Ferromagnetism of ZnO and GaN: A Review

The observation of ferromagnetism in magnetic ion doped II–VI diluted magnetic semiconductors (DMSs) and oxides, and later in (Ga,Mn)As materials has inspired a great deal of research interest in a field dubbed “spintronics” of late, which could pave the way to exploit spin in addition to charge in semiconductor devices. The main challenge for practical application of the DMS materials is the attainment of a Curie temperature at or preferably above room temperature to be compatible with junction temperatures. Among the studies of transition-metal doped conventional III–V and II–VI semiconductors, transition-metal-doped ZnO and GaN became the most extensively studied topical materials since the prediction by Dietl et al., based on mean field theory, as promising candidates to realize a diluted magnetic material with Curie temperature above room temperature. The underlying assumptions, however, such as transition metal concentrations in excess of 5% and hole concentrations of about 10²⁰ cm⁻³, have not gotten as much attention. The particular predictions are predicated on the assumption that hole mediated exchange interaction is responsible for magnetic ordering. Among the additional advantages of ZnO-and GaN-based DMSs are that they can be readily incorporated in the existing semiconductor heterostructure systems, where a number of optical and electronic devices have been realized, thus allowing the exploration of the underlying physics and applications based on previously unavailable combinations of quantum structures and magnetism in semiconductors. This review focuses primarily on the recent progress in the theoretical and experimental studies of ZnO- and GaN-based DMSs. One of the desirable outcomes is to obtain carrier mediated magnetism, so that the magnetic properties can be manipulated by charge control, for example through external electrical voltage. We shall first describe the basic theories forwarded for the mechanisms producing ferromagnetic behavior in DMS materials, and then review the theoretical results dealing with ZnO and GaN. The rest of the review is devoted to the structural, optical, and magnetic properties of ZnO- and GaN-based DMS materials reported in the literature. A critical review of the question concerning the origin of ferromagnetism in diluted magnetic semiconductors is given. In a similar vein, limitations and problems for identifying novel ferromagnetic DMS are briefly discussed, followed by challenges and a few examples of potential devices.     

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.     

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.     

Large anomalous Hall effect in a silicon-based magnetic semiconductor

Magnetic semiconductors are attracting great interest because of their potential use for spintronics, a new technology that merges electronics with the manipulation of conduction electron spins. (GaMn)As and (GaMn)N have recently emerged as the most popular materials for this new technology, and although their Curie temperatures are rising towards room temperature, these materials can only be fabricated in thin-film form, are heavily defective, and are not obviously compatible with Si. We show here that it is productive to consider transition metal monosilicides as potential alternatives. In particular, we report the discovery that the bulk metallic magnets derived from doping the narrow-gap insulator FeSi with Co share the very high anomalous Hall conductance of (GaMn)As, while displaying Curie temperatures as high as 53 K. Our work opens up a new arena for spintronics, involving a bulk material based only on transition metals and Si, which displays large magnetic-field effects on its electrical properties.     

Effects of Transition Metal (TM = V,Cr, Mn,Fe, Co,and Ni) Elements on Magnetic Mechanism of LiZnP with Decoupled Charge and Spin Doping

The electronic structure and magnetism of a series of 111-type diluted magnetic semiconductors Li(Zn,TM)P (TM = V, Cr, Mn, Fe, Co, and Ni) are investigated on the basis of density functional theory. Our results indicate that V-, Cr-, Mn-, and Fe-doped LiZnP are magnetic while Co- and Ni-doped LiZnP systems show no magnetisms. But all TM-doped LiZnP systems prefer antiferromagnetic behavior by magnetic coupling calculations. In contrast, V/Li- and Cr/Li-codoped LiZnP prefer ferromagnetic ordering, and Mn/Li-, Fe/Li- and Co/Li-codoped LiZnP display antiferromagnetic spin ordering. Hence, Li dopant is very vital for the ferromagnetic formation of Li(Zn,TM)P materials. It is revealed that the magnetic moments come mainly from the TM 3d orbitals. The ferromagnetic coupling between the TM atoms is explained by through-bond spin polarization. Our work demonstrates that the magnetic properties of Li(Zn,TM)P can be mediated by doping different TM atoms. These results may provide theoretical guidance for further experimental research on DMS.     

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.     

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.     

Hydrogen in semiconductors

Hydrogen in crystalline semiconductors has become a recent curiosity because of its high diffusivity and strong chemical activity in such materials. In contrast to the proton motion in ionic materials which gives rise to an enhanced conductivity, hydrogen in electronic materials interact with structural disorders and chemical impurities to control the electronic flow. Deep gap states in crystalline semiconductors due to various disorders such as surface/interface, grain boundaries, dislocations, irradiation and implantation damage etc. have been removed due to hydrogen bondings. Hydrogen incorporation is done by plasma and direct ion beam hydrogenation methods, implantation technique and by a novel technique of damage free introduction. The most studied materials are silicon and gallium arsenide.I - V,C - V, DLTS and IR studies have been carried out on hydrogenated semiconductors to characterize the electronic flow, gap states and the nature of chemical bonds. Improvement in ideality factors of diodes, reduction in free carrier concentration, removal or reduction of deep states and appearance of new bondings such as Si-H, P-H, B-H etc. have been observed from various techniques. The present paper reviews the various features of hydrogenation studies in crystalline silicon and gallium arsenide and highlights our results of hydrogenation studies on Pd/semiconductor devices.     

Density Functional Calculations for III–V Diluted Ferromagnetic Semiconductors: A Review

In this paper we review the latest achievements of density functional theory in understanding the physics of diluted magnetic semiconductors. We focus on transition-metal-doped III–V semiconductors, which show spontaneous ferromagnetic order at relatively high temperature and good structural compatibility with existing III–V devices. We show that density functional theory is a very powerful tool for (i) studying the effects of local doping defects and disorder on the magnetic properties of these materials, (ii) predicting properties of new materials, and (iii) providing parameters, often not accessible from experiments, for use in model Hamiltonian calculations. Such studies are facilitated by recent advances in numerical implementations of density functional theory, which make the study of systems with a very large number of atoms possible.     

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.     

Towards dilute magnetic semiconductors: Fe and Co substituted inorganic-organic hybrid materials based on ZnSe

Inorganic-organic hybrid nanostructures doped with magnetic ions have been synthesized via substitution of Zn by Co or Fe in the ZnSe(L)0.5 systems under solvothermal conditions. These dilute magnetic semiconductors (DMS), Zn(1-x)MxSe(L)0.5 (M = Co, Fe; L = ethylenediamine or en, 1,3-propanediamine or pda; 0 < x < 1), are composed of perfectly ordered Zn(1-x)MxSe semiconductor monolayers interconnected by organic diamine molecules. The large blue shifts in their optical absorption edges (approximately 1.1-1.5 eV) compared to the bulk ZnSe are a direct result of a very strong quantum confinement effect (QCE). Magnetic studies show that there exist antiferromagnetic interactions between the Co or Fe centers in the structures and the interaction is enhanced as the doping concentration increases. The introduction of Fe or Co to hybrid inorganic-organic semiconductors provides a promising route to generate materials that combine the advantageous features of inorganic, organic, and magnetic functionalities in a single structure.     

Charge transport physics of conjugated polymer field-effect transistors

Field‐effect transistors based on conjugated polymers are being developed for large‐area electronic applications on flexible substrates, but they also provide a very useful tool to probe the charge transport physics of these complex materials. In this review we discuss recent progress in polymer semiconductor materials, which have brought the performance and mobility of polymer devices to levels comparable to that of small‐molecule organic semiconductors. These new materials have also enabled deeper insight into the charge transport physics of high‐mobility polymer semiconductors gained from experiments with high charge carrier concentration and better molecular‐scale understanding of the electronic structure at the semiconductor/dielectric interface.     

Half-Metallic Ferromagnetism in Strontium-Doped III–V: Ab Initio Calculations

First-principle calculations are employed by means of an all-electron full-potential linearized augmented plane wave to investigate the electronic structure and magnetic properties of AlP, AlAs, GaP, GaAs, InP, and InAs-based dilute magnetic semiconductors (DMS) with Sr impurities. It is shown that, in all the cases the ferromagnetic phase is energetically favored with respect to the paramagnetic one. In addition, these alloys are found to be half-metallic ferromagnets with a net total magnetic moment of 1.00 μ _B when they assume the zinc-blende structure at the equilibrium lattice constant. Ferromagnetism is induced by the spin polarization of the p shells of anions; the magnetic moment mainly comes from anion atoms surrounding the dopant atom, which is different from conventional DMS. These theoretical results make these materials interesting candidates for spin injection in spintronic devices.     

Tailoring ferromagnetic chalcopyrites

If magnetic semiconductors are ever to find wide application in real spintronic devices, their magnetic and electronic properties will require tailoring in much the same way that bandgaps are engineered in conventional semiconductors. Unfortunately, no systematic understanding yet exists of how, or even whether, properties such as Curie temperatures and bandgaps are related in magnetic semiconductors. Here we explore theoretically these and other relationships within 64 members of a single materials class, the Mn-doped II-IV-V(2) chalcopyrites (where II, IV and V represent elements from groups II, IV and V, respectively); three of these compounds are already known experimentally to be ferromagnetic semiconductors. Our first-principles results reveal a variation of magnetic properties across different materials that cannot be explained by either of the two dominant models of ferromagnetism in semiconductors. On the basis of our results for structural, electronic and magnetic properties, we identify a small number of new stable chalcopyrites with excellent prospects for ferromagnetism.     

A Critical Review of Current Studies on Hydrogen Defect in Diluted Magnetic Semiconductors and Relative Ferroelectric Materials for Smart Electronic Applications

Experimental and theoretical studies on hydrogen in diluted magnetic semiconductors and related materials have been reviewed. A strong modification of magnetic order has been found by co-doping of hydrogen and magnetic ions in diluted magnetic semiconductors, which depended on the states of hydrogen acting in both crystalline and amorphous. In addition, the hydrogen was found to be strongly active with the magnetic ions resulting in modification of the electrical, magnetic, band structure properties, etc. We expect that our review could help to make a direction for the experimental and theoretical guide to develop advanced functional materials in silicon technology.

     

Organic multiferroic tunnel junctions with ferroelectric poly(vinylidene fluoride) barriers

Organic materials are promising for applications in spintronics due to their long spin-relaxation times in addition to their chemical flexibility and relatively low production costs. Most studies of organic materials for spintronics focus on nonpolar dielectrics or semiconductors, serving as passive elements in spin transport devices. Here, we demonstrate that employing organic ferroelectrics, such as poly(vinylidene fluoride) (PVDF), as barriers in magnetic tunnel junctions (MTJs) allows new functionality in controlling the tunneling spin polarization via the ferroelectric polarization of the barrier. Using first-principles methods based on density functional theory we investigate the spin-resolved conductance of Co/PVDF/Co and Co/PVDF/Fe/Co MTJs as model systems. We show that these tunnel junctions exhibit multiple resistance states associated with different magnetization configurations of the electrodes and ferroelectric polarization orientations of the barrier. Our results indicate that organic ferroelectrics may open a new and promising route in organic spintronics with implications for low-power electronics and nonvolatile data storage.     

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.     

Developments of Diketopyrrolopyrrole-Dye-Based Organic Semiconductors for a Wide Range of Applications in Electronics

In recent times, fused aromatic diketopyrrolopyrrole (DPP)-based functional semiconductors have attracted considerable attention in the developing field of organic electronics. Over the past few years, DPP-based semiconductors have demonstrated remarkable improvements in the performance of both organic field-effect transistor (OFET) and organic photovoltaic (OPV) devices due to the favorable features of the DPP unit, such as excellent planarity and better electron-withdrawing ability. Driven by this success, DPP-based materials are now being exploited in various other electronic devices including complementary circuits, memory devices, chemical sensors, photodetectors, perovskite solar cells, organic light-emitting diodes, and more. Recent developments in the use of DPP-based materials for a wide range of electronic devices are summarized, focusing on OFET, OPV, and newly developed devices with a discussion of device performance in terms of molecular engineering. Useful guidance for the design of future DPP-based materials and the exploration of more advanced applications is provided.     

Flexible Electronics Based on Organic Semiconductors: from Patterned Assembly to Integrated Applications

Organic flexible electronic devices are at the forefront of the electronics as they possess the potential to bring about a major lifestyle revolution owing to outstanding properties of organic semiconductors, including solution processability, lightweight and flexibility. For the integration of organic flexible electronics, the precise patterning and ordered assembly of organic semiconductors have attracted wide attention and gained rapid developments, which not only reduces the charge crosstalk between adjacent devices, but also enhances device uniformity and reproducibility. This review focuses on recent advances in the design, patterned assembly of organic semiconductors, and flexible electronic devices, especially for flexible organic field-effect transistors (FOFETs) and their multifunctional applications. First, typical organic semiconductor materials and material design methods are introduced. Based on these organic materials with not only superior mechanical properties but also high carrier mobility, patterned assembly strategies on flexible substrates, including one-step and two-step approaches are discussed. Advanced applications of flexible electronic devices based on organic semiconductor patterns are then highlighted. Finally, future challenges and possible directions in the field to motivate the development of the next generation of flexible electronics are proposed.