The properties of GaMnN lms grown by metalorganic chemical vapour deposition using Raman spectroscopy

An investigation of room-temperature Raman scattering is carried out on ferromagnetic semiconductor GaMnN films grown by metalorganic chemical vapour deposition with different Mn content values. New bands around 300 and 669 cm^-1, that are not observed in undoped GaN, are found. They are assigned to disorder-activated mode and local vibration mode (LVM), respectively. After annealing, the intensity ratio between the LVM and E₂(high) mode, i.e., I_LVM=I_E2(high), increases. The LO phonon-plasmon coupled (LOPC) mode is found in GaMnN, and the frequency of the LOPC mode of GaMnN shifting toward higher side is observed with the increase in the Mn doping in GaN. The ferromagnetic character and the carrier density of our GaMnN sample are discussed.     

Characterizations of n-type ferromagnetic GaMnN thin film grown on GaN/Al2O3 (0 0 0 1) by metal-organic chemical vapor deposition

A high-quality ferromagnetic GaMnN (Mn=2.8 at%) film was deposited onto a GaN buffer/Al₂O₃(0 0 0 1) at 885 °C using the metal-organic chemical vapor deposition (MOCVD) process. The GaMnN film shows a highly c-axis-oriented hexagonal wurtzite structure, implying that Mn doping into GaN does not influence the crystallinity of the film. No Mn-related secondary phases were found in the GaMnN film by means of a high-flux X-ray diffraction analysis. The composition profiles of Ga, Mn, and N maintain nearly constant levels in depth profiles of the GaMnN film. The binding energy peak of the Mn 2p_3/2 orbital was observed at 642.3 eV corresponding to the Mn (III) oxidation state of MnN. The presence of metallic Mn clusters (binding energy: 640.9 eV) in the GaMnN film was excluded. A broad yellow emission around 2.2 eV as well as a relatively weak near-band-edge emission at 3.39 eV was observed in a Mn-doped GaN film, while the undoped GaN film only shows a near-band-edge emission at 3.37 eV. The Mn-doped GaN film showed n-type semiconducting characteristics; the electron carrier concentration was 1.2×10²¹/cm³ and the resistivity was 3.9×10⁻³ Ω cm. Ferromagnetic hysteresis loops were observed at 300 K with a magnetic field parallel and perpendicular to the ab plane. The zero-field-cooled and field-cooled curves at temperatures ranging from 10 to 350 K strongly indicate that the GaMnN film is ferromagnetic at least up to 350 K. A coercive field of 250 Oe and effective magnetic moment of 0.0003 μ_B/Mn were obtained. The n-type semiconducting behavior plays a role in inducing ferromagnetism in the GaMnN film, and the observed ferromagnetism is appropriately explained by a double exchange mechanism.     

Preparation and characterization of room-temperature ferromagnetism GaMnN based on ion implantation

This paper reports the fabrication of GaMnN ferromagnetic semiconductor on GaN substrate by high-dose Mn ion implantation. Both the structural and optical properties for Mn+-implanted GaN material were studied by X-ray diffraction, Raman scattering and photolumi-nescence. The results reveal that the implanted manganese incorporates on Ga site and GaMnN ternary phase is formed in the substrate. The magnetic behavior has been characterized by superconducting quantum interference device. The material shows room-temperature ferromagnet-ism. The temperature-dependent magnetization indicates different mechanism for ferromagnetism in Mn+-implanted GaN.     

Optical and Structural Properties of Mn-Doped GaN Grown by Metal Organic Chemical Vapour Deposition

Mn-doped GaN epitaxial films were grown by metal organic chemical vapour deposition （MOCVD）. Microstructural properties of films are investigated using Raman scattering. It is found that with increasing Mn-dopants levels, longitudinal optical phonon mode A1 （LO） of films is broadened and shifted towards lower frequency. This phenomenon possibly derives from the difference in bonding strength between Ga-N pairs and Mn-N pairs in host lattice. In addition, optical properties of films are investigated using cathodoluminescence and absorption spectroscopy. Mn-related both emission band around 3.0eV and absorption bands around 1.5 and 2.95eV are observed. By studies on structural and optical properties of Mn-doped GaN, we find that Mn ions substitute for Ga sites in host lattice. However, carrier-mediated ferromagnetic exchange seems unlikely due to deep levels of Mn acceptors.     

Phenomenological band structure model of magnetic coupling in semiconductors

A unified band structure model is proposed to explain the magnetic ordering in Mn-doped semiconductors. This model is based on the p-d and d-d level repulsions between the Mn ions and host elements and can successfully explain magnetic ordering observed in all Mn doped II-VI and III-V semiconductors such as CdTe, GaAs, ZnO, and GaN. The model can also be used to explain the interesting behavior of GaMnN, which changes from ferromagnetic ordering to antiferromagnetic ordering as the Mn concentration increases. This model, therefore, is useful to provide a simple guideline for future band structure engineering of magnetic semiconductors.     

Role of vacancy-type defects in magnetism of GaMnN

Role of vacancy-type(N vacancy(VN) and Ga vacancy(VGa)) defects in magnetism of GaMnN is investigated by first-principle calculation.Theoretical results show that both the VNand VGainfluence the ferromagnetic state of a system.The VNcan induce antiferromagnetic state and the VGaindirectly modify the stability of the ferromagnetic state by depopulating the Mn levels in GaMnN.The transfer of electrons between the vacancy defects and Mn ions results in converting Mn~(3+)(d~4) into Mn~(2+)(d5).The introduced VNand the ferromagnetism become stronger and then gradually weaker with Mn concentration increasing,as well as the coexistence of Mn~(3+)(d~4) and Mn~(2+)(d~5) are found in GaMnN films grown by metal–organic chemical vapor deposition.The analysis suggests that a big proportion of Mn~(3+)changing into Mn~(2+)will reduce the exchange interaction and magnetic correlation of Mn atoms and lead to the reduction of ferromagnetism of material.     

Plasma-assisted molecular beam epitaxy of wurtzite GaMnN displaying ferromagnetism assessed by means of X-ray magnetic circular dichroism

We report on the optimization of the growth conditions of wurtzite GaMnN grown by plasma-assisted molecular beam epitaxy in order to obtain intrinsic ferromagnetic behavior. By growing with a Ga/N ratio lower than unity and by introduction of periodic growth interruptions, we succeed in synthesizing single-phase GaMnN epilayers containing up to 6.3 at.% of Mn. The structural quality of the GaMnN epilayer and the absence of secondary phases are demonstrated by means of X-ray diffraction experiments and X-ray linear dichroism measurements performed at the Mn and Ga K-edges. The intrinsic ferromagnetism for 6.3 at.% of Mn in our GaMnN epilayer is demonstrated by means of magnetization measurements in a 5 T Quantum Design superconducting quantum interference device (SQUID) and X-ray magnetic circular dichroism investigations performed at the K-edge of Mn. The Curie temperature thus determined is equal to 8 K and a spontaneous magnetic moment of 2.4μ_B per Mn atom is found at 2 K.     

基于电子回旋共振-等离子体增强金属有机物化学气相沉积技术生长GaMnN稀磁半导体的研究

利用电子回旋共振-等离子体增强金属有机物化学气相沉积 (ECR-PEMOCVD)方法,采用二茂锰(Cp₂Mn)作为Mn源,高纯氮气作为氮源,三乙基镓(TEGa)作为Ga源,在蓝宝石(α-Al₂O₃)(0001)衬底上外延生长GaMnN稀磁半导体薄膜.反射高能电子衍射(RHEED)、X射线衍射(XRD)、原子力显微镜(AFM)表征了GaMnN薄膜的晶体结构和表面形貌.GaMnN薄膜均表现出良好的(0002)择优取向,表明制备的薄膜倾向于 关键词： GaMnN薄膜 稀磁半导体 铁磁性 居里温度     

Study of （Ga,Mn）N prepared by Mn-ion implantation using optical techniques

This paper reports that （Ga, Mn）N is prepared using implantation of 3at.% Mn Ions into undoped GaN. Structural characterization of the crystals was performed using x-ray diffraetion（XRD）. Detailed XRD measurements have revealed the characteristic of Mn-ion implanted GaN with a small contribution of other compounds. With Raman spectroscopy measurements, the spectra corresponding to the intrinsic GaN layers demonstrate three Raman active excitations at 747, 733 and 566 cm-1 identified as EI（LO）, A1 （LO） and E~, respectively. The Mn-doped GaN layers exhibit additional excitations at 182, 288, 650 725, 363, 506cm^-1 and the vicinity of E~ mode. The modes observed at 182, 288, 650 725em 1 are assigned to macroscopic disorder or vacancy-related defects caused by Mn-ion implantation. Other new phonon modes are assigned to Mnx-Ny, Gax-Mny modes and the local vibrational mode of Mn atoms in the （Ga, Mn）N, which are in fair agreement with the standard theoretical results.     

The magnetic properties of Be-codoped GaMnN grown via molecular beam epitaxy

GaMnN and Be-codoped GaMnN were grown via molecular beam epitaxy using a single GaN precursor and their structural and magnetic properties were examined. X-ray diffraction and superconducting quantum interference device (SQUID) measurements revealed that the grown layers are homogeneous without precipitates. The saturation magnetization of GaMnN has increased from ∼4 to ∼16 emu/cm³ via codoping of Be. The d–d exchange interaction between Mn atoms was discussed for the ferromagnetism of GaMnN.     

Magnetic, optical and transport properties of GaMnN films

GaMnN films with 1-3% Mn deposited on Si(100) and Al₂O₃(0001) substrates, by the technique of nebulized spray pyrolysis by employing acetylacetonate precursors, have been characterized by X-ray diffraction, photoluminescence spectra and other techniques. The films are ferromagnetic and show magnetic hysteresis. The ferromagnetic T_C increases with the Mn content, with the 3% Mn film showing a T_C of ∼250 K. Anomalous Hall effect is observed below T_C where the films exhibit a small negative magnetoresistance.     

金属有机化学气相淀积技术制备GaMnN薄膜材料光学性质研究

研究由MOCVD 技术制备的 GaMnN 外延薄膜光吸收谱.实验发现Mn掺杂后较未掺杂GaN吸收系数在近紫外区增加,在吸收谱低能区144 eV附近观察到吸收峰,吸收系数随Mn浓度的增加而增大.实验结果与基于密度泛函理论的第一性原理计算结果一致,结合理论计算分析认为144 eV附近的吸收峰源于Mn³⁺离子e态与t₂态间的带内跃迁⁵T₂→⁵E. 关键词： GaMnN MOCVD 密度泛函理论 光学性质     

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.     

GaMnN铁磁共振隧穿二极管自旋电流输运以及极化效应的影响

通过理论计算研究GaMnN铁磁共振隧穿二极管自旋电流输运特性.理论结果表明在电流特性曲线上出现两个明显的自旋分裂峰.该电流自旋分裂峰和相应的自旋极化随温度的升高而逐渐减小消失.当进一步考虑到GaN异质结界面极化电荷影响时,自旋向下的电流共振峰得到明显增强,同时电流的自旋极化也得到相应的提高.在一定的极化电荷条件下,可以获得较高的自旋极化电流. 关键词： GaMnN 共振隧穿 自旋电流 极化电荷     

Reconstruction control of magnetic properties during epitaxial growth of ferromagnetic Mn3-deltaGa on Wurtzite GaN(0001)

Binary ferromagnetic Mn(3-delta)Ga (1.2<3-delta< or =1.5) crystalline thin films have been epitaxially grown on wurtzite GaN(0001) surfaces using rf N-plasma molecular beam epitaxy. The film structure is face-centered tetragonal with CuAu type-I (L1(0)) ordering with (111) orientation. The in-plane epitaxial relationship to GaN is nearly ideal with [110](MnGa) parallel[1100](GaN) and [112](MnGa) parallel[1120](GaN). We observe magnetic anisotropy along both the in-plane and out-of-plane directions. The magnetic moments are found to depend on the Mn/(Mn+Ga) flux ratio and can be controlled by observation of the surface reconstruction during growth, which varies from 1x1 to 2x2 with increasing Mn stoichiometry.     

Comparative Analysis of Temperature-dependent Raman Spectra of GaN and GaN/Mg Films

The Raman spectra of unintentionally doped gallium nitride (GaN) and Mg-doped GaN films were investigated and compared at room temperature and low temperature. The differences of E₂ and A₁(LO) mode in two samples are discussed. Stress relaxation is observed in Mg-doped GaN, and it is suggested that Mg-induced misfit dislocation and electron–phonon interaction are the possible origins. A peak at 247 cm^?1 is observed in both the Raman spectra of GaN and Mg-doped GaN. Temperature-dependent Raman scattering experiment of Mg-doped GaN shows the frequency and intensity changes of this peak with temperature. This peak is attributed to the defect-induced vibrational mode.     

GaN薄膜拉曼散射光谱的研究

利用拉曼散射光谱对在SiC衬底上采用MOCVD异质外延的未故意掺杂GaN薄膜特性进行研究发现E2模式向频率低的方向漂移表明在GaN薄膜中存在张力,由于SiC衬底不平整度增加引起更多位错的出现,从而引起拉曼谱中E2模式的加宽,因此通过选择平整度较好的衬底可以减小缺陷密度,提高薄膜的质量,此外A1(LO)模式的出现与强度可以用来表征未掺杂GaN的薄膜质量。     

Comparative Analysis of Temperature-dependent .Raman Spectra of GaN and GaN/Mg Films

The Raman spectra of unintentionally doped gallium nitride (GaN) and Mg-doped GaN films were investigated and compared at room temperature and low temperature. The differences of E₂ and A₁(LO) mode in two samples are discussed. Stress relaxation is observed in Mg-doped GaN, and it is suggested that Mg-induced misfit dislocation and electron–phonon interaction are the possible origins. A peak at 247 cm⁻¹ is observed in both the Raman spectra of GaN and Mg-doped GaN. Temperature-dependent Raman scattering experiment of Mg-doped GaN shows the frequency and intensity changes of this peak with temperature. This peak is attributed to the defect-induced vibrational mode. Translated from Chinese Journal of Semiconductors, 2005, 26(4) (in Chinese)     

GaN layers with different polarities prepared by radio frequency molecular beam epitaxy and characterized by Raman scattering

GaN layers with different polarities have been prepared by radio-frequency molecular beam epitaxy (RF-MBE) and characterized by Raman scattering. Polarity control are realized by controlling Al/N flux ratio during high temperature AlN buffer growth. The Raman results illustrate that the N-polarity GaN films have frequency shifts at $A_{1}$(LO) mode because of their high carrier density; the forbidden $A_{1}$(TO) mode occurs for mixed-polarity GaN films due to the destroyed translation symmetry by inversion domain boundaries (IDBS); Raman spectra for Ga-polarity GaN films show that they have neither frequency shifts mode nor forbidden mode. These results indicate that Ga-polarity GaN films have a better quality, and they are in good agreement with the results obtained from the room temperature Hall mobility. The best values of Ga-polarity GaN films are 1042 cm$^{2}$/Vs with a carrier density of 1.0$\times $10$^{17}$~cm$^{ - 3}$.     

Concerted diffusion, clustering, and magnetic properties of Mn dopants on a 2 x 2-T4 GaN(0001) substrate

Based on first-principles calculations within density functional theory, we propose a kinetic pathway for Mn incorporation on reconstructed 2 x 2-T4 GaN(0001), characterized by concerted substitution of a Ga atom by a Mn adatom via a precursor surface site T4. The Mn dopants at low densities are randomly distributed, resulting in intrinsic diluted magnetic semiconductors (DMS). At high Mn densities, planar ferromagnetic clusters oriented in the (0001) plane can be readily formed at relatively low growth temperatures, but ferrimagnetic zigzag columns along the growth orientation will be formed at high temperatures. Furthermore, intrinsic DMS are more likely to be formed via codeposition of Mn+Ga+N at high growth rates. These findings help to explain the observed variations in both the magnetic ordering temperature TC and the magnetic nature of Ga1-xMnxN.