-point probe technique were used to study the microstructures, surface morphology, composition and electrical properties, respectively. The results show that the films grown above 400 °C are of chalcopyrite structure and Cu (In_0.7Ga_0.3) Se₂ thin film was obtained at annealing temperature of 550 °C. With the increase in annealing temperature, the resistivity of the films decreases while the component is nearly steady. The degree of crystallization of the thin films increased at first with increasing of the annealing time and then decreased with the annealing time increasing further. It was demonstrated that the structural and electrical properties of the films improved significantly with adding selenium amount by sputtering selenium.