Ga vacancy induced ferromagnetism enhancement and electronic structures of RE-doped GaN

Because of their possible applications in spintronic and optoelectronic devices, GaN dilute magnetic semiconductors (DMSs) doped by rare-earth (RE) elements have attracted much attention since the high Curie temperature was obtained in RE-doped GaN DMSs and a colossal magnetic moment was observed in the Gd-doped GaN thin film. We have systemically studied the GaN DMSs doped by RE elements (La, Ce–Yb) using the full-potential linearized augmented plane wave method within the framework of density functional theory and adding the considerations of the electronic correlation and the spin-orbital coupling effects. We have studied the electronic structures of DMSs, especially for the contribution from f electrons. The origin of magnetism, magnetic interaction and the possible mechanism of the colossal magnetic moment were explored. We found that, for materials containing f electrons, electronic correlation was usually strong and the spin–orbital coupling was sometimes crucial in determining the magnetic ground state. It was found that GaN doped by La was non-magnetic. GaN doped by Ce, Nd, Pm, Eu, Gd, Tb and Tm are stabilized at antiferromagnetic phase, while GaN doped by other RE elements show strong ferromagnetism which is suitable materials for spintronic devices. Moreover, we have identified that the observed large enhancement of magnetic moment in GaN is mainly caused by Ga vacancies (3.0μB per Ga vacancy), instead of the spin polarization by magnetic ions or originating from N vacancies. Various defects, such as substitutional Mg for Ga, O for N under the RE doping were found to bring a reduction of ferromagnetism. In addition, intermediate bands were observed in some systems of GaN:RE and GaN with intrinsic defects, which possibly opens the potential application of RE-doped semiconductors in the third generation high efficiency photovoltaic devices.     

Oscillatory ferromagnetic interlayer coupling in [Pt(5 Å)/Co(4 Å)]3/Cr(x Å)/[Co(4 Å)/Pt(12 Å)]3 multilayers with perpendicular anisotropy

Investigation has been performed on the interlayer coupling between two Co/Pt multilayers with perpendicular anisotropy separated by Cr spacers. As a function of the Cr spacer thickness, only ferromagnetic interlayer coupling has been observed between the two Co/Pt multilayers in contrast to the oscillatory interlayer coupling between ferromagnetic and antiferromagnetic observed in ferromagnetic layers with in-plane anisotropy separated by Cr spacers. It is the strength of the ferromagnetic interlayer coupling that has been observed to be oscillatory as a function of the Cr spacer thickness with a period of about 7 Å.     

MFM and Raman studies in PEMBE-grown (Ga,Mn)N thin films showing room-temperature ferromagnetism

We present the room-temperature ferromagnetism in the (Ga,Mn)N films grown on n-type GaN templates by plasma-enhanced molecular beam epitaxy for semiconductor spintronic device applications. Despite of the possible interface effects between the (Ga,Mn)N layers and n-type GaN templates, the (Ga,Mn)N films were found to exhibit the ferromagnetic ordering above room temperature. The magnetic force microscopy identified the magnetic domains with the different magnetic orientations at room temperature, indicating the existence of the ferromagnetic long-range ordering. In Raman spectra, an additional peak at 578 cm⁻¹ was observed, which is attributed to the local vibration of substitutional Mn in the (Ga,Mn)N lattice. Therefore, it is believed that the ferromagnetic ordering in (Ga,Mn)N is due to the carrier-mediated Ruderman-Kittle-Kasuya-Yosida interaction.     

Tuning magnetism of monolayer GaN by vacancy and nonmagnetic chemical doping

In view of important role of inducing and manipulating the magnetism in 2D materials for the development of low-dimensional spintronic devices, the magnetism of GaN monolayer with Ga vacancy and nonmagnetic chemical doping are investigated using first-principles calculations. It is found that pure GaN monolayer has graphene-like structure and is nonmagnetic. While, a neutral Ga vacancy can induce 3 μ_B intrinsic magnetic moment, localized mainly on the neighboring N atoms. Interestingly, after one Mg or Si atom doping in g-GaN with Ga vacancy, the magnetic moment can be modified to 4 μ_B or 2 μ_B respectively due to the change in hole number. Meantime, Mg-doped g-GaN with Ga vacancy shows half-metal character. With the increasing of doping concentrations, the magnetic moment can be further tuned. The results are interesting from a theoretical point of view and may open opportunities for these 2D GaN based materials in magnetic devices.     

Intrinsic magnetism induced by vacancy in GaN

We performed total energy electronic-structure calculations based on DFT that clarify the intrinsic magnetism of undoped GaN. The magnetism is due to Ga, instead of N, vacancies. The origin of magnetism arises from the unpaired 2p electrons of N surrounding Ga vacancy. At a vacancy concentration of 5.6%, the ferromagnetic state is 181 meV lower than the antiferromagnetic state. Our findings are helpful to gain a more novel understanding of structural and spin properties of Ga vacancy in wurtzite GaN and also provide a possible way to generate magnetic GaN by introducing Ga vacancies instead of doping with transition-metal atoms.     

Electronic structure of p-type (Ga,Fe)N diluted magnetic semiconductors

By ab-initio calculation we show that the (Ga,Fe)N ground state may be changed from anti-ferromagnetic to ferromagnetic by acceptor defect like Ga vacancies. The electronic structures are calculated by using the Korringa-Kohn-Rostoker (KKR) method combined with coherent potential approximation (CPA). We show that we can increase the magnetic moment of Fe in p-type GaN by oxygen co-doping. Mechanism of exchange interactions between magnetic ions in p-type (Ga,Fe)N is also studied. The effect of external magnetic field on the electronic structure of (Ga, Fe)N and p-type (Ga, Fe)N is investigated.     

Magnetic properties of Ni doped gallium nitride with vacancy induced defect

Investigations have been carried out to study the ferromagnetic properties of transition metal (TM) doped wurtzite GaN from first principle calculations using tight binding linear muffin-tin orbital (TBLMTO) method within the density functional theory. The present calculation reveals ferromagnetism in nickel doped GaN with a magnetic moment of 1.13 μ_B for 6.25% of Ni doping and 1.32 μ_B for 12.5% of nickel doping, there is a decrease of magnetic moment when two Ni atoms are bonded via nitrogen atom. The Ga vacancy (V_Ga) induced defect shows ferromagnetic state. Here the magnetic moment arises due to the tetrahedral bonding of three N atoms with the vacancy which is at a distance of 3.689 Å and the other N atom which is at a distance of 3.678 Å .On the other hand the defect induced by N vacancy (V_N) has no effect on magnetic moment and the system shows metallic character. When Ni is introduced into a Ga vacancy (V_Ga) site, charge transfer occur from the Ni ‘d’ like band to acceptor level of V_Ga and formed a strong Ni–N bond. In this Ni–V_Ga complex with an Ni ion and a Ga defect, the magnetic moment due to N atom is 0.299 μ_B .In case of Ni substitution in Ga site with N vacancy, the system is ferromagnetic with a magnetic moment of 1 μ_B.     

Ferromagnetism driven by cation vacancy in GaN thin films and nanowires

The first-principles calculations have been performed to understand the origin of magnetism in undoped GaN thin films. The results show that Ga vacancy, rather than that of N contributes the observed magnetism, and the magnetic moments mainly come from the unpaired 2p electrons at nearest-neighbor N atoms of the Ga vacancy. Calculations and discussions are also extended to bare and passivated GaN nanowires, We find that per Ga vacancy on the surface sites products the total magnetic moment of 1.0  while that inside of the nanowires can lead to the formation of a net moment of 3.0 . The coupling between two Ga vacancies is also studied and we found that the coupling is ferromagnetic coupling. The surface passivation with hydrogen is shown to strongly enhance the ferromagnetism. Our theoretical study not only demonstrates that GaN nanowire can be magnetic even without transition-metal doping, but also suggests that introducing Ga vacancy is a natural and an effective way to fabricate low-dimensional magnetic GaN nanostructures.     

Structure and interlayer coupling in Co/V multilayers

Two series of sputtered Co/V multilayers were investigated by X-ray diffraction, ferromagnetic resonance (FMR) and magnetic measurements. The multilayers are found severely alloyed, resulting in two FMR peaks of uniform mode. Spin-wave resonance (SWR) spectra were observed when the thickness of vanadium is thin, indicating interlayer coupling. The data of SWR were treated approximately respectively by volume inhomogeneity (VI) and volume homogeneity and entire surface pinning (SP) models. The relatively small calculated effective exchange constants showed weak exchange coupling between Co layers across V spacers.     

Vacancy defects as compensating centers in Mg-doped GaN

We apply positron annihilation spectroscopy to identify V(N)-Mg(Ga) complexes as native defects in Mg-doped GaN. These defects dissociate in postgrowth annealings at 500-800 degrees C. We conclude that V(N)-Mg(Ga) complexes contribute to the electrical compensation of Mg as well as the activation of p-type conductivity in the annealing. The observation of V(N)-Mg(Ga) complexes confirms that vacancy defects in either the N or Ga sublattice are abundant in GaN at any position of the Fermi level during growth, as predicted previously by theoretical calculations.     

Magnetic Properties and Spin State Transition of Gallium Doped Perovskite Cobaltite Oxide

A series of Ga doping perovskite cobaltite La2/3Sr1/3 （Co1-y Gay）03 （y = 0, 0.1, 0.2, 0.3 and 0.4） are prepared by the standard solid-state reaction method. Their magnetic properties and Co ions spin state transitions are studied. Upon doping, no appreciable structure changes can be found. However, the corresponding Curie temperature sharply decreases and the magnetization is greatly reduced, indicating that Ga doping destroys the ferromagnetic interaction in the system. In addition, the high temperature magnetization data follow the Curie-Weiss law. At least one kind of Co ions （Co^3＋ or Co^4＋） favours the mixed spin state, and most Co ions are at the lower spin state （low and intermediate state）. With increasing Ga content, more Co ions transit to the higher spin state.     

射频等离子体辅助MBE生长GaN及Mg掺杂的光致发光

采用射频等离子体辅助分子束外延(RF plasma-assisted MBE)系统生长非故意掺杂GaN和p型GaN,并且通过室温和低温光致发光(PL)谱测试研究了材料的发光特性及与杂质态的关系,对于GaN外延层出现的黄带发光进行分析。结果表明,富Ga条件下生长的GaN材料特性要优于富N生长的材料;非故意掺杂的富Ga样品中出现的黄带发光(YL)与GaN中生成能最低的氮空位(V_N)缺陷有关;不同的Mg掺杂浓度对样品的PL特性有较大的影响;结合Hall效应测量结果,认为在Mg重掺杂的样品中出现的黄带发光,与GaN的自补偿效应以及重掺杂导致的晶体质量下降有关。     

Magnetic properties of (Ga,Mn)N ternaries and structural,electronic, and magnetic properties of cation-mixed (Ga,Mn)(As,N) and (In,Mn)(As,N) quaternaries

ABINIT simulation package with built in local density, generalized gradient, and spin local density approximations was used to investigate the structural, electronic, and magnetic properties of cation mixed (Ga,Mn)(As,N) and (In,Mn)(As,N) quaternaries with equal and fixed compositions of Ga, In, and Mn atoms. In particular, total energy minimization approach was used to compute the equilibrium structural parameters of zinc-blende (GaAs, InAs, and MnAs), wurtzite (GaN, InN, and MnN) binary parent compounds, as well as, the corresponding equilibrium parameters of (Ga,Mn)(As,N) and (In,Mn)(As,N) quaternary systems. The band structures of zinc-blende GaAs, InAs, and MnAs binary parent compounds were computed and analyzed. Spin polarized band structures of the cation mixed (Ga,Mn)(As,N) and (In,Mn)(As,N) quaternaries with equal compositions of Ga, In, and Mn cations were computed and analyzed using spin local density approximation based calculations. Moreover, the magnetic properties of (Ga,Mn)(As,N) and (In,Mn)(As,N) quaternaries with equal concentration of Ga, In, and Mn cations were investigated. Our results suggest that the two quaternary systems are nonmagnetic. An interpretation of our results is presented. In addition, the magnetic properties of (Ga,Mn)N nanocrystal ternaries constructed from doping GaN with one or two Mn atoms were investigated using Vienna Ab-initio Simulation Package (VASP) and compared with those of (Ga,Mn)(As,N) quaternaries.     

XPS study of the formation of ultrathin GaN film on GaAs(1 0 0)

The nitridation of GaAs(1 0 0) surfaces has been studied using XPS spectroscopy, one of the best surface sensitive techniques. A glow discharge cell was used to produce a continuous plasma with a majority of N atomic species. We used the Ga3d and As3d core levels to monitor the chemical state of the surface and the coverage of the species. A theoretical model based on stacked layers allows to determine the optimal temperature of nitridation. Moreover, this model permits the determination of the thickness of the GaN layer. Varying time of nitridation from 10 min to 1 h, it is possible to obtain GaN layers with a thickness between 0.5 nm and 3 nm.     

Role of defect sites and Ga polarization in the magnetism of Mn-doped GaN

We report a study of the Mn local structure, magnetism, and Ga moments in molecular beam epitaxy grown Mn-doped GaN films. Using x-ray absorption spectroscopy and magnetic circular dichroism, we find two distinct Mn sites and a Ga moment antiparallel to Mn. First-principles calculations reproduce this phenomenology and indicate that Mn preferentially populates Ga sites neighboring N split interstitial defects. These results show that defects may strongly affect the Mn ordering and magnetism, and that the GaN valence band is polarized, providing a long-range ferromagnetic ordering mechanism for Ga1-xMnxN.     

Element resolved spin configuration in ferromagnetic manganese-doped gallium arsenide

We report induced Ga and As moments in ferromagnetic Ga(1-x)MnxAs detected using x-ray magnetic circular dichroism at the Mn, Ga, and As L(3,2) edges. Across a broad composition range, we find As and Ga dichroism signals which indicate an As 4s moment coupled antiparallel to the Mn 3d moment, and a smaller parallel Ga 4s moment. The Ga moment follows that of Mn in both doping and temperature dependence. These results are consistent with recent predictions of induced GaAs host moments and support the model of carrier-mediated ferromagnetic ordering involving As-derived valence band states.     

MAGNETIC POLARIZATION OF Pd SPACERS AND OSCILLATORY EXCHANGE COUPLING BETWEEN Fe AND Pd LAYERS IN Fe/Pd MULTILAYERS

Ay oscillatory behavior in specific saturation magnetization of Fe/Pd multilayers is observed. The conversion electron M?ssbauer spectroscopy and other experiments indicate that this behavior is caused by the magnetic polarization of Pd spacers, which alternates between positive and negative polarization with respect to the magnetic moments of Fe layers. The interlayer coupling between two Fe layers always keeps ferromagnetic. Then, the interlayer couplings in ferromagnetic metal/nearly ferromagnetic metal multilayers were calculated By using the model of Barnas. The results of calculation prove that the above phenomenon might appear under some condition. The influence of magnetic polarization potential of spacers and interface chemical potential on the interlayer couplings is also discussed.     

Magnetic and structural properties of Fe ion-implanted GaN

The magnetic and structural properties of Fe ion-implanted GaN was investigated by various measurements. XRD results did not show any peaks associated with second phase formation. The magnetization curve at 5 K showed ferromagnetic behavior for 900 °C-annealed sample. In zero-field-cooled (ZFC) and field-cooled (FC) magnetization measurements, the irreversibility and a cusp-like behavior of the ZFC curve were observed for 900 °C-annealed sample. These behaviors are typically observed in superparamagnetic or spin glass phase. While the temperature dependence magnetization of 800 °C-annealed sample showed non-Brillouin-like curve and it is not exhibited ferromagnetic hysteresis at 5 K. In XPS measurement, the coexistence of metallic Fe (Fe⁰) and Fe–N bond (Fe²⁺ and Fe³⁺) for Fe 2p core level spectra is observed in as-implanted sample. But 700–900 °C-annealed samples showed only Fe–N bond (Fe²⁺ and Fe³⁺) spectra. For Ga 3d core level spectra only Ga–N bonds showed for as implanted with 700–900 °C-annealed samples. From XPS results, it could be explained that magnetic property of our films originated from FeN structures.     

Low-temperature activation of Mg-doped GaN with thin Co and Pt films

The activation of metallorganic chemical vapor deposition-grown Mg-doped GaN by N₂ annealing with thin Co and Pt films has been investigated. The Hall effect measurements revealed that both the Co and Pt films enhance activation of Mg acceptors as catalysts at low temperatures. A maximum hole concentration of p-type GaN was achieved at annealing temperature of 600 °C for the samples activated with both the Co and Pt films. It was also revealed that the activation of the acceptors is strongly affected by the thickness of the Co film.     

Ultrathin Co/Cu(110) film as a lattice of ferromagnetic grains with dipolar interaction

The well-known fact of magnetic ordering in ultrathin Co films (with an effective thickness of several monoatomic layers) on a single-crystal Cu(110) substrate is described quantitatively using the model according to which the thin film is a lattice of three-dimensional ferromagnetic grains with dipole-dipole interactions. The critical film thickness corresponding to the ferromagnetic transition and the corresponding Curie temperature were calculated.