Ultrafast photoelectric effects and high-sensitive photovoltages in perovskite oxides and heterojunctions

Perovskite oxides and heterojunctions have attracted much attention due to their multifunctional properties of electricity and optics and magnetic as well as the very good chemical and thermal stability. In this brief review, we describe the novel progress of researches in the optical characteristic, including ultrafast photoelectric effects of picosecond order in perovskite oxide single crystals, thin-films and heterojunctions, high-sensitive photovoltages, the enhanced transient lateral photovoltages in perovskite oxide thin-films and heterojunctions, and the high-sensitive ultraviolet (UV) photodetectors based on perovskite oxides. The recent advances present in this paper not only could stimulate theoretical studies on the mechanism but also would open up the possibilities in the developments of optoelectronic devices based on perovskite oxides and heterojunctions.     

Band structure of cubic NaxWO3

The band structures of cubic WO₃ and NaWO₃ have been calculated, and they are shown to be nearly identical, demonstrating the validity of the rigid band model for different sodium concentrations. To elucidate the nature of the bonding, the density of states is decomposed into its s, p, and d contributions from each atomic site.     

Photon-interactions with perovskite oxides

Photons with variable energy, high coherency, and switchable polarization provide an ideal tool-kits for exploring the cutting-edge scientific questions in the condensed matter physics and material sciences. Over decades, extensive researches in the sample fabrication and excitation have employed the photon as one of the important means to synthesize and explore the low-dimensional quantum materials. In this review, we firstly summarize the recent progresses of the state-of-the-art thin-film deposition methods using excimer pulsed laser, by which syntactic oxides with atomic-unit-cell-thick layers and extremely high crystalline quality can be programmatically fabricated. We demonstrate that the artificially engineered oxide quantum heterostructures exhibit the unexpected physical properties which are absent in their parent forms. Secondly, we highlight the recent work on probing the symmetry breaking at the surface/interface/interior and weak couplings among nanoscale ferroelectric domains using optical second harmonic generation. We clarify the current challenges in the in-situ characterizations under the external fields and large-scale imaging using optical second harmonic generation. The improvements in the sample quality and the non-contact detection technique further promote the understanding of the mechanism of the novel properties emerged at the interface and inspire the potential applications, such as the ferroelectric resistive memory and ultrahigh energy storage capacitors.     

Study of band offsets in InN/Ge heterojunctions

InN layers were directly grown on Ge substrate by plasma-assisted molecular beam epitaxy (PAMBE). The valence band offset (VBO) of wurtzite InN/Ge heterojunction is determined by X-ray photoemission spectroscopy (XPS). The valence band of Ge is found to be 0.18 ± 0.04 eV above that of InN and a type-II heterojunction with a conduction band offset (CBO) of ~ 0.16 eV is found. The accurate determination of the VBO and CBO is important for the design of InN/Ge based electronic devices.     

Relationship between local structure and relaxor behavior in perovskite oxides

Despite intensive investigations over the past five decades, the microscopic origins of the fascinating dielectric properties of ABO3 relaxor ferroelectrics are currently poorly understood. Here, we show that the frequency dispersion that is the hallmark of relaxor behavior is quantitatively related to the crystal chemical characteristics of the solid solution. Density functional theory is used in conjunction with experimental determination of cation arrangement to identify the 0 K structural motifs. These are then used to parametrize a simple phenomenological Landau theory that predicts the universal dependence of frequency dispersion on the solid solution cation arrangement and off-center cation displacements.     

Relaxation processes in the paraelectric phase of ceramic oxides with a perovskite structure

Solid solutions of barium, strontium, and lead titanate ceramics with a perovskite structure are studied using impedance spectroscopy in the frequency range 10²–10⁶ Hz at temperatures from 20 to 450°C. The experimental data represented by the dispersion of the electric modulus are compared with the results of calculations performed for different mechanisms of the non-Debye relaxation in terms of the Havrilyak-Negami empirical formulas and the Jonscher universal dielectric response with the aim of determining a more adequate approach. The activation energy of relaxation processes in the paraelectric phase of the samples under investigation are calculated.     

钙钛矿氧化物异质结自旋极化输运机制研究

文章介绍了一个基于弱Hund耦合规则以及载流子漂移扩散机制所提出的关于钙钛矿氧化物p-n异质结构的自旋极化输运机制的物理模型.该理论不仅可以很好地解释由具有负磁阻效应的La0.9Sr0.1MnO3（LSMO）与非磁性的SrNb0.01Ti0.99O3（SNTO）所组成的异质结中所存在的正磁电阻效应,同时揭示了该体系中LSMO在界面区域的载流子与远离界面区域的载流子具有不同的自旋极化方向.这一结果将为理解钙钛矿氧化物异质结及多层膜的自旋极化输运机制开辟了一条新的途径.     

钙钛矿氧化物异质结自旋极化输运机制研究

文章介绍了一个基于弱Hund耦合规则以及载流子漂移扩散机制所提出的关于钙钛矿氧化物p-n异质结构的自旋极化输运机制的物理模型．该理论不仅可以很好地解释由具有负磁阻效应的La0.9Sr0．1MnO3（LSMO）与非磁性的SrNb0.01Ti0.99O3（SNTO）所组成的异质结中所存在的正磁电阻效应，同时揭示了该体系中LSMO在界面区域的载流子与远离界面区域的载流子具有不同的自旋极化方向．这一结果将为理解钙钛矿氧化物异质结及多层膜的自旋极化输运机制开辟了一条新的途径．     

Coupled-optical-phonon-mode electron scattering in perovskite oxides

Conductivity and Hall effect measurements were made on KTa_1?xNb_xO₃(x= 0.00,0.04,0.11 and 0.16) in the intermediate temperature range (77–300 K). It was found that the temperatures dependence of the Hall mobility obeyed a semiempirical relationship of Wemple et al. in this temperature range. The main scattering mechanism is proposed to be longitudinal optical phonons which are coupled to the “soft” transverse optical phonons associated with ferroelectricity.     

Resistance switching memory in perovskite oxides

The resistance switching behavior has recently attracted great attentions for its application as resistive random access memories (RRAMs) due to a variety of advantages such as simple structure, high-density, high-speed and low-power. As a leading storage media, the transition metal perovskite oxide owns the strong correlation of electrons and the stable crystal structure, which brings out multifunctionality such as ferroelectric, multiferroic, superconductor, and colossal magnetoresistance/electroresistance effect, etc. The existence of rich electronic phases, metal–insulator transition and the nonstoichiometric oxygen in perovskite oxide provides good platforms to insight into the resistive switching mechanisms.     

New ferromagnetic oxides derived from the perovskite structure prepared under high pressures

Abstract

Using a simple approach of ferromagnetic interactions through a 180° superexchange in a perovskite lattice a composition has been set-tip : La₂MnIrO₆. A band-structure calculation having confirmed such a simple approach, the compound was prepared and characterized. Structural and magnetic studies have confirmed the ferromagnetic behaviour of such an oxide. This methodology is now used to define a new class of ferromagnetic oxides.     

Universal octahedral-site distortion in orthorhombic perovskite oxides

Lattice parameters of the orthorhombic perovskites RMO3 (R=rare earth, M=Ti, V, ..., Ni, and Ga) have been simulated based on the ionic M-O bond length and rigid MO6/2 octahedra. Comparison with experimental data shows that the long-standing lattice-parameter anomaly generally found for the larger R3+ ions in these families is caused by a structural feature that is not revealed by the geometric tolerance factor widely used for the perovskites.     

Band structure engineering and defect control of oxides for energy applications

Metal oxides play an essential role in modern optoelectronic devices because they have many unique physical properties such as structure diversity, superb stability in solution, good catalytic activity, and simultaneous high electron conductivity and optical transmission. Therefore, they are widely used in energy-related optoelectronic applications such as photovoltaics and photoelectrochemical(PEC) fuel generation. In this review, we mainly discuss the structure engineering and defect control of oxides for energy applications, especially for transparent conducting oxides(TCOs) and oxide catalysts used for water splitting. We will review our current understanding with an emphasis on the contributions of our previous theoretical modeling, primarily based on density functional theory. In particular, we highlight our previous work:(i) the fundamental principles governing the crystal structures and the electrical and optical behaviors of TCOs;(ii) band structures and defect properties for n-type TCOs;(iii) why p-type TCOs are difficult to achieve;(iv) how to modify the band structure to achieve p-type TCOs or even bipolarly dopable TCOs;(v) the origin of the high-performance of amorphous TCOs; and(vi) band structure engineering of bulk and nano oxides for PEC water splitting. Based on the understanding above, we hope to clarify the key issues and the challenges facing the rational design of novel oxides and propose new and feasible strategies or models to improve the performance of existing oxides or design new oxides that are critical for the development of next-generation energy-related applications.     

Half-metallic ferromagnetism in cubic perovskite type NdInO3

ABSTRACT

Based on the full-potential linearised augmented plane wave plus local orbitals (FP-L/APW?+?lo) method within the density functional theory (DFT), the structural, electronic, and magnetic calculations of the cubic oxide perovskite NdInO₃ compound have been done under the generalised gradient approximation (GGA). The exchange and correlation (XC) potential is defined as GGA framework in the analyses of structural properties, while both GGA and GGA?+?U (U is the Hubbard correlation term) approximations are taken to treat the electronic and magnetic properties. It is found that ferromagnetic (FM) configuration is reported as the most stable ground state of the cubic NdInO₃ material; however, the equilibrium lattice parameters such as lattice constant (a₀ ), bulk modulus (B₀ ), its first-pressure derivative (B’), and the minimum of total energy (E₀ ) are given in paramagnetic (PM), ferromagnetic (FM), and anti-ferromagnetic (AFM) states. The spin-polarized electronic structure calculations (band structure and density of states) of the cubic oxide perovskite NdInO₃ compound verify the half-metallic feature due to the spin-up case which has the metallic nature, whereas the spin-down case presents the semiconducting character. Moreover, the magnetic properties show the integer value of the total magnetic moment for the studied compound (3μ_B ), where it is manly contributed by Nd atoms with apparition of weak local magnetic moments in non magnetic In and O sites.     

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.