Synergetic Behavior in 2D Layered Material/Complex Oxide Heterostructures

The marriage between a 2D layered material (2DLM) and a complex transition metal oxide (TMO) results in a variety of physical and chemical phenomena that cannot be achieved in either material alone. Interesting recent discoveries in systems such as graphene/SrTiO₃, graphene/LaAlO₃/SrTiO₃, graphene/ferroelectric oxide, MoS₂/SrTiO₃, and FeSe/SrTiO₃ heterostructures include voltage scaling in field‐effect transistors, charge state coupling across an interface, quantum conductance probing of the electrochemical activity, novel memory functions based on charge traps, and greatly enhanced superconductivity. In this context, various properties and functionalities appearing in numerous different 2DLM/TMO heterostructure systems are reviewed. The results imply that the multidimensional heterostructure approach based on the disparate material systems leads to an entirely new platform for the study of condensed matter physics and materials science. The heterostructures are also highly relevant technologically as each constituent material is a promising candidate for next‐generation optoelectronic devices.     

Structural and Electronic Properties of BaO/MgO(001)-type Interface Studied via Aberration-corrected Transmission Electron Microscopy and First-principles Calculations

The properties of BaO/MgO-type interface in the BaZrO3/MgO(001) heterostructure are studied by aberrationcorrected high-resolution transmission electron microscopy combined with first-principles calculations.Experimental evidence demonstrates that cation displacement and vacancies occur at the interface. Our firstprinciple calculations show that cation displacement results from the electrostatic potential effect at the interface,and cation vacancies could lower the interfacial work of separation and enhance the interfacial stability of BaO/MgO-type interface. The results highlight that the effect of interfacial defects should be taken into account in understanding the film growth kinetics and properties in oxide heteroepitaxy.     

Formation of Heteroepitaxy in Different Shapes of Au–CdSe Metal–Semiconductor Hybrid Nanostructures

Formation of heteroepitaxy and designing different‐shaped heterostructured nanomaterials of metal and semiconductor in solution remains a frontier area of research. However, it is evident that the synthesis of such materials is not straightforward and needs a selective approach to retain both metal and semiconductor identities in the reaction system during heterostructure formation. Herein, the epitaxial growth of semiconductor CdSe on selected facets of metal Au seeds is reported and different shapes (flower, tetrapod, and core/shell) hetero‐nanostructures are designed. These results are achieved by controlling the reaction parameters, and by changing the sequence and timing for introduction of different reactant precursors. Direct evidence of the formation of heteroepitaxy between {111} facets of Au and (0001) of wurtzite CdSe is observed during the formation of these three heterostructures. The mechanism of the evolution of these hetero‐nanostructures and formation of their heteroepitaxy with the planes having minimum lattice mismatch are also discussed. This shape‐control growth mechanism in hetero‐nanostructures should be helpful to provide more information for establishing the fundamental study of heteroepitaxial growth for designing new nanomaterials. Such metal–semiconductor nanostructures may have great potential for nonlinear optical properties, in photovoltaic devices, and as chemical sensors.     

Rational Kinetics Control toward Universal Growth of 2D Vertically Stacked Heterostructures

The rational control of the nucleation and growth kinetics to enable the growth of 2D vertical heterostructure remains a great challenge. Here, an in‐depth study is provided toward understanding the growth mechanism of transition metal dichalcogenides (TMDCs) vertical heterostructures in terms of the nucleation and kinetics, where active clusters with a high diffusion barrier will induce the nucleation on top of the TMDC templates to realize vertical heterostructures. Based on this mechanism, in the experiment, through rational control of the metal/chalcogenide ratio in the vapor precursors, effective manipulation of the diffusion barrier of the active clusters and precise control of the heteroepitaxy direction are realized. In this way, a family of vertical TMDCs heterostructures is successfully designed. Optical studies and scanning transmission electron microscopy investigations exhibit that the resulting heterostructures possess atomic sharp interfaces without apparent alloying and defects. This study provides a deep understanding regarding the growth mechanism in terms of the nucleation and kinetics and the robust growth of 2D vertical heterostructures, defining a versatile material platform for fundamental studies and potential device applications.     

Multiferroic Heterostructures Integrating Ferroelectric and Magnetic Materials

Multiferroic heterostructures can be synthesized by integrating monolithic ferroelectric and magnetic materials, with interfacial coupling between electric polarization and magnetization, through the exchange of elastic, electric, and magnetic energy. Although the nature of the interfaces remains to be unraveled, such cross coupling can be utilized to manipulate the magnetization (or polarization) with an electric (or magnetic) field, known as a converse (or direct) magnetoelectric effect. It can be exploited to significantly improve the performance of or/and add new functionalities to many existing or emerging devices such as memory devices, tunable microwave devices, sensors, etc. The exciting technological potential, along with the rich physical phenomena at the interface, has sparked intensive research on multiferroic heterostructures for more than a decade. Here, we summarize the most recent progresses in the fundamental principles and potential applications of the interface‐based magnetoelectric effect in multiferroic heterostructures, and present our perspectives on some key issues that require further study in order to realize their practical device applications.     

Transport at the Epitaxial Interface between Germanium and Functional Oxides

Combining functional oxides with conventional semiconductors provides the potential for transformational advancement of microelectronic devices. Harnessing the full spectrum of oxide functionalities requires current transport between the oxide and the semiconductor. This aspect is addressed by controlling the electronic barrier at an interface between a ferroelectric oxide, BaTiO₃, and germanium. For the aligned conduction bands of germanium and BaTiO₃, as measured by spectroscopy, current transport is controlled by the barrier between the top metal electrode and the bands of the BaTiO₃. Capacitance–voltage analysis of metal–oxide–semiconductor devices further shows that the semiconductor's Fermi level can be moved by a field effect. These results demonstrate a viable approach for electronically bridging the functionalities of oxides directly with a common semiconductor.     

Large-Area Synthesis of Ferromagnetic Fe5−xGeTe2/Graphene van der Waals Heterostructures with Curie Temperature above Room Temperature

Van der Waals (vdW) heterostructures combining layered ferromagnets and other 2D crystals are promising building blocks for the realization of ultracompact devices with integrated magnetic, electronic, and optical functionalities. Their implementation in various technologies depends strongly on the development of a bottom-up scalable synthesis approach allowing for realizing highly uniform heterostructures with well-defined interfaces between different 2D-layered materials. It is also required that each material component of the heterostructure remains functional, which ideally includes ferromagnetic order above room temperature for 2D ferromagnets. Here, it is demonstrated that the large-area growth of Fe_5−xGeTe₂/graphene heterostructures is achieved by vdW epitaxy of Fe_5−xGeTe₂ on epitaxial graphene. Structural characterization confirms the realization of a continuous vdW heterostructure film with a sharp interface between Fe_5−xGeTe₂ and graphene. Magnetic and transport studies reveal that the ferromagnetic order persists well above 300 K with a perpendicular magnetic anisotropy. In addition, epitaxial graphene on SiC(0001) continues to exhibit a high electronic quality. These results represent an important advance beyond nonscalable flake exfoliation and stacking methods, thus marking a crucial step toward the implementation of ferromagnetic 2D materials in practical applications.     

The influence of surface oxide on the growth of metal/semiconductor nanowires

We report the critical effects of oxide on the growth of nanostructures through silicide formation. Under an in situ ultrahigh vacuum transmission electron microscope, it is observed from the conversion of Si nanowires into the metallic PtSi grains epitaxially through controlled reactions between lithographically defined Pt pads and Si nanowires. With oxide, instead of contact area, single crystal PtSi grains start forming either near the center between two adjacent pads or from the ends of Si nanowires, resulting in the heterostructure formation of Si/PtSi/Si. Without oxide, transformation from Si into PtSi begins at the contact area between them, resulting in the heterostructure formation of PtSi/Si/PtSi. The nanowire heterostructures have an atomically sharp interface with epitaxial relationships of Si(20-2)//PtSi(10-1) and Si[111]//PtSi[111]. Additionally, it has been observed that the existence of oxide significantly affects not only the growth position but also the growth behavior and the growth rate by two orders of magnitude. Molecular dynamics simulations have been performed to support our experimental results and the proposed growth mechanisms. In addition to fundamental science, the significance of the study matters for future processing techniques in nanotechnology and related applications as well.     

Nanoscale ferroelectric field-effect writing and reading using scanning tunnelling spectroscopy

Control of the density of mobile charge carriers using electric fields is widely used in a variety of metal-insulator-semiconductor structures and is the governing principle behind the operation of field-effect transistors. Ferroelectric materials possessing a switchable and non-volatile polarization field can be used as insulating layers, revealing new opportunities for device applications. Advances in material processing and in particular complex oxide thin-film growth mean that high-quality field-effect devices can be based on ferroelectric/metallic oxide heterostructures. In addition, advances in local probe techniques such as atomic force microscopy allow them to be used in the imaging and study of small ferroelectric domain structures in bulk crystals and thin films. Meanwhile, scanning tunnelling microscopy and spectroscopy have established themselves as powerful techniques for atomic manipulation and nanometre-resolution electron tunnelling spectroscopy. Here, a scanning tunnelling microscope is used to investigate the ferroelectric field effect in all-perovskite heterostructures. Scanning tunnelling spectroscopy allows us to probe the local electronic properties of the polarized channel of a ferroelectric field-effect device as a function of the field orientation. This technique can be used to read and write ferroelectric field-induced regions with a size as low as 20 nm.     

Interfacial Charge Engineering in Ferroelectric‐Controlled Mott Transistors

Heteroepitaxial coupling at complex oxide interfaces presents a powerful tool for engineering the charge degree of freedom in strongly correlated materials, which can be utilized to achieve tailored functionalities that are inaccessible in the bulk form. Here, the charge‐transfer effect between two strongly correlated oxides, Sm_0.5Nd_0.5NiO₃ (SNNO) and La_0.67Sr_0.33MnO₃ (LSMO), is exploited to realize a giant enhancement of the ferroelectric field effect in a prototype Mott field‐effect transistor. By switching the polarization field of a ferroelectric Pb(Zr,Ti)O₃ (PZT) gate, nonvolatile resistance modulation in the Mott transistors with single‐layer SNNO and bilayer SNNO/LSMO channels is induced. For the same channel thickness, the bilayer channels exhibit up to two orders of magnitude higher resistance‐switching ratio at 300 K, which is attributed to the intricate interplay between the charge screening at the PZT/SNNO interface and the charge transfer at the SNNO/LSMO interface. X‐ray absorption spectroscopy and X‐ray photoelectron spectroscopy studies of SNNO/LSMO heterostructures reveal about 0.1 electron per 2D unit cell transferred between the interfacial Mn and Ni layers, which is corroborated by first‐principles density functional theory calculations. The study points to an effective strategy to design functional complex oxide interfaces for developing high‐performance nanoelectronic and spintronic applications.     

The morphology of axial and branched nanowire heterostructures

We present an extensive investigation of the epitaxial growth of Au-assisted axial heterostructure nanowires composed of group IV and III-V materials and derive a model to explain the overall morphology of such wires. By analogy with 2D epitaxial growth, this model relates the wire morphology (i.e., whether it is kinked or straight) to the relationship of the interface energies between the two materials and the particle. This model suggests that, for any pair of materials, it should be easier to form a straight wire with one interface direction than the other, and we demonstrate this for the material combinations presented here. However, such factors as kinetics and the use of surfactants may permit the growth of straight double heterostructure nanowires. Finally, we demonstrate that branched nanowire heterostructures, also known as nanotrees, can be successfully explained by the same model.     

Growth of straight InAs-on-GaAs nanowire heterostructures

One of the main motivations for the great interest in semiconductor nanowires is the possibility of easily growing advanced heterostructures that might be difficult or even impossible to achieve in thin films. For III-V semiconductor nanowires, axial heterostructures with an interchange of the group III element typically grow straight in only one interface direction. In the case of InAs-GaAs heterostructures, straight nanowire growth has been demonstrated for growth of GaAs on top of InAs, but so far never in the other direction. In this article, we demonstrate the growth of straight axial heterostructures of InAs on top of GaAs. The heterostructure interface is sharp and we observe a dependence on growth parameters closely related to crystal structure as well as a diameter dependence on straight nanowire growth. The results are discussed by means of accurate first principles calculations of the interfacial energies. In addition, the role of the gold seed particle, the effect of its composition at different stages during growth, and its size are discussed in relation to the results observed.     

Ultrahigh‐Sensitive Broadband Photodetectors Based on Dielectric Shielded MoTe2/Graphene/SnS2 p–g–n Junctions

2D atomic sheets of transition metal dichalcogenides (TMDs) have a tremendous potential for next‐generation optoelectronics since they can be stacked layer‐by‐layer to form van der Waals (vdW) heterostructures. This allows not only bypassing difficulties in heteroepitaxy of lattice‐mismatched semiconductors of desired functionalities but also providing a scheme to design new optoelectronics that can surpass the fundamental limitations on their conventional semiconductor counterparts. Herein, a novel 2D h‐BN/p‐MoTe₂/graphene/n‐SnS₂/h‐BN p–g–n junction, fabricated by a layer‐by‐layer dry transfer, demonstrates high‐sensitivity, broadband photodetection at room temperature. The combination of the MoTe₂ and SnS₂ of complementary bandgaps, and the graphene interlayer provides a unique vdW heterostructure with a vertical built‐in electric field for high‐efficiency broadband light absorption, exciton dissociation, and carrier transfer. The graphene interlayer plays a critical role in enhancing sensitivity and broadening the spectral range. An optimized device containing 5?7‐layer graphene has been achieved and shows an extraordinary responsivity exceeding 2600 A W^?1 with fast photoresponse and specific detectivity up to ≈10¹³ Jones in the ultraviolet–visible–near‐infrared spectrum. This result suggests that the vdW p–g–n junctions containing multiple photoactive TMDs can provide a viable approach toward future ultrahigh‐sensitivity and broadband photonic detectors.     

Resistive Switching Behavior in Ferroelectric Heterostructures

Resistive random‐access memory (RRAM) is a promising candidate for next‐generation nonvolatile random‐access memory protocols. The information storage in RRAM is realized by the resistive switching (RS) effect. The RS behavior of ferroelectric heterostructures is mainly controlled by polarization‐dominated and defect‐dominated mechanisms. Under certain conditions, these two mechanisms can have synergistic effects on RS behavior. Therefore, RS performance can be effectively improved by optimizing ferroelectricity, conductivity, and interfacial structures. Many methods have been studied to improve the RS performance of ferroelectric heterostructures. Typical approaches include doping elements into the ferroelectric layer, controlling the oxygen vacancy concentration and optimizing the thickness of the ferroelectric layer, and constructing an insertion layer at the interface. Here, the mechanism of RS behavior in ferroelectric heterostructures is briefly introduced, and the methods used to improve RS performance in recent years are summarized. Finally, existing problems in this field are identified, and future development trends are highlighted.     

Atomic-scale visualization of oxide thin-film surfaces

The interfaces of complex oxide heterostructures exhibit intriguing phenomena not observed in their constituent materials. The oxide thin-film growth of such heterostructures has been successfully controlled with unit-cell precision; however, atomic-scale understandings of oxide thin-film surfaces and interfaces have remained insufficient. We examined, with atomic precision, the surface and electronic structures of oxide thin films and their growth processes using low-temperature scanning tunneling microscopy. Our results reveal that oxide thin-film surface structures are complicated in contrast to the general perception and that atomically ordered surfaces can be achieved with careful attention to the surface preparation. Such atomically ordered oxide thin-film surfaces offer great opportunities not only for investigating the microscopic origins of interfacial phenomena but also for exploring new surface phenomena and for studying the electronic states of complex oxides that are inaccessible using bulk samples.     

Atomic scale characterization of complex oxide interfaces

Complex oxides exhibit the most disparate behaviors, from ferroelectricity to high T _c superconductivity, colossal magnetoresistance to insulating properties. For these reasons, oxide thin films are of interest for electronics and the emerging field of spintronics. But epitaxial complex oxide ultrathin films and heterostructures can be significantly affected or even dominated by the presence of interfaces and may exhibit intriguing new physical properties quite different from the bulk. A study of the relations between structure and chemistry at the atomic scale is needed to understand the macroscopic properties of such “interface-controlled” materials. For this purpose, the combination of aberration-corrected Z-contrast scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) represents a very powerful tool. The availability of sub-Ångström probes allows a level of unprecedented detail when analyzing not only the interface structure with sensitivity to single atoms, but also the interface chemistry. In this work state of the art STEM-EELS will be applied to the study of different oxide interfaces in heterostructures with titanates, manganites and cuprates based on the perovskite structure.     

Electric and Mechanical Switching of Ferroelectric and Resistive States in Semiconducting BaTiO3–δ Films on Silicon

Materials that can couple electrical and mechanical properties constitute a key element of smart actuators, energy harvesters, or many sensing devices. Within this class, functional oxides display specific mesoscale responses which often result in great sensitivity to small external stimuli. Here, a novel combination of molecular beam epitaxy and a water‐based chemical‐solution method is used for the design of mechanically controlled multilevel device integrated on silicon. In particular, the possibility of adding extra functionalities to a ferroelectric oxide heterostructure by n‐doping and nanostructuring a BaTiO₃ thin film on Si(001) is explored. It is found that the ferroelectric polarization can be reversed, and resistive switching can be measured, upon a mechanical load in epitaxial BaTiO_3?δ /La_0.7Sr_0.3MnO₃/SrTiO₃/Si columnar nanostructures. A flexoelectric effect is found, stemming from substantial strain gradients that can be created with moderate loads. Simultaneously, mechanical effects on the local conductivity can be used to modulate a nonvolatile resistive state of the BaTiO_3?δ heterostructure. As a result, three different configurations of the system become accessible on top of the usual voltage reversal of polarization and resistive states.     

Ag/Bi4Ti3O12/p-Si异质结的制备及其C-V特性研究

为制备符合铁电存储器件要求的高质量铁电薄膜,采用溶胶-凝胶(Sol-Gel)工艺,制备了Si基Bi4Ti3O12铁电薄膜及MFS结构的Ag/Bi4Ti3O12/P-Si异质结,对Bi4Ti3O12薄膜的相结构特征及异质结的C-V特性进行了测试与分析.XRD图谱显示,Si基Bi4Ti3O12薄膜具有沿c-轴择优取向生长的趋势,而Ag/Bi4Ti3O12/p-Si异质结顺时针回滞的C-V特性曲线则表明,该异质结可实现电极化存储.此外,对该异质结C-V特性曲线的非对称及向负偏压方向偏移的产生原因也进行了分析.在此基础上,为提高铁电薄膜的铁电性能及改善其C-V特性提出了合理的结构设想.     

Magnetic interaction in the manganite/intermetallic compound heterostructure

We investigate hybrid magnetic heterostructures consisting of thin epitaxial films of oxide ferromagnets La_0.7Sr_0.3MnO₃ and intermetallic superlattices (TeCo₂/FeCo) _n . The magnetic characteristics of the heterostructures were studied by the ferromagnetic resonance and magneto-optical Kerr effect techniques. The interlayer interaction in a heterostructure is shown to be antiferromagnetic. It was established that the interface with the intermetallic compound broadens the ferromagnetic resonance line of the manganite film.     

Growth and interfacial properties of epitaxial oxides on semiconductors: ab initio insights

Crystalline metal oxides display a large number of physical functionalities such as ferroelectricity, magnetism, superconductivity, and Mott transitions. High quality heterostructures involving metal oxides and workhorse semiconductors such as silicon have the potential to open new directions in electronic device design that harness these degrees of freedom for computation or information storage. This review describes how first-principles theoretical modeling has informed current understanding of the growth mechanisms and resulting interfacial structures of crystalline, coherent, and epitaxial metal oxide thin films on semiconductors. Two overarching themes in this general area are addressed. First, the initial steps of oxide growth involve careful preparation of the semiconductor surface to guard against amorphous oxide formation and to create an ordered template for epitaxy. The methods by which this is achieved are reviewed, and possibilities for improving present processes to enable the epitaxial growth of a wider set of oxides are discussed. Second, once a heterointerface is created, the precise interfacial chemical composition and atomic structure is difficult to determine unambiguously from experiment or theory alone. The current understanding of the structure and properties of complex oxide/semiconductor heterostructures is reviewed, and the main challenges to prediction—namely, (i) are these heterostructures in thermodynamic equilibrium or kinetically trapped, and (ii) how do the interfaces modify or couple to the degrees of freedom in the oxide?—are explored in detail for two metal oxide thin films on silicon. Finally, an outlook of where theoretical efforts in this field may be headed in the near future is provided.