钙钛矿型过渡金属氧化物界面二维电子态的研究进展

钙钛矿结构氧化物界面因其独特的强关联性质引起研究者的广泛关注。首先以SrTiO3/LaAlO3体系为例介绍了氧化物界面二维电子态独特的强关联性质,以及形成二维电子态的两种物理机制——"极化灾难"与氧缺陷理论;然后综述了SrTiO3/LaAlO3体系界面密度泛函理论计算的研究现状,包括3种计算模型的构建、界面处的能带偏移与电子分布、界面附近的离子弛豫及其对电子结构的影响等;最后简要介绍了其他钙钛矿结构氧化物界面体系,并展望了其发展前景。     

Creation and Control of Two-Dimensional Electron Gas Using Al-Based Amorphous Oxides/SrTiO(3) Heterostructures Grown by Atomic Layer Deposition

The formation of a two-dimensional electron gas (2-DEG) using SrTiO(3) (STO)-based heterostructures provides promising opportunities in oxide electronics. We realized the formation of 2-DEG using several amorphous layers grown by the atomic layer deposition (ALD) technique at 300 °C which is a process compatible with mass production and thereby can provide the realization of potential applications. We found that the amorphous LaAlO(3) (LAO) layer grown by the ALD process can generate 2-DEG (～1 × 10(13)/cm(2)) with an electron mobility of 4-5 cm(2)/V·s. A much higher electron mobility was observed at lower temperatures. More remarkably, amorphous YAlO(3) (YAO) and Al(2)O(3) layers, which are not polar-perovskite-structured oxides, can create 2-DEG as well. 2-DEG was created by means of the important role of trimethylaluminum, Me(3)Al, as a reducing agent for STO during LAO and YAO ALD as well as the Al(2)O(3) ALD process at 300 °C. The deposited oxide layer also plays an essential role as a catalyst that enables Me(3)Al to reduce the STO. The electrons were localized very near to the STO surface, and the source of carriers was explained based on the oxygen vacancies generated in the STO substrate.     

High Quality YBCO Film Growth on SrTiO_3-Buffered LaAlO_3 Substrate by Full Solution Method

A full solution method has been developed as a low cost process of YBa2Cu3OT-x （YBCO） coated conductor fabrication. In this study, highly biaxially textured SrTiO3 （STO） buffer layers were fabricated on LaAlO3 （LAO） single crystal substrates by sol-gel method using metal alkoxides as the staring precursor materials. High quality YBCO superconducting film was then fabricated on STO-buffered LAO substrate by trifluoroacetic metalorganic deposition （TFA-MOD） method. For the YBCO superconducting film, only （001） diffraction peaks can be detected by XRD （X-ray diffraction） analysis with no other phases detectable. Especially, Inplane texture of YBCO film is improved compared to that of STO buffer layer from phi scans analysis, which indicates the self-epitaxy phenomenon explained by considering interracial energy. STO and YBCO films both show c-axis oriented grains growth and have uniform surface microstructure. A critical transition temperature, TC （R=0） of 89.5 K and a critical current density of 2 mA/cm2 （77 K, self-field） were obtained for a 0.2μm thick YBCO film on STO-buffered LAO substrate. No reaction between YBCO and STO was detected by XRD analysis. This full solution process may provide a promising low cost fabrication route for YBCO coated conductors on metal tape.     

Mapping the spatial distribution of charge carriers in LaAlO3/SrTiO3 heterostructures

At the interface between complex insulating oxides, novel phases with interesting properties may occur, such as the metallic state reported in the LaAlO(3)/SrTiO(3) system . Although this state has been predicted and reported to be confined at the interface, some studies indicate a much broader spatial extension, thereby questioning its origin. Here, we provide for the first time a direct determination of the carrier density profile of this system through resistance profile mappings collected in cross-section LaAlO(3)/SrTiO(3) samples with a conducting-tip atomic force microscope (CT-AFM). We find that, depending on specific growth protocols, the spatial extension of the high-mobility electron gas can be varied from hundreds of micrometres into SrTiO(3) to a few nanometres next to the LaAlO(3)/SrTiO(3) interface. Our results emphasize the potential of CT-AFM as a novel tool to characterize complex oxide interfaces and provide us with a definitive and conclusive way to reconcile the body of experimental data in this system.     

Polarization and electric field dependence of electronic properties in LaAlO3/SrTiO3 heterostructures

We have done the detailed theoretical investigation by performing calculations for numerous LaAlO(3)/SrTiO(3) heterostructures using the generalized gradient approximation. We find that external electric field can cooperate or compete with spontaneous polarization and effectively modulate band dispersion around the Fermi level. Positive field can induce a reversible insulator-metal transition in insulating heterostructures. Rather than the Ti-d(xy) interface state that emerges in insulator-metal transition without external field, the pd-σ anti-bonding state composed of the O-p(z) and the Ti-d(3z(2)-1) at SrTiO(3) surface exchanges its hole with the electron of the O-p(x),p(y) orbitals (bonding states) at LaAlO(3) surface with the presence of positive field. Associated with insulator-metal transition, there is a remarkable change of local work functions in heterostructure, which suggests that LaAlO(3)/SrTiO(3) heterostructures are the promising candidates for novel nanoscale oxide electronic devices and technology, for instance, the Schottky diodes with adjustable barrier height.     

Metallic and insulating interfaces of amorphous SrTiO₃-based oxide heterostructures

The conductance confined at the interface of complex oxide heterostructures provides new opportunities to explore nanoelectronic as well as nanoionic devices. Herein we show that metallic interfaces can be realized in SrTiO(3)-based heterostructures with various insulating overlayers of amorphous LaAlO(3), SrTiO(3), and yttria-stabilized zirconia films. On the other hand, samples of amorphous La(7/8)Sr(1/8)MnO(3) films on SrTiO(3) substrates remain insulating. The interfacial conductivity results from the formation of oxygen vacancies near the interface, suggesting that the redox reactions on the surface of SrTiO(3) substrates play an important role.     

Scanning Probe Manipulation of Magnetism at the LaAlO(3)/SrTiO(3) Heterointerface

Manipulation of magnetism is a longstanding goal of research in exotic materials. In this work, we demonstrate that the small ferromagnetic patches in LaAlO(3)/SrTiO(3) heterostructures can be dramatically changed by in situ contact of a scanning probe. Our results provide a platform for manipulation of small magnets through either a strong magneto-elastic coupling or sensitivity to surface modification. The ability to locally control magnetism is particularly interesting due to the presence of superconductivity with strong spin-orbit coupling in LaAlO(3)/SrTiO(3).     

Giant thermoelectric Seebeck coefficient of a two-dimensional electron gas in SrTiO3

Enhancement of the Seebeck coefficient (S ) without reducing the electrical conductivity (sigma) is essential to realize practical thermoelectric materials exhibiting a dimensionless figure of merit (ZT=S2 x sigma x T x kappa-1) exceeding 2, where T is the absolute temperature and kappa is the thermal conductivity. Here, we demonstrate that a high-density two-dimensional electron gas (2DEG) confined within a unit cell layer thickness in SrTiO(3) yields unusually large |S|, approximately five times larger than that of SrTiO(3) bulks, while maintaining a high sigma2DEG. In the best case, we observe |S|=850 microV K-1 and sigma2DEG=1.4 x 10(3) S cm-1. In addition, by using the kappa of bulk single-crystal SrTiO(3) at room temperature, we estimate ZT approximately 2.4 for the 2DEG, corresponding to ZT approximately 0.24 for a complete device having the 2DEG as the active region. The present approach using a 2DEG provides a new route to realize practical thermoelectric materials without the use of toxic heavy elements.     

Creation and control of a two-dimensional electron liquid at the bare SrTiO3 surface

Many-body interactions in transition-metal oxides give rise to a wide range of functional properties, such as high-temperature superconductivity, colossal magnetoresistance or multiferroicity . The seminal recent discovery of a two-dimensional electron gas (2DEG) at the interface of the insulating oxides LaAlO(3) and SrTiO(3) (ref. 4) represents an important milestone towards exploiting such properties in all-oxide devices. This conducting interface shows a number of appealing properties, including a high electron mobility, superconductivity and large magnetoresistance, and can be patterned on the few-nanometre length scale. However, the microscopic origin of the interface 2DEG is poorly understood. Here, we show that a similar 2DEG, with an electron density as large as 8×10(13) cm(-2), can be formed at the bare SrTiO(3) surface. Furthermore, we find that the 2DEG density can be controlled through exposure of the surface to intense ultraviolet light. Subsequent angle-resolved photoemission spectroscopy measurements reveal an unusual coexistence of a light quasiparticle mass and signatures of strong many-body interactions.     

Nanoscale control of an interfacial metal-insulator transition at room temperature

Experimental and theoretical investigations have demonstrated that a quasi-two-dimensional electron gas (q-2DEG) can form at the interface between two insulators: non-polar SrTiO3 and polar LaTiO3 (ref. 2), LaAlO3 (refs 3-5), KTaO3 (ref. 7) or LaVO3 (ref. 6). Electronically, the situation is analogous to the q-2DEGs formed in semiconductor heterostructures by modulation doping. LaAlO3/SrTiO3 heterostructures have recently been shown to exhibit a hysteretic electric-field-induced metal-insulator quantum phase transition for LaAlO3 thicknesses of 3 unit cells. Here, we report the creation and erasure of nanoscale conducting regions at the interface between two insulating oxides, LaAlO3 and SrTiO3. Using voltages applied by a conducting atomic force microscope (AFM) probe, the buried LaAlO3/SrTiO3 interface is locally and reversibly switched between insulating and conducting states. Persistent field effects are observed using the AFM probe as a gate. Patterning of conducting lines with widths of approximately 3 nm, as well as arrays of conducting islands with densities >10(14) inch(-2), is demonstrated. The patterned structures are stable for >24 h at room temperature.     

新型脉冲激光能量计用无铅(Na_(1-x)K_x)_(0.5)Bi_(0.5)TiO_3铁电薄膜的制备及其激光感生热电电压信号的研究

采用脉冲激光沉积(PLD)技术,分别在LaA lO3(LAO)、(La,Sr)(A l,Ta)O3(LAST)及SrTiO3(STO)三种不同的单晶衬底上制备了一系列无铅(Na1-xKx)0.5B i0.5TiO3(x=0.00,0.08,0.19,0.30,NKBT)铁电薄膜材料。利用X射线衍射(XRD)仪对薄膜结构进行了分析,结果表明在单晶平衬底上生长的薄膜都是单取向生长的外延膜,其中摇摆曲线的半高宽(FWHM)显示在(La,Sr)(A l,Ta)O3单晶衬底上生长的薄膜结晶质量最好。另外,在20°倾斜的(La,Sr)(A l,Ta)O3单晶衬底上生长的(Na1-xKx)0.5B i0.5TiO3铁电薄膜中还首次观察到了激光感生热电电压(LITV)信号。发现在能量为0.48mJ/pulse的紫外脉冲激光辐照下,其最大激光感生热电电压为31mV,完全满足了制作脉冲激光能量计探测元件的要求,有望开发出可集成的新型脉冲激光能量计。     

LaAlO_3顶层对Pb(Zr,Ti)O_3薄膜微结构和性能的影响

利用脉冲激光沉积(PLD)法,在LaAlO3(LAO)基片上外延生长了高质量的PbZr0.52Ti0.48O3(PZT)薄膜。通过增加10nm厚的LAO顶层,所制备PZT薄膜的铁电剩余极化(Pr)由28.8μC/cm2增加为55.1μC/cm2。通过对微结构分析,表明薄膜电学性能的增强主要来源于LAO顶层对PZT薄膜表面形貌的优化。另外,与Pr不同,随LAO顶层厚度的增加,PZT薄膜的矫顽场单调增加。     

High-Mobility 2D Hole Gas at a SrTiO3 Interface

Strontium titanate (SrTiO₃ or STO) is important for oxide-based electronics as it serves as a standard substrate for a wide range of high-temperature superconducting cuprates, colossal magnetoresistive manganites, and multiferroics. Moreover, in its heterostructures with different materials, STO exhibits a broad spectrum of important physics such as superconductivity, magnetism, the quantum Hall effect, giant thermoelectric effect, and colossal ionic conductivity, most of which emerge in a two-dimensional (2D) electron gas (2DEG) formed at an STO interface. However, little is known about its counterpart system, a 2D hole gas (2DHG) at the STO interface. Here, a simple way of realizing a 2DHG with an ultrahigh mobility of 24 000 cm² V⁻¹ s⁻¹ is demonstrated using an interface between STO and a thin amorphous FeO_y layer, made by depositing a sub-nanometer-thick Fe layer on an STO substrate at room temperature. This mobility is the highest among those reported for holes in oxides. The carrier type can be switched from p-type (2DHG) to n-type (2DEG) by controlling the Fe thickness. This unprecedented method of forming a 2DHG at an STO interface provides a pathway to unexplored hole-related physics in this system and enables extremely low-cost and high-speed oxide electronics.     

Electronically coupled complementary interfaces between perovskite band insulators

Perovskite oxides exhibit a plethora of exceptional properties, providing the basis for novel concepts of oxide-electronic devices. The interest in these materials is even extended by the remarkable characteristics of their interfaces. Studies on single epitaxial connections between the wide-bandgap insulators LaAlO3 and SrTiO3 have revealed them to be either high-mobility electron conductors or insulating, depending on the atomic stacking sequences. For device applications, as well as for a basic understanding of the interface conduction mechanism, it is important to investigate the electronic coupling of closely spaced complementary interfaces. Here we report the successful realization of such coupled interfaces in SrTiO3-LaAlO3 thin-film multilayer structures. We found a critical separation distance of six perovskite unit cell layers, corresponding to approximately 23 A, below which a decrease of the interface conductivity and carrier density occurs. Interestingly, the high carrier mobilities characterizing the separate conducting interfaces are found to be maintained in coupled structures down to subnanometre interface spacing.     

GaN基底上集成介电薄膜材料的生长方法研究

将以极化为特征、具有丰富功能特性的介电氧化物材料通过外延薄膜的方式,在半导体GaN上制备介电氧化物/GaN集成薄膜,其多功能一体化与界面耦合效应可推动电子系统单片集成化的进一步发展。然而,由于2类材料物理、化学性质的巨大差异,在GaN上生长介电薄膜会出现严重的相容性生长问题。采用激光分子束外延技术(LMBE),通过弹性应变的TiO2的缓冲层来减小晶格失配度,降低介电薄膜生长温度,控制界面应变释放而产生的失配位错,提高了介电薄膜外延质量;通过低温外延生长MgO阻挡层,形成稳定的氧化物/GaN界面,阻挡后续高温生长产生的扩散反应;最终采用TiO2/MgO组合缓冲层控制介电/GaN集成薄膜生长取向、界面扩散,降低集成薄膜的界面态密度,保护GaN半导体材料的性能。所建立的界面可控的相容性生长方法,为相关集成器件的研发提供了一条可行的新途径。     

Enhanced Acousto-Optic Diffraction Efficiency in a Symmetric SrTiO(3)/BaTiO(3)/SrTiO(3) Thin-Film Heterostructure

Guided-wave acousto-optic Bragg diffraction and surface acoustic-wave propagation in epitaxially matched SrTiO(3)/BaTiO(3)(001)/SrTiO(3) thin-film heterostructures have been theoretically studied. The optimum electromechanical coupling and Bragg diffraction efficiency have been determined at several acoustic frequencies by means of varying the thickness of the SrTiO(3) overlayer and the BaTiO(3) waveguiding layer. A strain-controlling nonpiezoelectric SrTiO(3) overlayer upon the BaTiO(3)/SrTiO(3) structure is found to enhance the coupling coefficient (k(2)) and the diffraction efficiency significantly. A comparison of asymmetric and symmetric structures shows an increase in the diffraction efficiency from 10.5% to 43.0% and a decrease in the untuned-transducer conversion efficiency from 36 to 23 dB at an operating frequency of 1 GHz with an interaction length of 1 mm and an acoustic power of 1 mW.     

Electronic effects in manganite/insulator interfaces: interfacial enhancement of the insulating tunneling barriers

The transport properties across perovskite oxides heterointerfaces are analyzed. Epitaxial La(2/3)Ca(1/3)MnO3/SrTiO3 (LCMO/STO) heterostructures with different STO insulating-barrier thicknesses are systematically investigated and their behavior compared with LCMO/metal junctions. Atomic force microscopy (AFM) measurements in current-sensing mode show typical features associated with tunneling conduction. Careful analysis of the I-V curves across LCMO/STO heterointerfaces, using the Simmons model in the intermediate voltage range, clearly shows the existence of an interface-induced enhancement of the tunneling barrier of about 1.6 nm on the LCMO side. These results confirm recent theoretical studies predicting electronic phase segregation and the formation of an orbital-ordered insulating phase at the manganite-insulator interface that is a result of the reduction in the number of charge carriers at the interface.     

铁磁(La0.7Ca0.3MnO3)/高温超导（YBa2Cu3O7）双层薄膜微结构的高分辨电镜研究

采用脉冲激光沉积法在LaAlO3(LAO)衬底上生长了YBa2Cu3O7/La0.7Ca0.3MnO3(YBCO/LC-MO)和La0.7Ca0.3MnO3/YBa2Cu3O7(LCMO/YBCO)两种外延薄膜,利用高分辨电子显微镜研究了其微观结构。在YBCO/LCMO/LAO薄膜中,LCMO以层-岛模式生长,并形成层状取向畴结构。YBCO层均由c轴取向晶粒组成,其中含有c/3平移畴界、额外CuO层及Y2O3第二相等缺陷结构。在LCMO/YBCO/LAO薄膜中,LAO衬底上初始生长的YBCO为c轴取向,至一定厚度(几个纳米)转为c与a轴混合生长。LCMO层在YBCO上外延生长并具有[100]m与[011]m混合取向畴结构。在LCMO/YBCO界面未观察到失配位错,因此二者界面属应变型界面。     

Low-noise solar-blind photodetectors based on LaAlO3 single crystal with transparent indium-tin-oxide electrode as detection window

The low-noise solar-blind photodetectors of indium-tin-oxide/LaAlO(3)/Ag (ITO/LAO/Ag) have been fabricated based on the properties of LAO bandgap excitation and the transparent conductance of ITO thin film. The ITO thin films are epitaxially grown on LAO wafers as the electrodes and detection windows of the photodetectors. The photodetectors have low noise and excellent electromagnetic shielding. The influence of the thickness of ITO thin films on the responsivity of the photodetectors has been studied. The photocurrent responsivity can reach 10.3 mA/W under the irradiation of 200-220 nm for a photodetector with 5 nm thick ITO film. The noise current is 1 pA order magnitude under the sunlight at midday. The experiment results suggest that ITO/LAO/Ag is one of the promising structures for the solar-blind deep-ultraviolet photodetectors.     

Electronic structure, electron field emission and magnetic behaviors of carbon nanotubes fabricated on La0.66Sr0.33MnO3 (LSMO) for spintronics application

This work elucidates the electronic structure, electron field emission and magnetic anisotropic behaviors of single wall carbon nanotubes (SWCNTs) for the spin-electronics device application grown on the La0.66Sr0.33MnO3 (LSMO)/SrTiO3 (STO) substrate. Micro-Raman spectroscopy, X-ray absorption near-edge structure (XANES) and valence-band photoemission spectroscopy (VBPES) were used for the study of electronics structure. The field emission characteristics were studied from the electron field emission current density (J) versus applied electric field (E(A)) from which the turn-on electric field (E(TOE)) was evaluated. The magnetization behaviors are also presented by the M-H hysteresis loop and were obtained by applying the magnetic field in the parallel and perpendicular direction of the CNTs at 305 K and 5 K temperatures. A magnetic measurement shows that the coercivity of the CNTs/LSMO/STO is higher and has hig anisotropic-nature than the composite LSMO/STO that could be the good material for the future possible spin-electronics device applications.