Band offsets in heterojunctions formed by oxides with cubic perovskite structure

A number of recent discoveries on heterostructures formed by oxides suggest the emergence of a new direction in microelectronics, the oxide electronics. In the present work, band offsets in nine heterojunctions formed by titanates, zirconates, and niobates with the cubic perovskite structure are calculated from first principles. The effect of strain in contacting oxides on their energy structure; the GW corrections to the band edge positions resulting from many-body effects; and the conduction band edge splitting resulting from spinorbit coupling are consistently taken into account. It is shown that the neglect of the many-body effects can cause errors in the determination of the band offsets, reaching 0.36 eV. The fundamental inapplicability of the transitivity rule often used to determine the band offsets in heterojunctions by comparing the band offsets in a pair of heterojunctions formed by the components of the heterojunction under study with a third common component is demonstrated. The cause of the inapplicability is explained.     

钙钛矿氧化物异质结的研究进展

在过去几年中,为了研究钙钛矿氧化物异质结的物性和潜在的应用前景,我们进行了许多探索。在本文中,我们总结了对钙钛矿氧化物异质结一些物理性质的理论描述,揭示了La0.9Sr0.1MnO3/SrNb0.01Ti0.99O3异质结中发现的正磁电阻效应和横向光电效应的物理起源。我们提出的理论模型将有助于理解界面对钙钛矿氧化物异质结各种性质的影响。     

利用PNA添加剂来调控钙钛矿薄膜结晶和覆盖率实现高效太阳能电池

钙钛矿薄膜形貌的控制是一个提高太阳能电池能量转换效率的关键问题,而引入添加剂是解决这一问题的一种有效而简便的方法。利用聚丙烯腈（PNA）作为CH₃NH₃PbI₃前驱体溶液溶剂添加剂,通过其浓度可以调控钙钛矿薄膜结晶和表面的覆盖率。本文通过SEM、XRD以及UV-Vis研究了PNA掺杂CH₃NH₃PbI₃钙钛矿薄膜后的表面形貌、结晶度和光学性能的变化。结果表明,通过添加少量的PNA可以优化钙钛矿薄膜的性能,其强烈影响薄膜的结晶过程,有助于形成均匀连续的薄膜,减少针孔,从而增强了钙钛矿层的覆盖率和光吸收。当PNA 的含量为1%（质量分数）时,钙钛矿太阳能电池的各项性能最佳,能量转换效率达到了8.38%。与未加PNA 的电池效率（1.31%） 相比,提高了540%。这些结果表明,PNA可以有效调控钙钛矿薄膜的晶体生长和薄膜形貌,在钙钛矿太阳能电池的大规模生产过程中是一种可以改善钙钛矿薄膜质量的有效添加剂。     

Electrochromic materials: Microstructure,electronic bands,and optical properties

Crystals of all the well known electrochromic metal (Me) oxides are composed of MeO₆ octahedra in various corner-sharing and edge-sharing arrangements. Cluster-type and columnar microstructures, based on the MeO₆ units, exist in electrochromic films. The coordination of the ions leads to schematic electronic band structures that, at least for the (defect) perovskite and rutile lattices, are able to explain the presence or absence of cathodic and anodic electrochromism. Small polaron absorption prevails in disordered oxides, while crystalline tungsten oxide can show free-electron effects.     

Dependence of Photovoltaic Property of ZnO/Si Heterojunction Solar Cell on Thickness of ZnO Films

N-ZnO/p-Si heterojunctions are prepared by sputtering deposition of intrinsic ZnO films on p-Si substrates. Thicknesses of ZnO films are altered by varying the deposition time from I h to 3h. The electrical properties of these structures are analysed from capacitance-voltage （C V） and current-voltage （I-V） characteristics performed in a dark room. The results demonstrated that all the samples show strong rectifying behaviour. Photovoltaie property for the samples with different thicknesses of ZnO films are investigated by measuring open circuit voltage and short circuit current. It is found that photovoltages are kept to be almost constant of 320 m V along with the thickness while photoeurrents changing a lot. The variation mechanism of the photovoltade effect as a function of thickness of ZnO films is investigated.     

Ab initio design of high-k dielectrics: La(x)Y1-xAlO3

We use calculations based on density-functional theory in the virtual crystal approximation for the design of high-k dielectrics, which could offer an alternative to silicon dioxide in complementary metal-oxide semiconductor devices. We show that aluminates LaxY1-xAlO3 alloys derived by mixing aluminum oxide with lanthanum and yttrium oxides have unique physical attributes for a possible application as gate dielectrics when stabilized in the rhombohedral perovskite structure, and which are lost in the orthorhombic modification. Stability arguments locate this interesting composition range as 0.2相似文献   

La1.3Sr1.7Mn2O7/SrTiO3-Nb异质结的整流和光伏特性

采用脉冲激光沉积法在SrTiO₃:0.7%Nb(100)单晶衬底上生长了La_1.3Sr_1.7Mn₂O₇(LSMO)薄膜, 并 研究了LSMO/SrTiO₃-Nb异质结的输运性质和光伏效应. 研究发现, 异质结具有良好的整流特征和明显的光生伏特效应. 在532 nm激光辐照下, 光生电压随温度升高先增大后减小, 并且在150 K达到最大值400 mV, 此温度点与LSMO薄膜发生金属-绝缘体转变的温度一致, 这表明异质结的光生伏特效应受LSMO薄膜内部的输运特征调控. 进一步, 从光生电压随时间的变化曲线中分析发现, 上升沿符合一阶指数函数, 这与载流子的迁移过程相关; 而下降沿符合二阶指数函数, 这与结两侧载流子的外部回路中和以及材料内部的电子-空穴湮灭有关. 值得注意的是, 上升沿和下降沿的时间常数均随着温度先增大后减小, 且最大值均出现在LSMO薄膜的金属-绝缘转变温度.     

Preparation and magnetocaloric effect of (La0.67-XGdX)Sr0.33MnO3 (X =0.1,0.15) nanoparticles

We report a new route to synthesize nanosized (La_0.67-XGd_X)Sr_0.33MnO₃ (X=0.1,0.15) perovskite crystalline complex oxides at calcination temperatures of 600–900 °C using amorphous molecular alloy as precursor. The precursor could completely decompose into oxide at temperatures below 500 °C according to thermogravimetric analysis and differential thermal analysis results. X-ray diffraction demonstrated that the decomposed species was composed of perovskite structure at a calcination temperature of 600 °C for 2 h. The size and topography of the oxides are dependent on the calcination temperature of the precursor. The resulting particle size is in the range of 40–120 nm as determined by a transmission electron microscope. This method is effective and can be easily quantitatively controlled to synthesize nanosized perovskite complex oxides. The Curie temperature T_C and the magnetocaloric effect of (La_0.67-XGd_X)Sr_0.33MnO₃ (X=0.1,0.15) nanoparticles are discussed based on the measurement of the low-field magnetization curve and the isothermal magnetization curve. PACS 61.46.+w; 61.10.Nz; 75.75.+a; 81.20.Ka; 81.70.Pg     

Oxide anode materials for solid oxide fuel cells

A major advantage of solid oxide fuel cells (SOFCs) over polymer electrolyte membrane (PEM) fuel cells is their tolerance for the type and purity of fuel. This fuel flexibility is due in large part to the high operating temperature of SOFCs, but also relies on the selection and development of appropriate materials — particularly for the anode where the fuel reaction occurs. This paper reviews the oxide materials being investigated as alternatives to the most commonly used nickel–YSZ cermet anodes for SOFCs. The majority of these oxides form the perovskite structure, which provides good flexibility in doping for control of the transport properties. However, oxides that form other crystal structures, such as the cubic fluorite structure, have also shown promise for use as SOFC anodes. In this paper, oxides are compared primarily in terms of their transport properties, but other properties relative to SOFC anode performance are also discussed.     

Bipolar resistive switching in heterostructures: Bismuth oxide/normal metal

Thin filmed heterojunctions Ag/Bi/BiOx/Ag were fabricated and the effect of frequency of applied ac voltage on bipolar resistive switching in the obtained heterojunctions was observed for the first time. It has been found that the frequency dependence of the effect has a universal character for some oxide compounds. This observation confirms the significant role of oxygen-ion migration in the resistive switching phenomena in structures based on oxide compounds.     

Efficient design of perovskite solar cell using mixed halide and copper oxide

Solar cells based on perovskites have emerged as a transpiring technology in the field of photovoltaic. These cells exhibit high power conversion efficiency. The perovskite material is observed to have good absorption in the entire visible spectrum which can be well illustrated by the quantum efficiency curve. In this paper, theoretical analysis has been done through device simulation for designing solar cell based on mixed halide perovskite. Various parameters have efficacy on the solar cell efficiency such as defect density, layer thickness, doping concentration, band offsets, etc. The use of copper oxide as the hole transport material has been analyzed. The analysis divulges that due to its mobility of charge carriers, it can be used as an alternative to spiro-OMeTAD. With the help of simulations, reasonable materials have been employed for the optimal design of solar cell based on perovskite material. With the integration of copper oxide into the solar cell structure, the results obtained are competent enough. The simulations have shown that with the use of copper oxide as hole transport material with mixed halide perovskite as absorber, the power conversion efficiency has improved by 6%.The open circuit voltage has shown an increase of 0.09 V, short circuit current density has increased by 2.32 m A/cm~2, and improvement in fill factor is 8.75%.     

Large grained and high charge carrier lifetime CH3NH3PbI3 thin-films: implications for perovskite solar cells

Spin coated perovskite thin films are known to have an issue of pinholes & poor morphology control which lead to poor device-to-device repeatability, that is an impediment to scale-up. In this work, Methylamine vapor annealing process is demonstrated which consistently leads to high-quality perovskite thin-films with an average grain-size of 10–15 μm. The improvement in film morphology enables improvement in effective carrier recombination lifetime, from 21 μs in as-deposited films to 54 μs in vapor-annealed films. The annealed films with large-grains are also more stable in ambient conditions. Devices made on annealed perovskite films are very consistent, with a standard deviation of only 0.7%. Methylamine vapor annealing process is a promising method of depositing large-grain CH₃NH₃PbI₃ films with high recombination lifetime and the devices with improved performance.     

Photoelectric parameters of the heterojunctions ITO-CdGeP2

Photosensitive n-n and n-p structures based on CdGeP₂ crystals and layers of indium and tin oxides were prepared by the method of reactive cathodic sputtering. The photoelectric properties of the structures in natural and linearly polarized light were studied, and the temperature dependence of the photosensitivity in the interval 80–400 K was also measured. The polarization parameters of heterojunctions were determined, and the results were analyzed based on a model of the band spectrum and the selection rules for interband transitions in CdGeP₂. It is shown that n-n heterojunctions can be employed as polarimetric photodetectors.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 39–44, August, 1988.     

R & D for intermediate temperature solid state fuel cells

Although some solid oxide fuel cells (SOFCs) are in the process of ommercialization, this technology still faces serious technical challenge due to the special high temperature (1000 °C) requirement resulting in high costs as well. It has thus been a strong tendency to develop intermediate temperature (400 to 800 °C) solid state fuel cells (ITSSFCs). ITSSFCs use either oxide ionic conductors, e.g. fluorite or perovskite oxides or proton conducting oxyacid salts and salt-oxide composites as electrolytes that have a high protonic or oxide ionic conductivity of 10⁻² to 10⁻¹ S/cm in the IT region. The ITSSFCs may provide new opportunities for SSFC (including SOFC) commercialization. This paper gives a brief overview of the current ITSSFC status and activities of research and development mainly based on our work. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June 14–17, 1998.     

Resistance switching in oxides with inhomogeneous conductivity

Electric-field-induced resistance switching （RS） phenomena have been studied for over 60 years in metal/dielectrics/metal structures. In these experiments a wide range of dielectrics have been studied including binary transition metal oxides, perovskite oxides, chalcogenides, carbon- and silicon-based materials, as well as organic materials. RS phenomena can be used to store information and offer an attractive performance, which encompasses fast switching speeds, high scalability, and the desirable compatibility with Si-based complementary metal-oxide-semiconductor fabrication. This is promising for nonvolatile memory technology, i.e., resistance random access memory （RRAM）. However, a comprehensive understanding of the underlying mechanism is still lacking. This impedes faster product development as well as accurate assessment of the device performance potential. Generally speaking, RS occurs not in the entire dielectric but only in a small, confined region, which results from the local variation of conductivity in dielectrics. In this review, we focus on the RS in oxides with such an inhomogeneous conductivity. According to the origin of the conductivity inhomogeneity, the RS phenomena and their working mechanism are reviewed by dividing them into two aspects： interface RS, based on the change of contact resistance at metal/oxide interface due to the change of Schottky barrier and interface chemical layer, and bulk RS, realized by the formation, connection, and disconnection of conductive channels in the oxides. Finally the current challenges of RS investigation and the potential improvement of the RS performance for the nonvolatile memories are discussed.     

Evidence for an oxygen diffusion model for the electric pulse induced resistance change effect in transition-metal oxides

Electric-pulse induced resistance hysteresis switching loops for Pr0.7Ca0.3MnO3 perovskite oxide films were found to exhibit an additional sharp "shuttle tail" peak around the negative pulse maximum for films deposited in an oxygen-deficient ambient. The resistance relaxation in time of this "shuttle tail" peak as well as resistance relaxation in the transition regions of the resistance hysteresis loop show evidence of oxygen diffusion under electric pulsing, and support a proposed oxygen diffusion model with oxygen vacancy pileup at the metal electrode interface region as the active process for the nonvolatile resistance switching effect in transition-metal oxides.     

First principles study of electronic structure and optical properties of double perovskite Ba2(InM)O6 [M=Nb,Ta]

The structural, electronic and optical properties of double perovskite oxides Ba₂(InNb)O₆ and Ba₂(InTa)O₆ are investigated by full-potential linearized augmented plane wave method based on density functional theory under generalized gradient approximation. The real and imaginary parts of the dielectric function and the optical constant (refractive index) are calculated. The calculated spectra are compared with the experimental results and are found to be in reasonable agreement. The interband contributions to the optical properties of these perovskite oxides have been analyzed.     

Electrical and electrochemical properties of SrBiMTiO<Subscript>6</Subscript> (M = Fe,Mn, Cr) as potential cathodes for solid oxide fuel cells

A series of perovskite oxides SrBiMTiO₆ (M = Fe, Mn, Cr) have been synthesized and characterized towards application as cathode materials for solid oxide fuel cells (SOFCs). X-ray diffraction (XRD) patterns reveal that all samples are stabilized in \( \mathrm{Pm}\ \overline{3}\mathrm{m} \) space group. Electrical conductivity, AC impedance characteristics, and thermal and chemical stability have been studied in order to assess their possible use as SOFC cathode materials. In comparison with other low electrical conductivity cathodes of SOFC, our results suggest that SrBiMnTiO₆, which has the highest electrical conductivity (4.02 S cm^?1) and moderate polarization resistance (0.104 Ω cm²) at 850 °C, is the most promising candidate among the three perovskite oxides for further study and optimization as a SOFC cathode material.     

Solitons and solar cells: The non-equilibrium thermodynamics of the photovoltaic effect in polyacetylene

The production of photovoltages by trans-(CH)_x based devices is analyzed in terms of the non-equilibrium thermodynamics of the photovoltaic effect and compared with the model of photogenerated charged soliton pairs. It is concluded that the source of (CH)_x photovoltages is a photo-reaction channel in which photoexcitations remain as band electrons and holes for appreciable lifetimes.     

Amorphization of oxides under irradiation with fast neutrons

A variant of the solid-state radiation amorphization as a result of accumulation of the critical concentration of defects in the crystal has been considered using the example of oxides with the garnet and perovskite structures irradiated by fast neutrons. It has been shown that such defects can be antisite defects, the formation of which leads to considerable static displacements from the equilibrium sites of nearest ions and, consequently, to the loss of stability of the crystalline structure. The dependences of the root-mean-square displacements of oxygen ions on the concentration of the antisite defects are constructed based on the analysis of the experimental data. It has been established that the so-called critical concentrations of antisite defects, at which the spontaneous amorphization occurs, differ for oxides with the garnet and perovskite structures. As the criterion of the spontaneous radiation amorphization, it is proposed to consider the critical static displacement of the ions, which is identical for studied oxides and equal to ～0.28 Å, or ～0.14 in fractions of interatomic distances, which is close to the well-known Lindemann melting criterion.