Curie Temperatures of III–V Diluted Magnetic Semiconductors Calculated from First-Principles in Mean Field Approximation

Electronic structure and ferromagnetism in III–V compound-based diluted magnetic semiconductors (DMS) are investigated based on first-principles calculations by using the Korringa-Kohn-Rostoker method combined with the coherent-potential-approximation. The stability of the ferromagnetic phase in GaN-, GaAs-, GaP-, GaSb-based DMS is investigated systematically. The calculations show that 3d-impurities from the first-half of the transition metal series favor the ferromagnetic state, while impurities from the latter-half of the series exhibit spin-glass behavior. This chemical trend in the magnetism is explained by the double exchange mechanism taking the local symmetry at the impurity gap states into account. Curie temperatures of GaAs- and GaN-based DMS are estimated by using the Heisenberg model in a mean field approximation with the parameters calculated from first-principles. It is suggested that room-temperature ferromagnetism can be realized in these systems.     

ZnO基稀磁半导体磁性机理研究进展

稀磁半导体是指在非磁性化合物半导体中通过掺杂引入部分磁性离子所形成的一类新型功能材料.目前,稀磁半导体的磁性来源和机理一直是该领域的研究热点,掺杂的磁性离子通过怎样的交换方式实现铁磁性一直存有争议.本文对近几年来ZnO基稀磁半导体磁性机理研究进展作一综述,着重阐述了代表性的RRKY理论、平均场理论、双交换理论和磁极子理论,对实验和理论方面的热点和存在问题作一评价,对磁性理论的研究提出了新思路.     

Electronic structure origins of polarity-dependent high-TC ferromagnetism in oxide-diluted magnetic semiconductors

Future spintronics technologies based on diluted magnetic semiconductors (DMSs) will rely heavily on a sound understanding of the microscopic origins of ferromagnetism in such materials. Discoveries of room-temperature ferromagnetism in wide-bandgap DMSs hold great promise, but this ferromagnetism remains poorly understood. Here we demonstrate a close link between the electronic structures and polarity-dependent high-TC ferromagnetism of TM(2+):ZnO DMSs, where TM(2+) denotes 3d transition metal ions. Trends in ferromagnetism across the 3d series of TM(2+):ZnO DMSs predicted from the energies of donor- and acceptor-type excited states reproduce experimental trends well. These results provide a unified basis for understanding both n- and p-type ferromagnetic oxide DMSs.     

Magnetic two-dimensional systems

Two-dimensional (2D) systems have considerably strengthened their position as one of the premier candidates to become the key material for the proposed spintronics technology, in which computational logic, communications and information storage are all processed by the electron spin. In this article, some of the most representative 2D materials including ferromagnetic metals (FMs) and diluted magnetic semiconductor (DMSs) in their thin film form, magnetic topological insulators (TIs), magnetic graphene and magnetic transition metal dichalcogenides (TMDs) are reviewed for their recent research progresses. FM thin films have spontaneous magnetization and usually high Curie temperature (T_c), though this can be strongly altered when bonded with semiconductors (SCs). DMS and magnetic TIs have the advantage of easy integration with the existing SC-based technologies, but less robust magnetism. Magnetic ordering in graphene and TMDs are even more fragile and limited to cryogenic temperatures so far, but they are particularly interesting topics due to the desired long spin lifetime as well as the outstanding mechanical and optical properties of these materials.     

基于从头算法的TM金属共掺杂的ZnO基稀磁半导体的磁性研究(英文)

本文采用从头计算的方法研究了基于过渡性金属共掺杂Ⅱ-Ⅵ族稀释半导体的磁性和电子结构.并系统的研究了氧化锌基的稀释半导体铁磁态的稳定性和对其材料设计.在所有的共掺杂体系中,发现(Mn,Co),(Co,Ni)和(Mn,Ni)共掺杂体系是铁磁态的,而(Fe,Ni)共掺杂体系是自旋玻璃态.另一方面,Fe-,Co-和Ni掺杂ZnO基系统的稳态是铁磁态.同时,本文研究了ZnO基稀释半导体的载流子传导铁磁性,计算分析了电子态密度,铁磁态的稳定性.结合双交换和超交换理论解释共掺杂稀释半导体的磁性机理.     

Ferromagnetic transition metal implanted ZnO: A diluted magnetic semiconductor?

Recent theoretical works have predicted that some semiconductors (e.g. ZnO) doped with magnetic ions are diluted magnetic semiconductors (DMS). In DMS, magnetic ions substitute cation sites of the host semiconductor and are coupled by free carriers, resulting in ferromagnetism. One of the main obstacles in creating DMS materials is the formation of secondary phases because of the solid–solubility limit of magnetic ions in semiconductor hosts. In our study transition metal ions were implanted into ZnO single crystals with the peak concentrations of 0.5–10 at.%. We established a correlation between structural and magnetic properties. By synchrotron radiation X-ray diffraction (XRD) secondary phases (Fe, Ni, Co and ferrite nanocrystals) were observed and have been identified as the source for ferromagnetism. Due to their different crystallographic orientation with respect to the host crystal, these nanocrystals in some cases are very difficult to be detected by a simple Bragg–Brentano scan. This results in the pitfall of using XRD to exclude secondary phase formation in DMS materials. For comparison, the solubility of Co diluted in ZnO films ranges between 10 and 40 at.% using different growth conditions pulsed laser deposition. Such diluted, Co-doped ZnO films show paramagnetic behavior. However, only the magnetoresistance of Co-doped ZnO films reveals possible s–d exchange interaction as compared to Co-implanted ZnO single crystals.     

New semiconductor materials for magnetoelectronics at room temperature

Most of the semiconductor materials are diamagnetic by nature and therefore cannot take active part in the operation of the magneto electronic devices. In order to enable them to be useful for such devices a recent effort has been made to develop diluted magnetic semiconductors (DMS) in which small quantity of magnetic ion is introduced into normal semiconductors. The first known such DMS are II-VI and III-V semiconductors diluted with magnetic ions like Mn, Fe, Co, Ni, etc. Most of these DMS exhibit very high electron and hole mobility and thus useful for high speed electronic devices. The recent DMS materials reported are (CdMn)Te, (GaMn)As, (GaMn)Sb, ZnMn(or Co)O, TiMn(or Co)O etc. They have been produced as thin films by MBE and other methods. This paper will discuss the details of the growth and properties of the DMS materials and some of their applications.     

Ferroelectric polymer gates for non-volatile field effect control of ferromagnetism in (Ga, Mn)As layers

(Ga, Mn)As and other diluted magnetic semiconductors (DMS) attract a great deal of attention for potential spintronic applications because of the possibility of controlling the magnetic properties via electrical gating. Integration of a ferroelectric gate on the DMS channel adds to the system a non-volatile memory functionality and permits nanopatterning via the polarization domain engineering. This topical review is focused on the multiferroic system, where the ferromagnetism in the (Ga, Mn)As DMS channel is controlled by the non-volatile field effect of the spontaneous polarization. Use of ferroelectric polymer gates in such heterostructures offers a viable alternative to the traditional oxide ferroelectrics generally incompatible with DMS. Here we review the proof-of-concept experiments demonstrating the ferroelectric control of ferromagnetism, analyze the performance issues of the ferroelectric gates and discuss prospects for further development of the ferroelectric/DMS heterostructures toward the multiferroic field effect transistor.     

Defects-Driven Ferromagnetism in Undoped Dilute Magnetic Oxides:A Review

In the past several decades, dilute magnetic semiconductors, particularly the dilute magnetic oxides have evolved into an important branch of materials science due to their potential application in spintronic devices combining of properties of semiconductors and ferromagnets. In spite of a major effort devoted to the mechanism of ferromagnetism with a high Curie temperature in these materials, it still remains the most controversial research topic, especially given the unexpected d0 ferromagnetism in a series of undoped wide-band-gap oxides films or nanostructures. Recently, an abundance of research has shown the critical role of various defects in the origin and control of spontaneous magnetic ordering, but contradicting views from intertwined theoretical calculations and experiments require more in-depth systematic research. In our previous work, considerable efforts have been focused on two major oxides, i.e. ZnO and ZrO 2. This review will present a summary of current experimental status of this defect-driven ferromagnetism in dilute magnetic oxides(DMOs).     

Mn and other magnetic impurities in GaN and other III–V semiconductors – perspective for spintronic applications

III–V semiconductors doped with magnetic ions have been attracting interest of many laboratories all over the world during more than thirty years. At the beginning the reason was the will to understand influence of omnipresent unintentional, as well as intentionally introduced, impurities of transition metals or rare earths on electrical and optical properties of semiconductors commonly applied in electronic and optoelectronic devices. In the last years the subject of III–V semiconductors highly doped with magnetic ions, the so-called diluted magnetic semiconductors, has revived rapidly again in the context of the newborn branch of electronics, called spintronics. Diluted magnetic semiconductors based on III–V compounds are regarded as prospect candidates for applications in spintronic devices. The results of studies performed on III–V semiconductors, doped or diluted with different magnetic ions, are presented. Special attention is put to GaN because of a strong hope, based on theoretical calculations, for high temperature ferromagnetism. Reasons for difficulties with obtaining high temperature ferromagnetic semiconductors are shown. A possible mechanism of magnetic ordering in III–V semiconductors doped with Mn is presented.     

Magnetic Properties of Chalcopyrite-Based Diluted Magnetic Semiconductors

We calculated the chemical trends of transition metal-doped chalcopyrite DMS (diluted magnetic semiconductors) by the use of KKR–CPA–LDA method. The ferromagnetism was stable in V- and Cr-doped chalcopyrite DMS. In the case of Fe and Co doping, however, the spinglass-like state was realized. On the other hand, in the cases of Mn doped I-III-VI₂ and II-IV-V₂ type DMS, the ground state was ferromagnetic and spinglass-like, respectively.     

Magneto-Optical Study of Multiple Layers of Self-Assembled Quantum Dots Involving Diluted Magnetic Semiconductors

Magneto-optical experiments were carried out on structures comprised of multiple layers of self-assembled quantum dots (QDs) involving diluted magnetic semiconductors (DMSs). Photoluminescence (PL) from interband ground state transitions was clearly observed in these DMS-based QD systems. The PL energy from QD multilayers appears at a lower energy than that emitted by a single QD layer, suggesting that there exists electronic coupling between the QD layers. When an external magnetic field is applied, the PL peaks from QDs both in single-layer and in multilayer form exhibit large Zeeman shifts and a significant enhancement of intensity, a behavior that is typical for many low dimensional systems involving DMSs. In contrast to this behavior, however, we have observed a decrease of the PL intensity as a function of magnetic field in multilayer structures where alternating QW layers contain DMS and non-DMS QDs. We will show evidence that this effect arises from carrier transfer between pairs of QDs from adjacent layers (double QDs) due to the large Zeeman shifts of the conduction and valence bands characteristic of DMS QDs.     

New ferromagnetics based on manganese-alloyed chalcopyrites A<Superscript>II</Superscript>B<Superscript>IV</Superscript>C<Stack><Subscript>2</Subscript><Superscript>V</Superscript></Stack>

This review describes the principles of semiconductor spintronics, represents the physicochemical properties of materials based on manganese-alloyed A^IIB^IVC₂^V compounds, considers the results from theoretical simulation of magnetic properties of A^IIB^IVC₂^V alloyed with 3d metals, summarizes the basic approaches to explanation of ferromagnetism with Curie points above room temperature arising in A^IIB^IVC₂^V:Mn, and indicates promising ways to synthesize and study magnetic semiconductors based on chalcopyrites A^IIB^IVC₂^V in order to produce a suitable material for spintronic devices.     

Structure, stability and magnetism of cobalt doped (ZnO)n clusters

Clusters of magnetic impurities are believed to play an important role in retaining ferromagnetism in diluted magnetic semiconductors (DMS), the origin of which has been a long debated issue. Controlling the dopant homogeneity in magnetic semiconductors is therefore a critical issue for the fabrication of high performance DMS. The current paper presents a first principle study on the stability and magnetic properties of Co doped (ZnO)n (n = 12 and 15) clusters using density functional theory. The results show that cobalt ions in these clusters tend to increase their stabilities by maximizing their co-ordination numbers to oxygen. This will likely to be the case for (ZnO)n clusters with n other than 12 and 15 in order for Co to reside in a stable local crystal field. Expansive (shrinkage) stress is introduced when cobalt resides in exohedral substitutional (endohedral interstitial) sites; such strain can be offset by the cluster deformation. Bidoped cluster is found to be unstable due to the increase of system strain energy. All the doped clusters were found to preserve 3 microg of magnetic moments from Co in the overall clusters, but with part of the local moments on cobalt re-distributed onto neighboring oxygen atoms. Current findings may provide a better understanding on the structural chemistry of magnetic dopants in nanocrystallined DMS materials.     

From nanoelectronics to nano-spintronics

Today's electronics uses electron charge as a state variable for logic and computing operation, which is often represented as voltage or current. In this representation of state variable, carriers in electronic devices behave independently even to a few and single electron cases. As the scaling continues to reduce the physical feature size and to increase the functional throughput, two most outstanding limitations and major challenges, among others, are power dissipation and variability as identified by ITRS. This paper presents the expose, in that collective phenomena, e.g., spintronics using appropriate order parameters of magnetic moment as a state variable may be considered favorably for a new room-temperature information processing paradigm. A comparison between electronics and spintronics in terms of variability, quantum and thermal fluctuations will be presented. It shows that the benefits of the scalability to smaller sizes in the case of spintronics (nanomagnetics) include a much reduced variability problem as compared with today's electronics. In addition, another advantage of using nanomagnets is the possibility of constructing nonvolatile logics, which allow for immense power savings during system standby. However, most of devices with magnetic moment usually use current to drive the devices and consequently, power dissipation is a major issue. We will discuss approaches of using electric-field control of ferromagnetism in dilute magnetic semiconductor (DMS) and metallic ferromagnetic materials. With the DMSs, carrier-mediated transition from paramagnetic to ferromagnetic phases make possible to have devices work very much like field effect transistor, plus the non-volatility afforded by ferromagnetism. Then we will describe new possibilities of the use of electric field for metallic materials and devices: Spin wave devices with multiferroics materials. We will also further describe a potential new method of electric field control of metallic ferromagnetism via field effect of the Thomas Fermi surface layer.     

Fabrication of GaN/GaN:Mn core/shell nanowires and their photoluminescences

We report on the fabrication of GaN/GaN:Mn core/shell nanowires (NWs) using a two-step metalorganic chemcial vapor deposition (MOCVD) and chloride-based chemical vapor transport (CVT) process. Structural analyses indicated that the heterostructure NWs were single crystalline and exhibited a core/shell and lozenge structure. The photoluminescence (PL) of the core/shell NWs showed a peak at a center wavelength of 454 nm, which was red-shifted compared to those of GaN and GaN:Mn NWs. This outcome indicates the accumulation of excited carriers at the interfaces that would be helpful in developing novel magnetism in diluted magnetic GaN:Mn semiconductors.     

Exciton Spin Manipulation in ZnMnSe-Based Structures

Strong effect of structural design on spin functionality is observed in quantum structures based on II–VI semiconductors. Spin switching is realized when using a thin layer of Zn^0.95Mn^0.05Se diluted magnetic semiconductor (DMS) as a spin manipulator. This is evident from the polarization of photoluminescence related to a spin detector (an adjacent nonmagnetic quantum well (QW)) measured under the resonant excitation of the spin-up and spin-down states of the DMS, which is identical in value but opposite in sign. The achieved spin switching is suggested to reflect fast carrier diffusion from the DMS due to the absence of an energy barrier between the upper spin state of the DMS layer and the QW. On the other hand, the spin alignment is accomplished in the tunneling structures where the presence of the energy barrier inserted between a spin manipulator (i.e., a ZnMnSe/CdSe DMS superlattice) and a spin detector ensures a slow escape rate from the DMS layer.     

氧化物稀磁半导体材料的理论与实验研究进展

以氧化物宽禁带半导体为基体,通过掺杂磁性元素,可将非磁性半导体转变成铁磁性半导体,利用这些铁磁性半导体,能将新型的自旋电子器件集成到传统的微电子器件上,构成功能丰富的新型器件.由于稀磁半导体材料在自旋电子学中的重要作用,近年来受到广泛的关注.简要总结了有关氧化物稀磁半导体研究的发展状况;分析了制备条件对其磁性的可能影响;重点介绍了该系统中有关磁性起源的理论模型,包括双交换机制、磁极化子模型、RKKY模型等;比较了2种磁极化子理论模型,并对这些模型的适用范围进行了分析讨论.另外,还介绍了该体系微结构和磁结构的一些检测方法以及与磁性相关的输运性质、反常霍尔效应等.     

Donor impurity band exchange in dilute ferromagnetic oxides

Dilute ferromagnetic oxides having Curie temperatures far in excess of 300 K and exceptionally large ordered moments per transition-metal cation challenge our understanding of magnetism in solids. These materials are high-k dielectrics with degenerate or thermally activated n-type semiconductivity. Conventional super-exchange or double-exchange interactions cannot produce long-range magnetic order at concentrations of magnetic cations of a few percent. We propose that ferromagnetic exchange here, and in dilute ferromagnetic nitrides, is mediated by shallow donor electrons that form bound magnetic polarons, which overlap to create a spin-split impurity band. The Curie temperature in the mean-field approximation varies as (xdelta)(1/2) where x and delta are the concentrations of magnetic cations and donors, respectively. High Curie temperatures arise only when empty minority-spin or majority-spin d states lie at the Fermi level in the impurity band. The magnetic phase diagram includes regions of semiconducting and metallic ferromagnetism, cluster paramagnetism, spin glass and canted antiferromagnetism.     

Magnetic effects at the interface between non-magnetic oxides

The electronic reconstruction at the interface between two insulating oxides can give rise to a highly conductive interface. Here we show how, in analogy to this remarkable interface-induced conductivity, magnetism can be induced at the interface between the otherwise non-magnetic insulating perovskites SrTiO3 and LaAlO3. A large negative magnetoresistance of the interface is found, together with a logarithmic temperature dependence of the sheet resistance. At low temperatures, the sheet resistance reveals magnetic hysteresis. Magnetic ordering is a key issue in solid-state science and its underlying mechanisms are still the subject of intense research. In particular, the interplay between localized magnetic moments and the spin of itinerant conduction electrons in a solid gives rise to intriguing many-body effects such as Ruderman-Kittel-Kasuya-Yosida interactions, the Kondo effect and carrier-induced ferromagnetism in diluted magnetic semiconductors. The conducting oxide interface now provides a versatile system to induce and manipulate magnetic moments in otherwise non-magnetic materials.