Energy level engineering of charge selective contact and halide perovskite by modulating band offset:Mechanistic insights

Mixed cation and anion based perovskites solar cells exhibited enhanced stability under outdoor conditions,however,it yielded limited power conversion efficiency when TiO_(2) and Spiro-OMeTAD were employed as electron and hole transport layer(ETL/HTL)respectively.The inevitable interfacial recombination of charge carriers at ETL/perovskite and perovskite/HTL interface diminished the efficiency in planar(n-i-p)perovskite solar cells.By employing computational approach for uni-dimensional device simulator,the effect of band offset on charge recombination at both interfaces was investigated.We noted that it acquired cliff structure when the conduction band minimum of the ETL was lower than that of the perovskite,and thus maximized interfacial recombination.However,if the conduction band minimum of ETL is higher than perovskite,a spike structure is formed,which improve the performance of solar cell.An optimum value of conduction band offset allows to reach performance of 25.21%,with an open circuit voltage(VOC)of 1231 mV,a current density JSC of 24.57 mA/cm^(2) and a fill factor of 83.28%.Additionally,we found that beyond the optimum offset value,large spike structure could decrease the performance.With an optimized energy level of Spiro-OMeTAD and the thickness of mixed-perovskite layer performance of 26.56% can be attained.Our results demonstrate a detailed understanding about the energy level tuning between the charge selective layers and perovskite and how the improvement in PV performance can be achieved by adjusting the energy level offset.

Effect of deposited temperatures of the buffer layer on the band offset of CZTS/In2S3 heterostructure and its solar cell performance

The effect of the deposition temperature of the buffer layer In_2S_3 on the band alignment of CZTS/In_2S_3 heterostructures and the solar cell performance have been investigated.The In_2S_3 films are prepared by thermal evaporation method at temperatures of 30,100,150,and 200 ℃,respectively.By using x-ray photoelectron spectroscopy（XPS）,the valence band offsets（VBO） are determined to be-0.28 ±0.1,-0.28 ±0.1,-0.34 ±0.1,and-0.42 ±0.1 eV for the CZTS/In_2S_3heterostructures deposited at 30,100,150,and 200 ℃,respectively,and the corresponding conduction band offsets（CBO）are found to be 0.3 ±0.1,0.41 ±0.1,0.22±0.1,and 0.01 ±0.1 eV,respectively.The XPS study also reveals that interdiffusion of In and Cu occurs at the interface of the heterostructures,which is especially serious at 200 ℃ leading to large amount of interface defects or the formation of CuInS_2 phase at the interface.The CZTS solar cell with the buffer layer In_2S_3 deposited at 150 ℃ shows the best performance due to the proper CBO value at the heterostructure interface and the improved crystal quality of In_2S_3 film induced by the appropriate deposition temperature.The device prepared at 100 ℃presents the poorest performance owing to too high a value of CBO.It is demonstrated that the deposition temperature is a crucial parameter to control the quality of the solar cells.

Band offsets engineering at Cd_xZn_(1-x)S/Cu_2ZnSnS_4 heterointerface

Cd1-xZnxS/Cu2ZnSnS4 （CZTS）-based thin film solar cells usually use CdS as a buffer layer, but due to its smaller band gap （2.4 eV）, CdS film has been replaced with higher band gap materials. The cadmium zinc sulfide （CdZnS） ternary compound has a higher band gap than other compounds, which leads to a decrease in window absorption loss. In this paper, the band offsets at Cd1-xZnxS/CuzZnSnS4 （CZTS） heterointerface are calculated by the first-principles, density- functional and pseudopotential method. The band offsets at Cdl xZnxS/CZTS heterointerface are tuned by controlling the composition of Zn in Cd1-xZnxS alloy, the calculated valence band offsets are small, which is consistent with the commonanion rule. The favorable heterointerface of type-I with a moderate barrier height （〈 0.3 eV） can be obtained by controlling the composition of Zn in Cdl-xZnxS alloy between 0.25 and 0.375.

Investigation of Zn(1-x)CdxO films bandgap and Zn(1-x)CdxO/ZnO heterojunctions band offset by x-ray photoelectron spectroscopy

A series of Zn_（1-x）Cd_xO thin films have been fabricated on sapphire by pulsed-laser deposition（PLD）, successfully. To investigate the effect of Cd concentration on structural and optical properties of Zn_（1-x）Cd_xO films, x-ray diffraction（XRD）,ultraviolet-visible spectroscopy（UV-vis）, and x-ray photoelectron spectroscopy（XPS） are employed to characterize the films in detail. The XRD pattern indicates that the Zn_（1-x）Cd_xO thin films have high single-orientation of the c axis. The energy bandgap values of ZnCdO thin films decrease from 3.26 eV to 2.98 eV with the increasing Cd concentration（x）according to the（αhν）~2–hν curve. Furthermore, the band offsets of Zn_（1-x）Cd_xO/ZnO heterojunctions are determinated by XPS, indicating that a type-I alignment takes place at the interface and the value of band offset could be tuned by adjusting the Cd concentration.

Influence of interface states, conduction band offset, and front contact on the performance of a-SiC：H(n)/c-Si(p)heterojunction solar cells

P-type silicon heterojunction（SHJ） solar cells with a-SiC：H（n） emitters were studied by numerical computer simulation in this paper. The influence of interface states, conduction band offset, and front contact on the performance of a-SiC：H（n）/c-Si（p） SHJ solar cells was investigated systematically. It is shown that the open circuit voltage（Voc） and fill factor（F F） are very sensitive to these parameters. In addition, by analyzing equilibrium energy band diagram and electric field distribution, the influence mechanisms that interface states, conduction band offset, and front contact impact on the carrier transport, interface recombination and cell performance were studied in detail. Finally, the optimum parameters for the a-SiC：H（n）/c-Si（p） SHJ solar cells were provided. By employing these optimum parameters, the efficiency of SHJ solar cell based on p-type c-Si was significantly improved.

Band offset and electronic properties at semipolar plane Al N(1ī01)/diamond heterointerface

Tailoring the electronic states of the Al N/diamond interface is critical to the development of the next-generation semiconductor devices such as the deep-ultraviolet light-emitting diode, photodetector, and high-power high-frequency field-effect transistor. In this work, we investigate the electronic properties of the semipolar plane Al N（11^-01）/diamond heterointerfaces by using the first-principles method with regard to different terminated planes of Al N and surface structures of diamond（100） plane. A large number of gap states exist at semi-polar plane Al N（11^-01）/diamond heterointerface, which results from the N 2 p and C 2 s2 p orbital states. Besides, the charge transfer at the interface strongly depends on the surface termination of diamond, on which hydrogen suppresses the charge exchange at the interface. The band alignments of semi-polar plane Al N（11^-01）/diamond show a typical electronic character of the type-Ⅱ staggered band configuration. The hydrogen-termination of diamond markedly increases the band offset with a maximum valence band offset of 2.0 e V and a conduction band offset of 1.3 e V for the semi-polar plane N–Al N（11^-01）/hydrogenated diamond surface. The unique band alignment of this Type-Ⅱ staggered system with the higher CBO and VBO of the semi-polar Al N/HC（100） heterostructure provides an avenue to the development of robust high-power high-frequency power devices.

Valence band offsets of the strained and longitudinally relaxed diamond/c-BN superlattices

The valence band offsets of the strained and longitudinally relaxed diamond/cubic boron-nitride （c-BN） （110） superlattice are investigated by the plane wave density functional theory approach and using the on-site core electron as a reference energy level. For the strained diamond/c-BN superlattice, the valence band offset of around 1.50 eV is in good agreement with those using all the electrons methods. As for the longitudinally relaxed superlattice, the valence band offset of around 1.28 eV is smaller than that of the strained superlattice. The reason for this is mainly due to the split of the valence band maximum caused by the anisotropic strain.

Direct calculations on the band offsets of large-latticemismatched and heterovalent Si and III-V semiconductors

Band offset in semiconductors is a fundamental physical quantity that determines the performance of optoelectronic devices.However,the current method of calculating band offset is difficult to apply directly to the large-lattice-mismatched and heterovalent semiconductors because of the existing electric field and large strain at the interfaces.Here,we proposed a modified method to calculate band offsets for such systems,in which the core energy level shifts caused by heterovalent effects and lattice mismatch are estimated by interface reconstruction and the insertion of unidirectional strain structures as transitions,respectively.Taking the Si and III-V systems as examples,the results have the same accuracy as what is a widely used method for small-lattice-mismatched systems,and are much closer to the experimental values for the large-lattice-mismatched and heterovalent systems.Furthermore,by systematically studying the heterojunctions of Si and III-V semiconductors along different directions,it is found that the band offsets of Si/InAs and Si/InSb systems in[100],[110]and[111]directions belong to the type I,and could be beneficial for silicon-based luminescence performance.Our study offers a more reliable and direct method for calculating band offsets of large-lattice-mismatched and heterovalent semiconductors,and could provide theoretical support for the design of the high-performance silicon-based light sources.

Simplified Method of Valence Band Offset Calculation at Strained Layer Heterojunction

The average bond energy method is popularized and applied to study band offsets at strained layer heterojunctions. By careful examination of hydrostatic and uniaxial strain actions on the band offset parameter Emv,it is found that the average band offset parameter Emv,av=Em-Ev, av remains basically unchanged under different strain conditions. Therefore, provided the band offset parameter before strain Emv,0 of bulk material is calculated, and the experiment values of deformation potential b and spin-orbit （SO） splitting energy △0 are quoted, the Emv at strained layer can be obtained by a simple and convenient algebraic calculation. Thus the valence band offset △Ev at strained layer heterojunction can also be predicted conveniently. This simplified calculation method is characterized by decreased calculation amount and increased conviction due to use as many as possible the experiment values.

Study on Valence Band Offsets atStrained Heterojunctions

A method, which can predict the valence band offsets at strained layer heterojunctions under different strain situations only by calculating band structures and deformation parameters of the bulk materials, is suggested. The applicability of this method is verified by calculation of the valence band offsets at strained layer heterojuntions ,such as InP/InAs, InP/GaP, GaAs/InAs, GaP/GaAs and AlAs/InAs with various strain conditions.

Band offsets between amorphous La_2Hf_2O_7 and silicon

Abstract： Amorphous LazHf2O7 films were grown on Si（100） by pulsed laser deposition method. The valence and conduction band offsets between amorphous La2Hf2O7 film and silicon were determined by using synchrotron radiation photoemission spectroscopy. The energy band gap of amorphous La2Hf2O7 film was measured from the energy-loss spectra of O ls photoelectrons. The band gap of amorphous LazHf2O7 film was determined to be 5.4±0.2 eV. The valence and the conduction-band offsets of amorphous La2Hf2O7 film to Si were obtained to be 2.7±0.2 and 1.6±0.2 eV, respectively. These results indieated that the amorphous La2Hf2O7 film could be one promising candidate for high-k gate dielectrics.

Ab initio Calculation of Valence-band Offsets for Lattice-matched Heterojunctions

In the light of our previous result that the average bond energy E_h valuelines up across heterojunction interfaces,in this paper,the valence-band offsets in ten hete-rojunctions have been calculated using the E_h as a reference level with the LMTO-ASAband-structure method.The calculated results are in excellent agreement with those fromthe more elaborate first-principles self-consistent interface calculations.As the presentmethod requires by far the smaller computational effort,it is very convenient for usingon medium-sized computers.

Cs_(2)AgBi_(0.75)Sb_(0.25)Br_(6)钙钛矿太阳能电池的优化设计

双钙钛矿太阳能电池以其低成本、高性能、环境友好、稳定性强而备受关注.本研究使用Silvaco TCAD分析了Cs_(2)AgBi_(0.75)Sb_(0.25)Br_(6)太阳能电池的钙钛矿层厚度、能带偏移、金属电极功函数、传输层厚度及掺杂浓度与器件效率的关系,以提升器件性能.基于空穴传输层为Spiro-OMeTAD,电子传输层为ZnO的器件进行初始研究,其显示出12.66%的光电转换效率.结果表明,当钙钛矿层厚度大于500 nm时,效率趋于饱和.最佳导带偏移量为0—+0.5 eV,最佳价带偏移量为-0.1—+0.2 eV.在改变器件的电子传输层为ZnOS,空穴传输层分别为MoO_(3),Cu_(2)O和CuSCN的情况下,优化其厚度和掺杂浓度,最终空穴传输层为Cu_(2)O的双钙钛矿太阳能电池理论光电转换效率达22.85%,比目前报道的理论效率值相对提升了25.6%.此外,当金属电极功函数小于-4.9 eV时易实现最佳效率.本工作为开发高性能无铅钙钛矿太阳能电池提供了理论指导.

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.

Band alignment of p-type oxide/ε-Ga2O3 heterojunctions investigated by x-ray photoelectron spectroscopy

Theε-Ga2O3 p-n heterojunctions(HJ)have been demonstrated using typical p-type oxide semiconductors(NiO or SnO).Theε-Ga2O3 thin film was heteroepitaxial grown by metal organic chemical vapor deposition(MOCVD)with three-step growth method.The polycrystalline SnO and NiO thin films were deposited on theε-Ga2O3 thin film by electron-beam evaporation and thermal oxidation,respectively.The valence band offsets(VBO)were determined by x-ray photoelectron spectroscopy(XPS)to be 2.17 eV at SnO/ε-Ga2O3 and 1.7 eV at NiO/ε-Ga2O3.Considering the bandgaps determined by ultraviolet-visible spectroscopy,the conduction band offsets(CBO)of 0.11 eV at SnO/ε-Ga2O3 and 0.44 eV at NiO/ε-Ga2O3 were obtained.The type-Ⅱband diagrams have been drawn for both p-n HJs.The results are useful to understand the electronic structures at theε-Ga2O3 p-n HJ interface,and design optoelectronic devices based onε-Ga2O3 with novel functionality and improved performance.

Revisit of the band gaps of rutile SnO2 and TiO2: a first-principles study

From the recent experimentally observed conduction band offset and previously reported band gaps,one may deduce that the valence band offset between rutile SnO2 and TiO2 is around 1 eV,with TiO2 having a higher valence band maximum.This implication sharply contradicts the fact that the two compounds have the same rutile structure and the Γ3^+ VBM state is mostly an oxygen p state with a small amount of cation d character,thus one would expect that SnO2 and TiO2 should have small valence band offset.If the valence band offset between SnO2 and TiO2 is indeed small,one may question the correctness of the previously reported band gaps of SnO2 and TiO2.In this paper,using first-principles calculations with different levels of computational methods and functionals within the density functional theory,we reinvestigate the long-standing band gap problem for SnO2.Our analysis suggests that the fundamental band gap of SnO2 should be similar to that of TiO2,i.e.,around 3.0 eV.This value is significantly smaller than the previously reported value of about 3.6 eV,which can be attributed as the optical band gap of this material.Similar to what has been found in In2O3,the discrepancy between the fundamental and optical gaps of SnO2 can be ascribed to the inversion symmetry of its crystal structure and the resultant dipole-forbidden transitions between its band edges.Our results are consistent with most of the optical and electrical measurements of the band gaps and band offset between SnO2 and TiO2,thus provide new understanding of the band structure and optical properties of SnO2.Experimental tests of our predictions are called for.

Origin of the anomalous trends in band alignment of GaX/ZnGeX_2(X = N, P, As, Sb) heterojunctions

Utilizing first-principles band structure method, we studied the trends of electronic structures and band offsets of the common-anion heterojunctions GaX/ZnGeX_2(X = N, P, As, Sb). Here, ZnGeX_2 can be derived by atomic transmutation of two Ga atoms in GaX into one Zn atom and one Ge atom. The calculated results show that the valence band maximums(VBMs) of GaX are always lower in energy than that of ZnGeX_2, and the band offset decreases when the anion atomic number increases. The conduction band minimums(CBMs) of ZnGeX_2 are lower than that of GaX for X = P, As, and Sb, as expected. However, surprisingly, for ZnGeN2, its CBM is higher than GaN. We found that the coupling between anion p and cation d states plays a decisive role in determining the position of the valence band maximum, and the increased electronegativity of Ge relative to Ga explains the lower CBMs of ZnGeX_2 for X = P, As, and Sb. Meanwhile, due to the high ionicity, the strong coulomb interaction is the origin of the anomalous behavior for nitrides.

Effect of Defects at the Buffer Layer CdS/Absorber CIGS Interface on CIGS Solar Cell Performance

This scientific paper presents a study investigating the effects of defects at the CdS/CIGS and CdS/SDL interfaces on the performance of CIGS solar cells. The objective of this study is to analyze the influence of defects at the interface between the CdS buffer layer and the CIGS absorber, as well as the surface defect layer (SDL), on CIGS solar cell performance. The study explores three key aspects: the impact of the conduction band offset (CBO) at the CdS/CIGS interface, the effects of interface defects and defect density on performance, and the combined influence of CBO and defect density at the CdS/ SDL and SDL/CIGS interfaces. For interface defects not exceeding 1013 cm-2, we obtained a good efficiency of 22.9% when -0.1 eV analyzing the quality of CdS/SDL and SDL/CIGS junctions, it appears that defects at the SDL/CIGS interface have very little impact on the performances of the CIGS solar cell. By optimizing the electrical parameters of the CdS/SDL interface defects, we achieved a conversion efficiency of 23.1% when -0.05 eV < CBO < 0.05 eV.

Discussion on the Electron and Hole Effective Masses in Thermal Silicon

This review and research study provides conclusive discussion on the electron and hole effective masses in thermal silicon dioxide placing their values at 0.42m and 0.58m,where m is the free electron mass,correct to two decimal places.Only one of the masses needs to be determined as the electron and hole masses in materials add up to be equal to free electron mass with the hole effective mass being larger than the electron effective mass.The review also convinces the reader that the CBO(conduction band offset)or the Si-SiO2 barrier height at the oxide/silicon interface of a Si MOS(metal-oxide-semiconductor)device is 3.20 eV.

CIGS薄膜太阳电池异质结的结构初析

本论文通过实验制备得到CuIn0.7Ga0.3Se2(CIGs)、CdS、ZnO三种半导体材料,然后根据这三种半导体的相关材料参数和实验数据,得出了它们形成异质结前后的能带图,并计算它们的能带边失调值△EC、△EV。其中,CdS／CIGS的导带边失调值ΔEc对高效率CIGS薄膜太阳电池的影响作用最大,为-0.298eV(高效电池的理想值范围为0-0.4eV),说明这对电池整体性能不是很好。