Influence of growth temperature and thickness on the orientation of Cu(In,Ga)Se2 film

Cu(In,Ga)Se2(CIGS) films are deposited on the Na-free glass substrate using three-stage co-evaporation process,and the effects of thickness and growth temperature on the orientation of CIGS film are investigated by X-ray diffraction(XRD) and scanning electron microscopy(SEM).When the growth of CIGS film does not experience the Cu-rich process,the increase of the growth temperature at the second stage(Ts2) promotes the(112) orientation of CIGS film,and weakens the(220) orientation.Nevertheless,when the growth of CIGS film experiences Cu-rich process,the increase of Ts2 significantly promotes the(220) orientation.In addition,with the thickness of CIGS film decreasing,the extent of(In,Ga)2Se3(IGS) precursor orientation does not change except for the intensity of Bragg peak,yet the(220) orientation of following CIGS film is hindered,which suggests that(112) plane preferentially grows at the initial growth of CIGS film.     

Influence of Ni and Cr impurities on the electronic properties of Cu(In,Ga)Se2 thin film solar cells

Deposition of Cu(In,Ga)Se₂ (CIGS) thin film solar cells on metallic substrate is an attractive approach for development of low cost solar modules. However, in such devices, special care has to be taken to avoid diffusion of impurities, such as Fe, Ni, and Cr, from the substrate into the active layers. In this work, the influence of Ni and Cr impurities on the electronic properties of CIGS thin film solar cells is investigated in detail. Impurities were introduced into the CIGS layer by diffusion during the CIGS deposition process from a Ni or Cr precursor layer below the Mo electrical back contact. A high temperature and a low temperature CIGS deposition process were applied in order to correlate the changes in the photovoltaic parameters with the amount of impurities diffused into the absorber layer. Solar cells with Ni and Cr impurities show a reduction in the device performance, whereas the effect was most pronounced in Ni containing devices. The presence of deep defect levels in the absorber layer was identified with admittance spectroscopy and can be related to Ni and Cr impurities, which diffused into the CIGS layer according to secondary ion mass spectroscopy depth profiles and inductively coupled plasma mass spectrometry. Copyright © 2014 John Wiley & Sons, Ltd.     

Preferred orientation of Cu(In,Ga)Se2 thin film deposited on stainless steel substrate

The influences of process parameters and Fe diffusing into Cu(In,Ga)Se₂ (CIGS) films on the orientation of CIGS absorbers grown on the stainless steel (SS) foils are investigated. The structural properties, morphology, and elemental profiles are characterized using X‐ray diffraction, scanning electron microscopy, and second ion mass spectroscopy, respectively. The orientation of CIGS thin films on the SS substrates strongly depends on the texture of the (In,Ga)₂Se₃ precursor, determined by the substrate temperature at the first stage (Ts1) and the flux ratio of Se to (In + Ga). Among these factors, Ts1 is the prerequisite to achieve [300]‐oriented IGS layer, which will yield [200]‐oriented CIGS thin film in the later process. The results indicate that through the comparison of CIGS thin films on the Mo/SS substrates and on the Mo/ZnO/SS substrates and combined with simply calculation, Fe diffusing into the CIGS layer will hinder the growth of the CIGS grains along [112] orientation. The grazing‐incidence X‐ray diffraction results suggest that the surface of the [220]‐textured CIGS thin film on the SS substrate still has [220] predominance, whereas the surface texture of the [220]‐texture CIGS thin film on the Mo/soda‐lime glass substrate became [112] predominant, which is due to the different compensation ability between Fe and Na elements. Finally, the relations between the device parameters and the degrees of the preferred orientation of CIGS absorbers are investigated. Copyright © 2012 John Wiley & Sons, Ltd.     

聚酰亚胺衬底CIGS薄膜附着性的改善

为改善聚酰亚胺(PI)衬底Cu(In,Ga)Se2(CIGS)薄膜的附着性,提出在NaF沉积前预先在Mo层上蒸发沉积100nm厚的In-Ga-Se(IGS)薄膜的新掺Na工艺。结果表明:这种IGS-NaF-CIGS式新工艺可显著改善CIGS薄膜的附着,而且CIGS薄膜材料和器件特性没有显著退化;新工艺促进了NaInSe2的生成,减少了In-Se二元相的残余,但也造成薄膜电阻率的升高和电池填充因子的下降,进而导致制备的PI衬底CIGS电池的转换效率由9.8%降至9.0%。综合考虑附着性的改善和器件效率的轻微下降,新工艺利大于弊,有很好的应用前景。     

Morphology of CIGS thin films deposited by single-stage process and three-stage process at low temperature

Cu（In,Ga）Se2 （CIGS） thin films are prepared by a single-stage process and a three-stage process at low temperature in the co-evaporation equipment. The quite different morphologies of CIGS thin films deposited by two methods are characterized by scanning electron microscopy （SEM）. The orientation of CIGS thin films is identified by X-ray dif- fraction （XRD） and Raman spectrum, respectively. Through analyzing the film-forming mechanisms of two prepara- tion processes, we consider the cause of such differences is that the films deposited by three-stage process at low tem- perature evolve from Cu-poor to Cu-rich ones and then back to Cu-poor ones. The three-stage process at low tempera- ture results in the CIGS thin films with the （220）/（204） preferred orientation, and the ordered vacancy compound （OVC） layer is formed on the surface of the film. This study has great significance to large-scale industrial production.     

Sn doped ZnO thin films as high resistivity window layer for Cu(In,Ga)Se2 solar cells

For high efficiency Cu(In,Ga)Se2 (CIGS) solar cell, the high-resistivity layer with high optical transmittance has to be adopted between the buffer layer and the high-conductivity window layer. In this paper, we propose Sn doped ZnO (ZTO) film, instead of the traditional intrinsic ZnO (i-ZnO) film, as an alternative n-type high-resistivity window layer for CIGS solar cell. In this experiment, both ZTO and i-ZnO films are strong (002) oriented, and the surface morphologies of the two films are almost the same. The statistical roughnesses of i-ZnO film and ZTO film are 0.58 nm and 0.63 nm, respectively. However, the optical transmittance of ZTO film is higher than that of i-ZnO film with the same thickness. The efficiency of ZTO based CIGS cell was 14.24%, which is almost the same as the efficiency of i-ZnO based CIGS cell. These results fully suggest that it is very feasible to replace i-ZnO with ZTO as the high resistant window layer.     

Improvement of the cell performance in the ZnS/Cu(In,Ga)Se2 solar cells by the sputter deposition of a bilayer ZnO : Al film

ZnS is a candidate to replace CdS as the buffer layer in Cu(In,Ga)Se₂ (CIGS) solar cells for Cd‐free commercial product. However, the resistance of ZnS is too large, and the photoconductivity is too small. Therefore, the thickness of the ZnS should be as thin as possible. However, a CIGS solar cell with a very thin ZnS buffer layer is vulnerable to the sputtering power of the ZnO : Al window layer deposition because of plasma damage. To improve the efficiency of CIGS solar cells with a chemical‐bath‐deposited ZnS buffer layer, the effect of the plasma damage by the sputter deposition of the ZnO : Al window layer should be understood. We have found that the efficiency of a CIGS solar cell consistently decreases with an increase in the sputtering power for the ZnO : Al window layer deposition onto the ZnS buffer layer because of plasma damage. To protect the ZnS/CIGS interface, a bilayer ZnO : Al film was developed. It consists of a 50‐nm‐thick ZnO : Al plasma protection layer deposited at a sputtering power of 50 W and a 100‐nm‐thick ZnO : Al conducting layer deposited at a sputtering power of 200 W. The introduction of a 50‐nm‐thick ZnO : Al layer deposited at 50 W prevented plasma damage by sputtering, resulting in a high open‐circuit voltage, a large fill factor, and shunt resistance. The ZnS/CIGS solar cell with the bilayer ZnO : Al film yielded a cell efficiency of 14.68%. Therefore, the application of bilayer ZnO : Al film to the window layer is suitable for CIGS solar cells with a ZnS buffer layer. Copyright © 2012 John Wiley & Sons, Ltd.     

High rate (~7 nm/s), atmospheric pressure deposition of ZnO front electrode for Cu(In,Ga)Se2 thin‐film solar cells with efficiency beyond 15%

Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10⁻³ Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al₂O₃ barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al₂O₃ films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of Se flux on CuIn1‐xGaxSe2 film in reactive sputtering process

CuIn_1‐xGa_xSe₂ (CIGS) thin films were grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker was used to deliver reactive Se molecules. The Cu_0·6 Ga_0·4 and Cu_0·4In_0·6 targets were simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on CIGS film deposition were investigated. The CIGS film growth rate decreased, and the surface roughness of a film increased as the Se flux increased. The [112] crystal orientation was dominant, and metallic crystal phases such as Cu₉Ga₄ and Cu₁₆In₉ in a film were disappearing with increasing Se flux. A solar cell fabricated using a 900‐nm CIGS film showed the power conversion efficiency of 8·6%, the highest value found in a sub‐micron thick CIGS solar cell related to a reactive sputtering process with metallic targets. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of MoSe2 on the performance of CIGS solar cells

A CuIn1-xGaxSe2 (CIGS) thin film solar cell model with MoSe2 transition layer was established, using SCAPS-1D software. The influence of MoSe2 interface layer formed between absorption layer CIGS and the back contact Mo on the solar cell performance was investigated.By changing the doping concentration,thickness and bandgap of MoSe2 layer, it is found that the MoSe2 and the variation of parameters have a significant effect on the electrical characteristics and photovoltaic parameters of CIGS thin film solar cells. Based on the energy band, the interfaces of Mo/MoSe2 and MoSe2/CIGS are analyzed. It is considered that Mo/MoSe2 is a Schottky contact, MoSe2/CIGS is an ohmic contact. When suitable parameters of MoSe2 layer are formed into the interface, it will provide a new path for designing CIGS solar cells with thinner absorption layer.     

Locating the electrical junctions in Cu(In,Ga)Se2 and Cu2ZnSnSe4 solar cells by scanning capacitance spectroscopy

We determined the electrical junction (EJ) locations in Cu(In,Ga)Se₂ (CIGS) and Cu₂ZnSnSe₄ (CZTS) solar cells with ~20‐nm accuracy by developing scanning capacitance spectroscopy (SCS) applicable to the thin‐film devices. Cross‐sectional sample preparation for the SCS measurement was developed by high‐energy ion milling at room temperature for polishing the cross section to make it flat, followed by low‐energy ion milling at liquid nitrogen temperature for removing the damaged layer and subsequent annealing for growing a native oxide layer. The SCS shows distinct p‐type, transitional, and n‐type spectra across the devices, and the spectral features change rapidly with location in the depletion region, which results in determining the EJ with ~20‐nm resolution. We found an n‐type CIGS in the region next to the CIGS/CdS interface; thus, the cell is a homojunction. The EJ is ~40 nm from the interface on the CIGS side. In contrast, such an n‐type CZTS was not found in the CZTS/CdS cells. The EJ is ~20 nm from the CZTS/CdS interface, which is consistent with asymmetrical carrier concentrations of the p‐CZTS and n‐CdS in a heterojunction cell. Our results of unambiguously determination of the junction locations contribute significantly to understanding the large open‐circuit voltage difference between CIGS and CZTS. Copyright © 2016 John Wiley & Sons, Ltd.     

Electronic properties of Cu(In,Ga)Se2 solar cells on stainless steel foils without diffusion barrier

Compared with rigid glass, manufacturing of Cu(In,Ga)Se₂ (CIGS) solar cells on flexible stainless steel (SS) substrates has potential to reduce production cost because of the application of roll‐to‐roll processing. Up to now, high‐efficiency cells on SS could only be achieved when the substrate is coated with a barrier layer (e.g. SiO_x or Si₃N₄) for hindering the diffusion of impurities, especially Fe, into the CIGS layer. In this paper, the effect of these impurities on the electronic transport properties of the device is investigated. Using admittance spectroscopy, the presence of a deep defect level at around 320 meV is observed, which deteriorates the efficiency of the solar cells. Furthermore, it is shown that reducing substrate temperature during CIGS deposition is an effective alternative to a barrier layer for reducing diffusion of detrimental Fe impurities into the absorber layer. By applying a CIGS growth process for deposition at low substrate temperatures, an efficiency of 17.7%, certified by Fraunhofer Institute ISE, Freiburg, was achieved on Mo/Ti‐coated SS substrate without an additional metal‐oxide or metal‐nitride impurity diffusion barrier layer. Copyright © 2012 John Wiley & Sons, Ltd.     

The impact of Al2O3 back interface layer on low-temperature growth of ultrathin Cu(In,Ga)Se2 solar cells

With reducing the absorber layer thickness and processing temperature, the recombination at the back interface is severe, which both can result in the decrease of open-circuit voltage and fill factor. In this paper, we prepare Al2O3 by atomic layer deposition (ALD), and investigate the effect of its thickness on the performance of Cu(In,Ga)Se2 (CIGS) solar cell. The device recombination activation energy (EA) is increased from 1.04 eV to 1.11 eV when the thickness of Al2O3 is varied from 0 nm to 1 nm, and the height of back barrier is decreased from 48.54 meV to 38.05 meV. An efficiency of 11.57 % is achieved with 0.88-μm-thick CIGS absorber layer.     

Fabrication of high-quality ZnS buffer and its application in Cd-free CIGS solar cells

This paper provides the fabrication of Cd-free Cu（In,Ga）Se2 （CIGS） solar cells on soda-lime glass substrates. A high quality ZnS buffer layer is grown by chemical bath deposition （CBD） process with ZnSO4-NH3-SC （NH2）2 aqueous solution system. The X-ray diffraction （XRD） result shows that the as-deposited ZnS film has cubic （111） and （220） diffraction peaks. Scanning electron microscope （SEM） images indicate that the ZnS film has a dense and compact surface with good crystalline quality. Transmission measurement shows that the optical transmittance is about 90% when the wavelength is beyond 500 nm. The bandgap （Eg） value of the as-deposited ZnS film is estimated to be 3.54 eV. Finally, a competitive efficiency of 11.06% is demonstrated for the Cd-free CIGS solar cells with ZnS buffer layer after light soaking.     

Fabrication of thick, high-quality strained SiGe layer on ultra-thin silicon-on-insulator and modeling of film strain

Fabrication of a thick strained SiGe layer on bulk silicon is hampered by the lattice mismatch and difference in the thermal expansion coefficients between Si and SiGe, and a high Ge content leads to severe strain in the SiGe film. When the thickness of the SiGe film is above a critical value (90 nm for 18% Ge), drastic deterioration of the film properties as well as dislocations will result. In comparison, a silicon-on-insulator (SOI) substrate with a thin top Si layer can mitigate the problems and so a thick SiGe layer with high Ge concentration can conceivably be synthesized. In the work reported here, a 110 nm thick high-quality strained Si_0.82Ge_0.18 layer was fabricated on an ultra-thin SOI substrate with a 30 nm top silicon layer using ultra-high vacuum chemical vapor deposition (UHVCVD). The thickness of the SiGe layer is larger than the critical thickness on bulk Si. Cross-sectional transmission electron microscopy (XTEM) reveals that the SiGe layer is dislocation-free and the atoms at the SiGe/Si interface are well aligned, even though X-ray diffraction (XRD) data indicate that the SiGe film is highly strained. The strain factors determined from the XRD and Raman results agree well.     

钝化层对声表面波滤波器的影响

为了研究钝化层对声表面波(SAW)滤波器性能的影响,以二氧化硅(SiO₂)薄膜为钝化层,对厚度为12~80 nm 的SiO₂膜钝化层工艺数据进行分析。结果表明,当SiO₂膜钝化层覆膜厚度大于25 nm时其膜层质量均匀性好,致密度高。同时SiO₂膜钝化层厚度对膜层间的粘性、传播损耗、自身的质量负载及谐振峰处的频率均有影响,且会引起过渡带宽发生变化。     

Role of the CdS buffer layer as an active optical element in Cu(In,Ga)Se2 thin‐film solar cells

ZnO/CdS/Cu(In,Ga)Se₂ (CIGS) thin‐film heterojunction solar cells with CdS buffer layers of thicknesses between 0 and 85 nm are characterized by current–voltage, quantum efficiency, and optical reflection measurements. We investigate the correlation between the short‐circuit current density and the CdS layer thickness, focusing on the counteracting effects of light absorption and reduced optical reflection induced by the CdS layer. Both effects almost compensate each other for CdS layer thicknesses between 0 and 40 nm. Thus, an optimization of the short‐circuit current density is not achieved by omitting the CdS layer, but rather by replacing the CdS buffer with an alternative buffer material with higher bandgap energy and optical constants similar to those of CdS. Copyright © 2002 John Wiley & Sons, Ltd.     

Zn1?xMgxO用于 CIGS 太阳电池的研究进展

Zn1-xMgxO透过率高、带隙可调,且与CIGS太阳电池在晶格和能带结构上匹配良好,可用作CIGS太阳电池缓冲层、窗口层,因此制备高质量的Zn1-xMgxO薄膜是提高太阳电池性能的关键。文章介绍了Zn1-xMgxO薄膜的结构特性、光学特性及制备方法;从Mg含量、Zn1-xMgxO膜厚及Zn1-xMgxO/CIGS界面处缺陷密度等方面概述了Zn1-xMgxO用于CIGS太阳电池的研究进展,并比较了Zn1-xMgxO与In2S3,ZnS,CdS等其他材料作缓冲层的CIGS太阳电池性能的差别。     

CIGS Thin Films for Cd-Free Solar Cells by One-Step Sputtering Process

Cu(In_1?x Ga _x )Se₂ (CIGS) thin films were deposited by a one-step radio frequency (RF) magnetron sputtering process using a quaternary CIGS target. The influence of substrate temperature on the composition, structure, and optical properties of the CIGS films was investigated. All the CIGS films exhibited the chalcopyrite structure with a preferential orientation along the (112) direction. The CIGS film deposited at 623 K showed significant improvement in film crystallinity and surface morphology compared to films deposited at 523 and 573 K. To simplify the manufacturing procedure of solar cells and avoid the use of the toxic element Cd, the properties of ZnS films prepared by RF sputtering were also investigated. The results revealed that the sputtered ZnS film exhibits good lattice matching with the sputtered CIGS film with significantly lower optical absorption loss. Finally, all-sputtered Cd-free CIGS-based heterojunction solar cells with the structure SLG/Mo/CIGS/ZnS/AZO/Al grids were fabricated without post-selenization. Furthermore, the results demonstrated the feasibility of using a full sputtering process for the fabrication of Cd-free CIGS-based solar cell.     

Study on ALD In2S3/Cu(In,Ga)Se2 interface formation

The formation of the interface between In₂S₃ grown by atomic layer deposition (ALD) and co‐evaporated Cu(In,Ga)Se₂ (CIGS) has been studied by X‐ray and UV photoelectron spectroscopy. The valence band offset at 160°C ALD substrate temperature was determined as −1·2±0·2 eV for CIGS deposited on soda‐lime glass substrates and −1·4±0·2 eV when a Na barrier substrate was used. Wavelength dependent complex refractive index of In₂S₃ grown directly on glass was determined from inversion of reflectance and transmittance spectra. From these data, an indirect optical bandgap of 2·08±0·05 eV was deduced, independent of film thickness, of substrate temperature and of Na content. CIGS solar cells with ALD In₂S₃ buffer layers were fabricated. Highest device efficiency of 12·1% was obtained at a substrate temperature of 120°C. Using the bandgap obtained for In₂S₃ on glass and a 1·15±0·05 eV bandgap determined for the bulk of the CIGS absorber, the conduction band offset at the buffer interface was estimated as −0·25±0·2 eV (−0·45±0·2 eV) for Na‐containing (Na‐free) CIGS. Copyright © 2005 John Wiley & Sons, Ltd.