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.     

Structural, morphological, and magnetic characteristics of Cu-implanted nonpolar GaN films

Diluted magnetic nonpolar GaN:Cu films have been fabricated by implanting Cu ions into unintentionally doped nonpolar a-plane() GaN films and a subsequent thermal annealing process. The structural, morphological and magnetic characteristics of the samples have been investigated by means of high-resolution X-ray diffraction (HRXRD), atomic force microscopy (AFM), and superconducting quantum interference device (SQUID). The sample shows a clear ferromagnetism behavior at room temperature. It is significantly shown that with a Cu concentration as low as 0.75% the sample exhibits a saturation magnetization about 0.65 μ_B/Cu atom. Moreover, the possible origin of the ferromagnetism for the sample was also discussed briefly.     

Room-temperature ferromagnetism and in-plane magnetic anisotropy characteristics of nonpolar GaN:Mn films

Diluted magnetic nonpolar GaN:Mn films have been fabricated by implanting Mn ions into nonpolar a-plane () p-type GaN films and a subsequent rapid thermal annealing process. The ferromagnetism properties of the films were studied by means of superconducting quantum interference device (SQUID). Clearly in-plane magnetic anisotropy characteristics of the sample at 10 K were revealed with the direction of the applied magnetic field rotating along the in-plane [0 0 0 1]-axis. Moreover, obvious ferromagnetic properties of the sample up to 350 K were detected by means of the temperature-dependent SQUID.     

Cr-Doped InAs Self-Organized Diluted Magnetic Quantum Dots with Room-Temperature Ferromagnetism

Cr-doped InAs self-organized diluted magnetic quantum dots （QDs） are grown by low-temperature molecularbeam epitaxy. Magnetic measurements reveal that the Curie temperature of all the InAs：Cr QDs layers with Cr/In flux ratio changing from 0.026 to 0.18 is beyond 400 K. High-resolution cross sectional transmission electron microscopy images indicate that InAs：Cr QDs are of the zincblende structure. Possible origins responsible for the high Curie temperature are discussed.     

Growth and Characteristics of Epitaxial AlxGa1-xN by MOCVD

Al_xGa_1-xN epilayers with a wide Al composition range (0.2≤x≤ 0.68) were grown on AlN/sapphire templates by low-pressure metalorganic chemical vapour deposition (LP-MOCVD). X-ray diffraction results reveal that both the (0002) and (10^-15) full widths at half-maximum (FWHM) of the Al_xGa_1-xN epilayer decrease with increasing Al composition due to the smaller lattice mismatch to the AlN template. However, the surface morphology becomes rougher with increasing Al composition due to the weak migration ability of Al atoms. Low temperature photoluminescence (PL) spectra show pronounced near band edge (NBE) emission and the NBE FWHM becomes broader with increasing Al composition mainly caused by alloy disorder. Meanwhile, possible causes of the low energy peaks in the PL spectra are discussed.     

Synthesis and characterization of GaN nanowires

In this work, GaN nanowires were fabricated on Si substrates coated with NiCl₂ thin films using chemical vapor deposition (CVD) method by evaporating Ga₂O₃ powder at 1100 °C in ammonia gas flow. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM) and photoluminescence (PL) spectrum are used to characterize the samples. The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure. The growth mechanism of GaN nanowires is also discussed.     

Influence of Randomness and Localization on RKKY Interactions in Diluted Magnetic Semiconductors

We show that the spatially random distribution of magnetic moments of dopants in diluted magnetic semiconductors can partially localize the itinerant carriers and change the carrier-mediated indirect RKKY interaction. From numerical calculations of the electron states taking into account the interaction with magnetic impurities which are random both in spatial positions and in orientations of magnetic moments, we obtain the electron states and the RKKY interaction as a function of the distance between magnetic dopants L and of the sp - d exchange integral J. With the increase of disorder, the localization of itinerant electrons become stronger and the long-range regular oscillatory behaviour of the RKKY interaction gradually disappears and is replaced by severe fluctuations. The randomness and localization may enhance the RKKY interaction between dopants with short and middle distances and in favour of the ferromagnetism.     

Photoluminescence of ZnO and Mn-Doped ZnO Polycrystalline Films Prepared by Plasma Enhanced Chemical Vapour Deposition

ZnO and Mn-doped ZnO polycrystalline films are prepared by plasma enhanced chemical vapour deposition at low temperature （220℃）, and room-temperature photoluminescence of the films is systematically investigated. Analysis from x-ray diffraction reveals that a11 the prepared films exhibit the wurtzite structure of ZnO, and Mndoping does not induce the second phase in the films. X-ray photoelectron spectroscopy confirms the existence of Mn^2＋ ions in the films rather than metalic Mn or Mn^4＋ ions. The emission efficiency of the ZnO film is found to be dependent strongly on the post-treatment and to degrade with increasing temperature either in air or in nitrogen ambient. However, the enhancement of near band edge （NBE） emission is observed after hydrogenation in ammonia plasma, companied with more defect-related emission. Furthermore, the position of NBE shifts towards to high-energy legion with increasing Mn-doped concentration due to Mn incorporation into ZnO lattice.     

Three-Step Growth Optimization of AlN Epilayers by MOCVD

A three-step growth process is developed for depositing high-quality aluminium-nitride （AlN） epilayers on （001） sapphire by low pressure metalorganic chemical vapour deposition （LP-MOCVD）. We adopt a low temperature （LT） A1N nucleation layer （NL）, and two high temperature （HT） A1N layers with different V/Ⅲ ratios. Our results reveal that the optimal NL temperature is 840-880℃, and there exists a proper growth switching from low to high V/Ⅲ ratio for further reducing threading dislocations （TDs）. The screw-type TD density of the optimized AIN film is just 7.86×10^6 cm^-2, about three orders lower than its edge-type one of 2×10^9 cm^-2 estimated by high-resolution x-ray diffraction （HRXRD） and cross-sectional transmission electron microscopy （TEM）.     

Influence of Different Interlayers on Growth Mode and Properties of InN by MOVPE

We grow InN epilayers on different interlayers by metal organic vapour phase epitaxy （MOVPE） method, and investigate the effect of interlayer on the properties and growth mode of InN films. Three InN samples were deposited on nitrided sapphire, low-temperature InN （LT-InN） and high-temperature GaN （HT-GaN）, respectively. The InN layer grown directly on nitrided sapphire owns the narrowest x-ray diffraction rocking curve （XRC） width of 300 aresee among the three samples, and demonstrates a two-dimensional （2D） step-flow-like lateral growth mode, which is much different from the three-dimensional （3D） pillar-like growth mode of LT-InN and HT-GaN buffered samples. It seems that mismatch tensile strain is helpful for the lateral epitaxy of InN film, whereas compressive strain promotes the vertical growth of InN films.     

The important role of Mn in the room-temperature ferromagnetism of Mn-doped GaN films

Mn-doped GaN films (Ga_1−xMn_xN) were grown on sapphire (0 0 0 1) using Laser assisted Molecular Beam Epitaxy (LMBE). High-quality nanocrystalline Ga_1−xMn_xN films with different Mn concentration were then obtained by thermal annealing treatment for 30 min in the ammonia atmosphere. Mn ions were incorporated into the wurtzite structure of the host lattice by substituting the Ga sites with Mn³⁺ due to the thermal treatment. Mn³⁺, which is confirmed by XPS analysis, is believed to be the decisive factor in the origin of room-temperature ferromagnetism. The better room-temperature ferromagnetism is given with the higher Mn³⁺ concentration. The bound magnetic polarons (BMP) theory can be used to prove our room-temperature ferromagnetic properties. The film with the maximum concentration of Mn³⁺ presents strongest ferromagnetic signal at annealing temperature 950 °C. Higher annealing temperature (such as 1150 °C) is not proper because of the second phase Mn_xGa_y formation.     

Preparation of P-rich InP surfaces via MOCVD and surface characterization in UHV

For the first time direct contamination-free transfer to UHV was achieved for the P-rich InP(100) surface that is the easiest to prepare and control in the MOCVD environment. To avoid contamination during transfer a commercial MOCVD apparatus was modified to allow for transfer of samples to the 10^-9 mbar UHV range within a very short time (less than 20 s) [1]. Epitaxial InP(100) films were prepared with TBP (tertiarybutylphosphine) and TMIn (trimethylindium) as precursors. In situ reflectance anisotropy spectroscopy (RAS) was carried out in the MOCVD environment. After transfer of the sample to UHV the same RAS spectrum was recovered. Auger-electron spectra (AES) confirmed the P-termination of the surface reconstructions suggested by RAS. Received: 19 October 1998 / Accepted: 21 April 1999 / Published online: 14 July 1999     

Structural and Magnetic Properties of Sm Implanted GaN

The structural and magnetic properties of Sm ion-implanted GaN with different Sm concentrations are investigated. XRD results do not show any peaks associated with second phase formation. Magnetic investigations performed by superconducting quantum interference device reveal ferromagnetic behavior with an ordering tem- perature above room temperature in all the implanted samples, while the effective magnetic moment per Sin obtained from saturation magnetization gives a much higher value than the atomic moment of Sm. These results could be explained by the phenomenological model proposed by Dhar et al. [Phys. Rev. Lett. 94（2005）037205, Phys. Rev. B 72（2005）245203] in terms of a long-range spin polarization of the GaN matrix by the Sm atoms.     

Electronic States and Spatial Charge Distribution of Single Mn Impurity in Diluted Magnetic Semiconductors

The electronic and magnetic properties as well as the spatial charge distribution of single Mn impurity in III--V diluted magnetic semiconductors are obtained when the degeneracy of the p orbits contributed from the four nearest-neighbouring As(N) atoms is taken into account. We show that in the ground state, the Mn spin is strongly antiferromagnetically coupled to the surrounding As(N) atoms when the p-d hybridization V_pd is large and both the hole level E_v and the impurity level E_d are close to the Fermi energy. The spatial charge distribution of the Mn acceptor in the (110) plane is non-spherically symmetric, in good agreement with the recent STM images.     

Comparison of annealing effects on Zn-doped GaMnAs and undoped GaMnAs epilayers

To compare the annealing effects on GaMnAs-doped with Zn (GaMnAs:Zn) and undoped GaMnAs (u-GaMnAs) epilayers, we grew GaMnAs thin films at 200 °C by molecular beam epitaxy (MBE) on GaAs substrates, and they were annealed at temperatures ranging from 220 °C to 380 °C for 100 min in air. These epilayers were characterized by high-resolution X-ray diffraction (XRD), electrical, and magnetic measurements. A maximum resistivity at temperatures T_m close to the Curie temperatures T_c was observed from the measurement of the temperature-dependent resistivity ρ(T) for both the GaMnAs:Zn and the u-GaMnAs samples. We found, however, that the maximum temperature T_m observed for GaMnAs:Zn epilayers increased with increasing annealing temperature, which was different from the result with the u-GaMnAs epilayers. The formation of GaAs:Zn and MnAs or Mn-Zn-As complexes with increasing annealing temperature is most likely responsible for the differences in appearance.     

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.     

Luminescent Characteristics of Near Ultraviolet InGaN/GaN MQWs Grown on Grooved Sapphire Substrates Fabricated by Wet Chemical Etching

InGaN/GaN multiple quantum wells （MQWs） are grown on planar and maskless periodically grooved sapphires by metal organic vapour phase epitaxy （MOCVD）. High-resolution x-ray rocking curves and transmission electron microscopy （TEM） are adopted to characterize the film quality. Compared with the MQWs grown on planar sapphire, the sample grown on grooved sapphire shows better crystalline quality： a remarkable reduction of dislocation densities is achieved. Meanwhile, the MQWs grown on grooved sapphire show two times larger PL intensity at room temperature. Temperature-dependent PL measurements are adopted to investigate the luminescence properties. The luminescence thermal quenching based on a fit to the Arrhenius plot of the normalized integrated PL intensity over the measured temperature range suggests that the nonradiative recombination centres （NRCs） are greatly reduced for the sample grown on grooved sapphire. We assume that the reduction of dislocations which act as NRCs is the main reason for the sample grown on pattern sapphire having higher PL intensity.     

Adsorption and decomposition of triethylsilane on Si(1 0 0)

The adsorption and decomposition of triethylsilane (TES) on Si(1 0 0) were studied using temperature programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), electron stimulated desorption (ESD), and X-ray photoelectron spectroscopy (XPS). TPD and HREELS data indicate that carbon is thermally removed from the TES-dosed Si(1 0 0) surface via a β-hydride elimination process. At high exposures, TPD data shows the presence of physisorbed TES on the surface. These species are characterized by desorption of TES fragments at 160 K. Non-thermal decomposition of TES was studied at 100 K by irradiating the surface with 600 eV electrons. ESD of mass 27 strongly suggests that a β-hydride elimination process is a channel for non-thermal desorption of ethylene. TPD data indicated that electron irradiation of physisorbed TES species resulted in decomposition of the parent molecule and deposition of methyl groups on the surface that desorbed thermally at about 900 K. Without electron irradiation, mass 15 was not detected in the TPD spectra, indicating that the production of methyl groups in the TPD spectra was a direct result of electron irradiation. XPS data also showed that following electron irradiation of TES adsorbed on Si(1 0 0), carbon was deposited on the surface and could not be removed thermally.     

Properties of ZnO thin films grown on Si substrates by photo-assisted MOCVD

ZnO thin films were grown on (1 0 0) p-Si substrates by Photo-assisted Metal Organic Chemical Vapor Deposition (PA-MOCVD) using diethylzinc (DEZn) and O₂ as source materials and tungsten-halogen lamp as a light source. The effects of tungsten-halogen lamp irradiation on the surface morphology, structural and optical properties of the deposited ZnO films have been investigated by means of atomic force microscope (AFM), X-ray diffraction and photoluminescence (PL) spectra measurements. Compared with the samples without irradiation, the several characteristics of ZnO films with irradiation are improved, including an improvement in the crystallinity of c-axis orientation, an increase in the grain size and an improvement in optical quality of ZnO films. These results indicated that light irradiation played an important role in the growth of ZnO films by PA-MOCVD.