First-principles study of Cu2ZnSnS4 and the related band offsets for photovoltaic applications

First-principles calculations of the band offsets between Cu(2)ZnSnS(4) (CZTS) and XS (X = Cd, Zn) are performed. While the interface dipole contribution for the band offsets is calculated using the Perdew-Burke-Ernzerhof functional, the Heyd-Scuseria-Ernzerhof hybrid functional is employed to introduce the quasiparticle corrections to the band offsets. The calculated conduction band offset between CZTS and CdS is 0.2 eV, validating CdS for the buffer layer of the CZTS solar cell. The small conduction band offset stems from the band gap narrowing of CdS under the interface strain caused by the lattice misfit with CZTS. A large valence band offset over 0.9 eV between CZTS and ZnS indicates that precipitated ZnS is regarded as an inactive insulator phase in CZTS absorbers.     

Investigation of CdS and CdTe thin films and influence of CdCl2 on CdTe/CdS structure

CdTe/CdS heterojunction solar cell structure has been fabricated using simple, easy and low-cost methods. To fabricate this structure, CdS and CdTe thin films are deposited onto FTO-coated conducting glass substrates by chemical bath deposition (CBD) and electrodeposition method, respectively. The optimized growth conditions are chosen for both CdS and CdTe films by investigating the optical, structural and morphological properties of both the as-deposited and annealed films. Optical measurement showed that CdS films have higher transmittance and lower absorbance, and CdTe films have lower transmittance and higher absorbance in the near infrared region. The band gap of CdS films is estimated to lie in the range 2.29–2.41 eV and that of CdTe films is in the range 1.53–1.55 eV. X-ray diffraction (XRD) study reveals that CdS and CdTe films are polycrystalline with preferential orientation of (1 1 1) plane. Scanning electron microscopy (SEM) study reveals that both films are smooth, void-free and uniformly distributed over the surface of the substrate. Fabricated CdTe/CdS structure showed the anticipated rectifying behaviour, and the rectifying behaviour is observed to improve due to CdCl₂ treatment.     

Recombination-induced voltage-dependent photocurrent collection loss in CdTe thin film solar cell

Recently, the efficiency of CdTe thin film solar cell has been improved by using new type of window layer Mg_xZn_1-xO (MZO). However, it is hard to achieve such a high efficiency as expected. In this report a comparative study is carried out between the MZO/CdTe and CdS/CdTe solar cells to investigate the factors affecting the device performance of MZO/CdTe solar cells. The efficiency loss quantified by voltage-dependent photocurrent collection efficiency (η_C(V')) is 3.89% for MZO/CdTe and 1.53% for CdS/CdTe solar cells. The higher efficiency loss for the MZO/CdTe solar cell is induced by more severe carrier recombination at the MZO/CdTe p—n junction interface and in CdTe bulk region than that for the CdS/CdTe solar cell. Activation energy (E_a) of the reverse saturation current of the MZO/CdTe and CdS/CdTe solar cells are found to be 1.08 eV and 1.36 eV, respectively. These values indicate that for the CdS/CdTe solar cell the carrier recombination is dominated by bulk Shockley—Read—Hall (SRH) recombination and for the MZO/CdTe solar cell the carrier recombination is dominated by the p—n junction interface recombination. It is found that the tunneling-enhanced interface recombination is also involved in carrier recombination in the MZO/CdTe solar cell. This work demonstrates the poor device performance of the MZO/CdTe solar cell is induced by more severe interface and bulk recombination than that of the CdS/CdTe solar cell.     

基于氧化镍背接触缓冲层碲化镉薄膜太阳电池的研究

采用电子束蒸发法制备了NiO薄膜,并对其作为碲化镉薄膜太阳电池背接触缓冲层材料进行了相关研究.NiO缓冲层的加入使得碲化镉太阳电池开路电压显著增大.通过X射线光电子能谱测试得到的NiO/CdTe界面能带图表明NiO和CdTe的能带匹配度很好.NiO是宽禁带P型半导体材料,在电池背接触处形成背场,减少了电子在背表面处的复合,从而提高电池开路电压.通过优化NiO薄膜厚度,制备得到转换效率为12.2%、开路电压为789 mV的碲化镉太阳电池.研究证实NiO是用来制备高转换效率、高稳定性碲化镉薄膜太阳电池的一种极有前景的缓冲层材料.     

Short-circuit current improvement in CdTe solar cells by combining a ZnO buffer layer and a solution back contact

Conventional CdTe solar cells have a CdS window layer, in which an absorption loss of photons with more than 2.4 eV occurs through the CdS layer. A thinner CdS layer was applied to enhance light transmission and a ZnO buffer layer with a band gap of 3.3 eV was introduced to suppress shunting through the thinner CdS window layer. A 100-nm thick ZnO layer sputter-deposited at 300 °C had uniform coverage on a transparent conductive oxide (TCO) after a subsequent high-temperature process. The ZnO layer was effective in preventing shunting through the CdS window layer so that the open-circuit voltage and fill factor of the CdTe solar cells were recovered and the short-circuit current was enhanced over that of the conventional CdTe solar cell. In the ZnO/CdS/CdTe configuration, the short-circuit current was further improved throughout the visible wavelength region by replacing the Cu-metal contact with a Cu solution contact. As a result the short-circuit current from 21.7 to 26.1 mA/cm² and the conversion efficiency of the CdTe solar cell increased from 12 to 15% without antireflective coating. Our result indicates that the Cu solution back contact is a critical factor for achieving a higher cell efficiency in addition to ZnO buffer layer.     

Numerical simulation of ultra-thin CdTe solar cells with a buffer layer of MoOx in the backwall configuration

The software of Solar Cell Capacitance Simulator (SCAPS) is used to investigate the performance of ultra-thin CdTe solar cells in the backwall configuration (glass/ITO/MoO_x/CdTe/CdS/SnO₂/Ag). The backwall structure utilizes ultra-thin CdTe absorber layer instead of CdS film facing light illumination, which eliminates the absorption of CdS in short-wavelength region and improves the blue response of CdTe. A buffer layer of MoO_x is added to modify the contact between CdTe and ITO, reducing the valence band barrier height and simultaneously forming an electron reflector, which can reduce electron-hole recombination at this contact. When the thickness of MoO_x is 2 nm, the simulation results show that an efficiency can reach up to 25.5% with high ITO work function and ideal interface recombination velocity.     

Understanding the junction degradation mechanism in CdS/CdTe solar cells using a Cd-deficient CdTe layer

It is known that CdTe solar cells are often degraded under solar illumination. But the degradation mechanism is not fully proved because it does not appear consistently. The junction degradation in CdS/CdTe solar cells was investigated using a CdTe layer with Cd deficient composition, where Cd vacancy concentration is high. It was found that the Cu atoms easily filled the Cd vacancies in CdTe and transport to junction area from Cu back contact. PL measurement and spectral quantum efficiency measurement showed that the incorporation of Cu atoms in CdS forms a defect energy level at 1.55 eV below the conduction band in CdS. As a result, the junction built-in potential is decreased and light penetration into CdTe absorber is shielded. For reliable and stable CdTe cells, the formation of Cd vacancy in CdTe should be avoided by careful control of CdTe.     

利用同步辐射光电子能谱技术测量ZnO/PbTe异质结的能带带阶

异质结结构界面的能带带阶是一个非常重要的参数,该参数的精确确定直接影响异质结的光电性质研究以及异质结在光电器件上的应用.利用同步辐射光电子能谱技术测量了ZnO/PbTe异质结结构的能带带阶.测量得到该异质结价带带阶为2.56 eV,导带带阶为0.49 eV,是一个典型的类型I的能带排列.利用变厚度扫描的测量方法发现,ZnO/PbTe界面存在两种键,分别是Pb—O键(低结合能)和Pb—Te键(高结合能).在ZnO/PbTe异质结界面的能带排列中导带带阶较小,而价带带阶较大,这一能带结构有利于PbTe中的激发电子输运到ZnO导电层中.该类结构在新型太阳电池、中红外探测器、激光器等器件中具有潜在的应用价值.     

Energy band alignment of PbTe/CdTe(111) interface determined by ultraviolet photoelectron spectra using synchrotron radiation

The energy band structure with type-I alignment at the PbTe/CdTe(111) heterojunction interface is determined by the ultraviolet photoelectron spectrum using synchrotron radiation.The valence band and conduction band offsets are obtained to be 0.09±0.12 and 1.19±0.12 eV,respectively.These results are in agreement with theoretically predicted ones.The accurate determination of the valence band and conduction band offsets is useful for the fundamental understanding of the mid-infrared light emission from the PbTe/CdTe heterostructures and its application in devices.     

Spectroscopic analysis of CIGS2/CdS thin film solar cell heterojunctions on stainless steel foil

This paper presents a spectroscopic analysis of the interface between a CuIn_1−xGa_xS₂ (CIGS2) absorber and a CdS buffer layer on stainless steel foil by Auger electron spectroscopy (AES), inverse photoemission spectroscopy (IPES) and photoelectron spectroscopy (PES) such as X-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). By combining these spectroscopic techniques, detailed information about the electronic and chemical properties of the CIGS2 surface and the CdS/CIGS2 interface can be obtained. The gallium concentration in CIGS2 films was found to increase continuously towards the Mo back contact. XPS analysis showed the presence of KCO₃ on the surface of CdS, deposited on etched and un-oxidized samples indicating diffusion of potassium. No potassium was observed on oxidized as well as samples having thicker CdS (50 nm) indicating the effectiveness of oxidation and chemical bath deposition (CBD) process in cleaning the sample surface effectively. In addition, investigation of the electronic level alignment at the interface has been carried out by combining PES and IPES. Conduction band offset of −0.45 (±0.15) eV and a valence band offset of −1.06 (±0.15) eV were measured. These unfavorable conditions limit efficiency of CIGS2 thin film solar cells.     

Structural and electronic properties of PbTe (rocksalt)/CdTe (zinc-blende) interfaces

We study interfaces between highly ionic crystals with different crystal structure by first-principles total-energy calculations in the repeated-slab approximation and compare the results with experimental data extracted from high-resolution transmission electron micrographs. The non-polar (1 1 0) interface between PbTe (rocksalt) and CdTe (zinc-blende) crystals gives rise to a lateral spatial offset between the two crystal halves. At the polar (1 0 0) interfaces a strong variation of the interface extent with respect to the cation or anion termination is observed. Furthermore, we calculate band offsets and projected interface band-structures for PbTe/CdTe interfaces. The results are discussed versus the interface orientation.     

Interfacial properties of 2D WS2 on SiO2 substrate from X-ray photoelectron spectroscopy and first-principles calculations

Two-dimensional (2D) WS₂ films were deposited on SiO₂ wafers, and the related interfacial properties were investigated by high-resolution X-ray photoelectron spectroscopy (XPS) and first-principles calculations. Using the direct (indirect) method, the valence band offset (VBO) at monolayer WS₂/SiO₂ interface was found to be 3.97 eV (3.86 eV), and the conduction band offset (CBO) was 2.70 eV (2.81 eV). Furthermore, the VBO (CBO) at bulk WS₂/SiO₂ interface is found to be about 0.48 eV (0.33 eV) larger due to the interlayer orbital coupling and splitting of valence and conduction band edges. Therefore, the WS₂/SiO₂ heterostructure has a Type I energy-band alignment. The band offsets obtained experimentally and theoretically are consistent except the narrower theoretical bandgap of SiO₂. The theoretical calculations further reveal a binding energy of 75 meV per S atom and the totally separated partial density of states, indicating a weak interaction and negligible Fermi level pinning effect between WS₂ monolayer and SiO₂ surface. Our combined experimental and theoretical results provide proof of the sufficient VBOs and CBOs and weak interaction in 2D WS₂/SiO₂ heterostructures.     

Valence band offset in semimagnetic CdTe/(CdMn)To quantum wells

We present a comparative study of two different spectroscopic techniques in order to determine the valence band offset in CdTe/(CdMn)Te quantum wells. On the one hand the energy difference between heavy- and light-hole excitons as a function of the heavy-hole transition energy is employed. We determine a valence band offset of Q_v=0.30 for CdTe/(CdMn)Te, which is valid in the whole range of investigated Mn-contents up to x=0.27. An alternative determination of the valence band potential height is based on the tuning of potential heights due to external magnetic fields in semimagnetic quantum wells. Analysing the Zeeman splitting of the heavy-hole exciton in CdTe/(CdMn)Te quantum wells with different Mn-contents, we demonstrate a significant decrease of the valence band offset with increasing Mn-content in the barrier. From the comparison of the two different spectroscopic methodes including published data, we conclude that the valence band offset derived from the Zeeman splitting in CdTe/(CdMn)Te quantum wells with high Mn-content is strongly underestimated.     

基于GaSb/CdS薄膜热光伏电池的器件设计

基于GaSb薄膜热光伏器件是降低热光伏系统成本的有效途径之一, 本文主要针对GaSb/CdS薄膜热光伏器件结构进行理论分析. 采用AFORS-HET软件进行模拟仿真, 分析GaSb和CdS两种材料各自的缺陷态密度、界面态对电池性能的影响. 根据软件模拟可以得知, 吸收层GaSb的缺陷态密度以及GaSb与CdS之间的界面态密度是影响电池性能的重要因素. 当GaSb缺陷态增加时, 主要影响电池的填充因子, 电池效率明显下降. 而作为窗口层的CdS缺陷态密度对电池性能影响不明显, 当CdS缺陷态密度上升4个数量级时, 电池效率仅下降0.11%.     

The In2O3/CdTe interface: A possible contact for thin film solar cells?

Transparent conductive In₂O₃ films were deposited by reactive evaporation of In and analyzed in-situ with photoelectron spectroscopy. The interface formation of In₂O₃ with evaporated CdTe has been investigated using the same technique. A valence band offset ΔE_VB=2.1±0.1 eV is determined, resulting in a negligible conduction band offset. However, In₂O₃ will not provide an Ohmic contact to n-CdTe, due to the Fermi level position at the interface.     

氧对于在Ar/O氛围下用近空间升华法制备的CdS薄膜的影响

采用近空间升华法（CSS）在氩/氧气氛中制备了硫化镉（CdS）多晶薄膜.利用XRD,XPS,AFM,UV-VIS光谱和四探针技术等测试和分析手段系统研究了氧对薄膜的成分、结构、光学和电学等性质的影响.结果表明,用近空间升华法制备的CdS薄膜具有六方相结构,膜层致密、均匀,平均晶粒大小约为40 nm,富硫.氧掺入后部分与镉生成氧化镉,并随着氧含量的增加,薄膜的成分有趋于化学计量比的趋势,光学带隙加宽,光暗电导比增加.此外,还利用扫描电镜（SEM）观察了CdS/CdTe断面结合光谱响应（QE）的结果讨论了氧对CdS/CdTe界面互扩散的影响.发现,随着CdS薄膜制备气氛中氧分压的升高,CdS/CdTe界面的互扩散程度降低,有利于提高器件在500—600 nm波长范围内的光谱响应.认为,氧含量的增加不但使CdS薄膜在光伏应用方面的质量得到改善,而且CdTe太阳电池器件中的CdS/CdTe界面也得到了优化. 关键词： CdS多晶薄膜 近空间升华法 窗口层 界面     

Local density valence band offset in GaAs/AlAs: Role of interface dipole

The valence band offset, ΔE_V ,at the lattice-matched GaAs/AlAs(001) interface is derived from highly precise self- consistent all-electron local density band structure calculations of the (GaAs)_n(AlAs)_n(001) superlattices (with n ⩽ 3). Using the core levels as reference energies, we find that ΔE_V = 0.50 ± 0.05 eV, in very good agreement with recent experimental results (ΔE_V = 0.45 − 0.55 eV). The dependence of ΔE_V on the superlattice thickness is studied and related to the interface charge redistribution which produces an interface dipole potential estimated to be ∼ 0.14 eV.     

Photoluminescence quenching of CdTe/CdS core-shell quantum dots in aqueous solution by ZnO nanocrystals

Photoluminescence (PL) properties of 3-mercaptopropionic acid (MPA) coated CdTe/CdS core-shell quantum dots (QDs) in aqueous solution in the presence of ZnO colloidal nanocrystals were studied by steady-state and time-resolved PL spectroscopy. The PL quenching of CdTe/CdS core-shell QDs with addition of purified ZnO nanocrystals resulted in a decrease in PL lifetime and a small red shift of the PL band. It was found that CdTe(1.5 nm)/CdS type II core-shell QDs exhibited higher efficiency of PL quenching than the CdTe(3.0 nm)/CdS type I core-shell QDs, indicating an electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals. The experimental results indicated that the efficient electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals could be controlled by changing the CdTe core size on the basis of the quantum confinement effect.     

Effect of a buffer layer between the shell and ligand on the optical properties of an exciton and biexciton in type-II quantum dot nanocrystals

In this study, we have investigated the effect of the buffer layers on the electronic and optical properties of an exciton (X) and a biexciton (XX) in a type-II CdTe/CdSe quantum dot nanocrystal. In an experimental study, it has been reported that when a CdTe/CdSe quantum dot nanocrystal is coated by a ZnTe material as a buffer layer, the photoluminescence quantum yield is growing from 4 to 20%. We have confirmed theoretically this improvement and extended the calculations to an XX structure. In the calculations, two different semiconductor materials, CdS and ZnTe, have been considered for the buffer layer. We have theoretically shown that the buffer layer causes an increase in the radiative oscillator strength of both X and XX. When the ZnTe is used as the buffer layer, the oscillator strength becomes stronger when compared to CdSe buffer material because of higher conduction band offset between CdSe and ZnTe.     

Atomistic tight-binding computations of the structural and optical properties of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals

A study of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals is carried out using atomistic tight-binding theory and the configuration interaction method to provide information for applications in bioimaging, biolabeling, display devices and near-infrared electronic instruments. The calculations yield the dependences of the internal and external passivated shells on the natural behaviours of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals. The reduction of the optical band gaps is observed with increasing numbers of monolayers in the external ZnS shell due to quantum confinement. Interestingly, the optical band gaps of CdTe/CdS/ZnS core/shell/shell nanocrystals are greater than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. In the presence of an external ZnS-coated shell, electron–hole wave function overlaps, oscillation strengths, ground-state exchange energies and Stokes shift are improved, whereas ground-state coulomb energies and fine-structure splitting are reduced. The oscillation strengths, Stokes shift and fine-structure splitting are reduced with the increase in external ZnS shell thickness. The oscillation strengths, Stokes shift and fine-structure splitting of CdTe/CdS/ZnS core/shell/shell nanocrystals are larger than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. Reduction of the atomistic electron–hole interactions is observed with increasing external ZnS shell size. The strong electron–hole interactions are more probed in CdTe/CdS/ZnS core/shell/shell nanocrystals than in CdTe/CdSe/ZnS core/shell/shell nanocrystals.