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Functional oxides are an untapped resource for futuristic devices and functionalities. These functionalities can range from high temperature superconductivity to multiferroicity and novel catalytic schemes. The most prominent route for transforming these ideas from a single device in the lab to practical technologies is by integration with semiconductors. Moreover, coupling oxides with semiconductors can herald new and unexpected functionalities that exist in neither of the individual materials. Therefore, oxide epitaxy on semiconductors provides a materials platform for novel device technologies. As oxides and semiconductors exhibit properties that are complementary to one another, epitaxial heterostructures comprised of the two are uniquely poised to deliver rich functionalities. This review discusses recent advancements in the growth of epitaxial oxides on semiconductors, and the electronic and physical structure of their interfaces. Leaning on these fundamentals and practicalities, the material behavior and functionality of semiconductor–oxide heterostructures is discussed, and their potential as device building blocks is highlighted. The culmination of this discussion is a review of recent advances in the development of prototype devices based on semiconductor–oxide heterostructures, in areas ranging from silicon photonics to photocatalysis. This overview is intended to stimulate ideas for new concepts of functional devices and lay the groundwork for their realization.  相似文献   

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The annealing behavior of Ge native oxides has been studied with x-ray photoemission spectroscopy (XPS). The native oxides were primarily GeO2 with small amounts of GeOx (x<2). Annealing was performed using a rapid thermal processor (RTP) with a N2 purge at atmospheric pressure. Ion-implanted Ge substrates were used to investigate the loss of Ge from the surface due to thermal desorption of Ge oxides. It was found that thermal desorption of volatile Ge oxides and oxidization of Ge take place successively, which results in the loss of Ge from the surface.  相似文献   

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Integration of crystalline oxides with silicon provides a versatile platform to extend and advance silicon technology. The interface between oxide and Si controls the structure and functional properties of the resulting material. In particular, the formation of a submonolayer metal phase on silicon is the standard approach to stabilize the epitaxial growth of oxides. However, fundamental questions—a) whether the interface transforms in the process of the synthesis; and b) if it is possible to control the interface and its electronic structure by varying the submonolayer template—remain unanswered. The present study employs MBE synthesis of EuO and SrO on Si(001) to demonstrate that the structure of the oxide/Si interface does not depend on the type of the template, its symmetry, and stoichiometry. Chemical transformations of the templates converging into the same 2D product are detected in situ by electron diffraction. Then, the common interfacial structure of 1D periodicity is visualized by high-resolution electron microscopy. The study provides insights into the process of oxide integration with silicon but also sets the limits in designing oxide/Si interfaces.  相似文献   

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Doping of organic semiconductors (OSCs) with transition metal oxides such as molybdenum trioxide (MoO3) has been used as a powerful method to overcome common issues such as contact resistance and low conductivity, which are limiting factors in organic optoelectronic devices. In this study, the mechanism and efficiency of MoO3‐induced p‐type doping in OSCs are investigated by means of simultaneous electrical and spectroscopic measurements on lateral diodes. It is demonstrated that energetic changes in the MoO3 energy levels outside vacuum can limit charge‐transfer doping and device performance. It is shown and investigated that these changes crucially depend on the OSC. The time evolution of important OSC parameters such as induced charge density, doping concentration and efficiency, conductivity and mobility, is deduced. Moreover, the energetic and chemical changes in MoO3 are investigated via ultraviolet and x‐ray photoemission spectroscopy. Combining these experiments, important conclusions are drawn on the time‐dependence and stability of MoO3‐doping of OSCs, as well as on the processing conditions and device architectures suitable for high‐performance devices.  相似文献   

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The electronic structure of a semiconducting mixed-stack charge transfer (CT) complex composed of a 2,7-dialkyl[1]benzothieno[3,2-b][1] benzothiophene (diC8-BTBT) electron donor and a tetracyanoquinodimethane (TCNQ) electron acceptor, (diC8-BTBT)(TCNQ), was studied by ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. Compared with its components, the frontier electronic states observed for the (diC8-BTBT)(TCNQ) complex showed a large stabilization that originates from the reconstruction of electronic states by intermolecular donor-acceptor CT interactions. We discuss how the frontier electronic states of the complex are formed from those of the individual component molecules, and clarify the origin of the air-stable n-type organic field-effect transistor characteristics that the material exhibits when it is used as a channel semiconductor.  相似文献   

7.
We report a low-resistance ohmic contact on undoped ZnO using a promising contact scheme of Ti/Al. Specific-contact resistivity, as low as 9.0 × 10?7 ωcm2, was obtained from the Ti (300 Å)/Al (3,000 Å) contact annealed at 300°C. It was found that TiO was produced, and the atomic ratio of Zn/O was dramatically increased after annealing at 300°C. This provides the evidence that a number of oxygen vacancies, acting as donors for electrons, were produced below the contact. This leads to the increase of electron concentration via the reduction of contact resistivity.  相似文献   

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The interfacial electronic structure between oxide thin films and organic semiconductors remains a key parameter for optimum functionality and performance of next‐generation organic/hybrid electronics. By tailoring defect concentrations in transparent conductive ZnO films, we demonstrate the importance of controlling the electron transfer barrier at the interface with organic acceptor molecules such as C60. A combination of electron spectroscopy, density functional theory computations, and device characterization is used to determine band alignment and electron injection barriers. Extensive experimental and first principles calculations reveal the controllable formation of hybridized interface states and charge transfer between shallow donor defects in the oxide layer and the molecular adsorbate. Importantly, it is shown that removal of shallow donor intragap states causes a larger barrier for electron injection. Thus, hybrid interface states constitute an important gateway for nearly barrier‐free charge carrier injection. These findings open new avenues to understand and tailor interfaces between organic semiconductors and transparent oxides, of critical importance for novel optoelectronic devices and applications in energy‐conversion and sensor technologies.  相似文献   

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Silicene, a new 2D material has attracted intense research because of the ubiquitous use of silicon in modern technology. However, producing free-standing silicene has proved to be a huge challenge. Until now, silicene could be synthesized only on metal surfaces where it naturally forms strong interactions with the metal substrate that modify its electronic properties. Here, the authors report the first experimental evidence of silicene nanoribbons on an insulating NaCl thin film. This work represents a major breakthrough, for the study of the intrinsic properties of silicene, and by extension to other 2D materials that have so far only been grown on metal surfaces.  相似文献   

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Surfaces with extreme wetting properties are useful for the collection, manipulation, transport, and avoidance of aqueous and organic fluids of commercial and strategic importance. Two major obstacles to the deployment of synthetic non‐wetting materials in practical scenarios are their lack of mechanical durability and their susceptibility to fouling in contaminated or chemically complex media. Here, crosslinked and nanoporous polymer multilayers are reported that overcome these limitations and exhibit robust and tunable “underwater superoleophobicity”, or the ability to almost completely prevent contact with oils and other organic fluids when submerged in water. These entirely organic coatings mimic key chemical and structural features found on the scales of fish and other natural anti‐oil‐fouling surfaces, and are remarkably tolerant to physical, chemical, and environmental insults commonly encountered in natural and synthetic aqueous environments. This approach also permits facile manipulation and patterning of surface chemistry and, thus, tunable spatial control over other important aspects of interfacial behavior, such as underwater oil adhesiveness, that extend and expand the potential utility of synthetic anti‐oil‐fouling surfaces in aqueous, aquatic, and marine environments.  相似文献   

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The electronic properties of digital superlattices are reported, which are cation‐ordered analogs of the perovskite La1/3Sr2/3FeO3, a material that undergoes a charge‐ordering transition. Superlattices of LaFeO3 (LFO), an antiferromagnetic insulator, and SrFeO3 (SFO), a conductor with a helical magnetic ground state, are fabricated via oxide molecular beam epitaxy. Three isocompositional superlattices with repeat structures of SSLSSL (S2), SSSLSL (S3), and SSSSLL (S4) (S = SFO, L = LFO) are studied with cation orderings along the [001] and [111] directions for experimental and computational work, respectively. The experimental superlattice structures are confirmed via synchrotron X‐ray diffraction and corresponding simulations of (00L) crystal truncation rods. The S2 and S3 superlattices are found to undergo an electronic phase transition as measured by a discontinuity in the temperature‐dependent resistivity similar to the random alloy, indicating that the superlattices do not behave as a simple combination of LFO and SFO. The charge‐ordering transition is not observed in the S4 sample. The electronic structure calculations using density functional theory, confirming the energetic favorability of charge ordering in the S2 and S3 structures compared to the S4 structure, are consistent with experimental trends.  相似文献   

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Understanding the effects of X-rays on halide perovskite thin films is critical for accurate and reliable characterization of this class of materials, as well as their use in detection systems. In this study, advanced optical imaging techniques are employed, both spectrally and temporally resolved, coupled with chemical characterizations to obtain a comprehensive picture of the degradation mechanism occurring in the material during photoemission spectroscopy measurements. Two main degradation pathways are identified through the use of local correlative physico-chemical analysis. The first one, at low X-Ray fluence, shows minor changes of the surface chemistry and composition associated with the formation of electronic defects. Moreover, a second degradation route occurring at higher fluence leads to the evaporation of the organic cations and the formation of an iodine-poor perovskite. Based on the local variation of the optoelectronic properties, a kinetic model describing the different mechanisms is proposed. These findings provide valuable insight on the impact of X-rays on the perovskite layers during investigations using X-ray based techniques. More generally, a deep understanding of the interaction mechanism of X-rays with perovskite thin films is essential for the development of perovskite-based X-ray detectors and solar for space applications.  相似文献   

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Here we report investigation of valence band electronic states of ferromagnetic Ga0.96Mn0.04N by bulk-sensitive X-ray photoemission, which is realized at high flux X-ray undulator beamline BL29XU of SPring-8, at photon energy of 5.95 keV. We have observed that Mn doping introduces a new structure in the band gap region near the top of the valence band, and also a broader structure in deeper valence band region. Basing upon the first principle calculation, these structures are assigned as Ga 4s originated states, which are raised by hybridization between 3d orbitals of Mn with GaN host orbitals. The present result evidences the second nearest Ga bonds are affected by that Mn–N bond formation, suggesting the long-range interaction of Mn in this host material.  相似文献   

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Despite the striking increase in the power conversion efficiency (PCE) of lead-based perovskite solar cells (PSCs), their poor operational stability impedes their commercialization. Among the various factors that influence device stability, ion migration has been identified as a key driver of degradation. In this work, the focus is on studying ion migration-induced degradation in inverted architecture PSCs, which employ either a thin polymer layer or a self-assembled monolayer (SAM) for hole extraction. It is demonstrated that the difference in texture imposed by the use of these hole transport layers (HTL) is an important and thus far inconspicuous factor that impacts ion migration, and consequently device stability. By investigating the buried interface in detail, it is revealed that its texture has a strong impact on the vertical compositional stratification in the perovskite active layer. By monitoring bias-induced ion migration in devices with different hole extraction layers, it is demonstrated that the smooth polymer-based HTL results in a higher degree of ion migration than the rough SAM HTL, corresponding to a stronger degradation in the former. These results further indicate that the use of SAMs for hole extraction is a promising strategy to suppress ion migration and improve device efficiency.  相似文献   

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A chemical approach to controlling the work function of few‐layer graphene is investigated. Graphene films are synthesized on Cu foil by chemical vapor deposition. Six metal chlorides, AuCl3, IrCl3, MoCl3, OsCl3, PdCl2, and RhCl3, are used as dopants. The sheet resistance of the doped graphene decreases from 1100 Ω/sq to ≈500–700 Ω/sq and its transmittance at 550 nm also decreases from 96.7% to 93% for 20 mM AuCl3 due to the formation of metal particles. The sheet resistance and transmittance are reduced with increasing metal chloride concentration. The G peak in the Raman spectra is shifted to a higher wavenumber after metal chloride doping, which indicates a charge transfer from graphene to metal ions. The intensity ratio of IC?C/IC?C increases with doping, indicating an electron transfer from graphene sheets to metal ions. Ultraviolet photoemission spectroscopy data shows that the work function of graphene increases from 4.2 eV to 5.0, 4.9, 4.8, 4.68, 5.0, and 5.14 eV for the graphene with 20 mM AuCl3, IrCl3, MoCl3, OsCl3, PdCl2, and RhCl3, respectively. It is considered that spontaneous charge transfer occurs from the specific energy level of graphene to the metal ions, thus increasing the work function.  相似文献   

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Polydimethylsiloxanes (PDMS) foam as one of next-generation polymer foam materials shows poor surface adhesion and limited functionality, which greatly restricts its potential applications. Fabrication of advanced PDMS foam materials with multiple functionalities remains a critical challenge. In this study, unprecedented self-adhesive PDMS foam materials are reported with worm-like rough structure and reactive groups for fabricating multifunctional PDMS foam nanocomposites decorated with MXene/cellulose nanofiber (MXene/CNF) interconnected network by a facile silicone foaming and dip-coating strategy followed by silane surface modification. Interestingly, such self-adhesive PDMS foam produces strong interfacial adhesion with the hybrid MXene/CNF nano-coatings. Consequently, the optimized PDMS foam nanocomposites have excellent surface super-hydrophobicity (water contact angle of ≈159o), tunable electrical conductivity (from 10−8 to 10 S m−1), stable compressive cyclic reliability in both wide-temperature range (from −20 to 200 oC) and complex environments (acid, sodium, and alkali conditions), outstanding flame resistance (LOI value of >27% and low smoke production rate), good thermal insulating performance and reliable strain sensing in various stress modes and complex environmental conditions. It provides a new route for the rational design and development of advanced PDMS foam nanocomposites with versatile multifunctionalities for various promising applications such as intelligent healthcare monitoring and fire-safe thermal insulation.  相似文献   

18.
Although the density of states (DOS) distribution of charge transporting states in an organic semiconductor is vital for device operation, its experimental assessment is not at all straightforward. In this work, the technique of energy resolved–electrochemical impedance spectroscopy (ER-EIS) is employed to determine the DOS distributions of valence (highest occupied molecular orbital (HOMO)) as well as electron (lowest unoccupied molecular orbital (LUMO)) states in several organic semiconductors in the form of neat and blended films. In all cases, the core of the inferred DOS distributions are Gaussians that sometimes carry low energy tails. A comparison of the HOMO and LUMO DOS of P3HT inferred from ER-EIS and photoemission (PE) or inverse PE (IPE) spectroscopy indicates that the PE/IPE spectra are by a factor of 2–3 broader than the ER-EIS spectra, implying that they overestimate the width of the distributions. A comparison of neat films of MeLPPP and SF-PDI2 or PC(61)BM with corresponding blends reveals an increased width of the DOS in the blends. The results demonstrate that this technique does not only allow mapping the DOS distributions over five orders of magnitude and over a wide energy window of 7 eV, but can also delineate changes that occur upon blending.  相似文献   

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The correlated metal SrVO3 is an attractive earth‐abundant transparent conducting oxide (TCO), a critical component of many optoelectronic and renewable energy devices. A key challenge is to synthesize films with low resistivity, due to the prevalence of defects that cause electron scattering. In addition to the material's promise as a TCO, its interesting correlated‐electron physics is often obscured by a high defect concentration, which inhibits its further development into new types of devices. A route to synthesize low‐defect SrVO3 films by scalable, industry‐compatible molecular beam epitaxy (MBE) is demonstrated. The resulting films consistently exhibit a residual resistivity ratio in the excess of 10 and room temperature resistivity as low as 32 µΩ cm, an indication of their high quality and potential for applications. Analysis of the structural and electronic properties of SrVO3 films provides insights that are applicable to other conductive oxides, and highlights a route for further improvement in their quality and low temperature performance. MBE is the only growth method that allows atomically abrupt epitaxial interfaces between oxides and semiconductors such as Si and GaAs. Such interfaces are essential for efficient charge transport that is at the heart of the performance of most optoelectronic and solar devices.  相似文献   

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Morphology reshaping or reconfiguration, a concept widely used in plastic surgery, energy harvesting, and reconfigurable robots, is introduced for the first time to construct densified electrodes and realize compact Li‐ion storage desirable for high specific energy storage field. Hausmannite‐based hybrid materials, as a proof‐of‐concept prototype, engineered by 1‐methyl‐2‐pyrrolidinone‐soluble surface/interface organic encapsulation, which is crucial in reshaping, exhibit a remarkable increase in the volumetric capacity of more than five times after this process (≈1889 Ah L?1 vs ≈322 Ah L?1). With the simultaneous maintenance of the intrinsic nature, good contact, and no collapsed/agglomerated unit structures of the materials in electrodes, the design affords a maximal increase in the packing compactness and manifests no sacrifice of the reversible ion storage capability (1150 mAh g?1 at 40 mA g?1), stable cycling (≈100% capacity retention), high rate performance (185 mAh g?1 at 10 A g?1), and long lifespan (1000 cycles with 108% capacity retention, ≈455 mAh g?1 at 3 A g?1) for relatively highly loaded electrodes (active materials: 1.20–5.34 mg cm?2). The concept may not only shed new light on fabricating advanced Si‐based and other high capacity–related densified Li storage electrodes but also inject fresh vitality into the field of high‐density power sources.  相似文献   

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