Laser-plasma deposited nanosized layers of ferromagnetic semiconductors and silicon- and germanium-based Heusler alloys

The electric, magnetic resonance, and magneto-optical properties of thin laser-plasma deposited 50–100-nm layers of diluted magnetic semiconductors Ge:(Mn, Al)/GaAs, Ge:(Mn, Al)/Si, and Heusler alloys Co₂MnSi/Si, Co₂MnSi/GaAs, and Fe₂CrSi/GaAs with T _c > 293 K were studied. Anomalous ferromagnetic resonance in Ge:(Mn, Al) layers, ferromagnetism in CoSi/Si characterized by strong hysteresis in the magneto-optic Kerr effect, and the anomalous Hall effect at 293 K were observed.     

Ferromagnetism in epitaxial layers of gallium and indium antimonides and indium arsenide supersaturated by manganese impurity

We report on laser synthesis of thin 30–200 nm epitaxial layers with mosaic structure of diluted magnetic semiconductors GaSb:Mn and InSb:Mn with the Curie temperature T_C above 500 K and of InAs:Mn with T_C no less than 77 K. The concentration of Mn was ranged from 0.02 to 0.15. In the case of InSb:Mn and InAs:Mn films, the additional pulse laser annealing was needed to achieve ferromagnetic behavior. We used Kerr and Hall effects methods as well as ferromagnetic resonance (FMR) spectroscopy to study magnetic properties of the samples. The anisotropy FMR was observed for both layers of GaSb:Mn and InSb:Mn up to 500 K but it takes place with different temperature dependencies of absorption spectra peaks. The resonance field value and amplitude of FMR signal on the temperature is monotonically decreased with the temperature increase for InSb:Mn. In the case of GaSb:Mn, this dependence is not monotonic.     

Magnetic and optical properties of self-organized InMnAs quantum dots

Ten layers of self-assembled InMnAs quantum dots with InGaAs barrier were grown on high resistivity (1 0 0) p-type GaAs substrates by molecular beam epitaxy (MBE). The presence of ferromagnetic structure was confirmed in the InMnAs diluted magnetic quantum dots. The ten layers of self-assembled InMnAs quantum dots were found to be semiconducting, and have ferromagnetic ordering with a Curie temperature, T_C=80 K. It is likely that the ferromagnetic exchange coupling of sample with T_C=80 K is hole mediated resulting in Mn substituting In and is due to the bound magnetic polarons co-existing in the system. PL emission spectra of InMnAs samples grown at temperature of 275, 260 and 240 °C show that the interband transition peak centered at 1.31 eV coming from the InMnAs quantum dot blueshifts because of the strong confinement effects with increasing growth temperature.     

Ferromagnetism in epitaxial germanium and silicon layers supersaturated with managanese and iron impurities

The possibility of laser synthesis of diluted magnetic semiconductors based on germanium and silicon doped with manganese or iron up to 10–15 at % has been shown. According to data on the electronic levels of 3d atoms in semiconductors, Mn and Fe impurities are most preferable for realizing ferromagnetism in Ge and Si through the Ruderman-Kittel-Kasuya-Yosida mechanism. Epitaxial Ge and Si layers 50–110 nm in thickness were grown on gallium arsenide or sapphire single crystal substrates heated to 200–480°C. The content of a 3d impurity has been measured by x-ray spectroscopy. The ferromagnetism of layers and high magnetic and acceptor activities of Mn in Ge, as well as of Mn and Fe in Si, are manifested in the observation of the Kerr effect, anomalous Hall effect, high hole conductivity, and anisotropic ferromagnetic resonance at 77–500 K. According to the ferromagnetic resonance data, the Curie point of Ge:Mn and Si:Mn on a GaAs substrate and of Si:Fe on an Al₂O₃ substrate is no lower than 420, 500, and 77 K, respectively.     

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.     

Anomalous ferromagnetic resonance in manganese- and aluminum-doped germanium layers deposited from the laser plasma

Ferromagnetic resonance (FMR) with an anomalous angular dependence has been observed in the Ge:(Mn, Al)/GaAs nanolayers deposited from laser plasma at a reduced temperature of 150°C. The resonance is associated with the needle-like inclusions of a high-temperature ferromagnetic phase with the Curie temperature T _C > 293 K. Such a magnetic anisotropy is confirmed by the atomicforce and magneticforce microscopy of a side chip. A low-temperature ferromagnetic phase with normal FMR and T _C < 212 K is formed between the needle-like inclusions. This phase manifests itself in the anomalous Hall effect at 77 K and probably is a solid solution of manganese in germanium.

     

Anomalous ferromagnetic resonance in manganese- and aluminum-doped germanium layers deposited from the laser plasma

Ferromagnetic resonance (FMR) with an anomalous angular dependence has been observed in the Ge:(Mn, Al)/GaAs nanolayers deposited from laser plasma at a reduced temperature of 150°C. The resonance is associated with the needle-like inclusions of a high-temperature ferromagnetic phase with the Curie temperature T _C > 293 K. Such a magnetic anisotropy is confirmed by the atomicforce and magneticforce microscopy of a side chip. A low-temperature ferromagnetic phase with normal FMR and T _C < 212 K is formed between the needle-like inclusions. This phase manifests itself in the anomalous Hall effect at 77 K and probably is a solid solution of manganese in germanium.     

Magnetic behavior of MnAs precipitates in Ga1−xMnxAs diluted magnetic semiconductor

Ferromagnetic Ga_1−xMn_xAs layers (where x≈4.7–5.5%) were grown on (1 0 0) GaAs substrates by molecular beam epitaxy. These p-type (Ga,Mn)As films were revealed to have a ferromagnetic structure and ferromagnetism is observed up to a Curie temperature of 318 K, which is ascribed to the presence of MnAs secondary magnetic phases within the film. It is highly likely that the phase segregation occurs due to the high Mn cell temperature around 890–920 °C, as it is well established that GaMnAs is unstable at such a high temperature. The MnAs precipitate in the samples with x≈4.7–5.5% has a Curie temperature T_c≈318 K, which was characterized from field-cooled and zero-field-cooled magnetization curves.     

Strain relaxation of epitaxial SiGe layer and Ge diffusion during Ni silicidation on cap-Si/SiGe/Si(0 0 1)

Strain relaxation of the epitaxial SiGe layer and Ge diffusion during nickel silicidation by rapid thermal annealing the structure of Ni(≅14 nm)/cap-Si(≅26 nm)/Si_0.83Ge_0.17/Si(0 0 1) at the elevated annealing temperatures, T_A, were investigated by X-ray diffraction analyses of high-resolution ω-2θ scan and reciprocal space mapping. The analyses showed a much larger strain relaxation at a lower T_A and a reduction in Ge content in the SiGe layer of Ni/SiGe/Si(0 0 1) after thermal annealing compared to the case of cap-Si/SiGe/Si(0 0 1). The results indicate that the strain relaxation of the SiGe layers in NiSi/SiGe/Si(0 0 1) is related to the phenomena of NiSi agglomeration and penetration into the SiGe layer during silicidation at elevated anneal temperatures ≥750 °C. At elevated T_A ≥ 750 °C, Ge diffused into the intact cap-Si area during silicidation.     

Carrier spin polarization in ferromagnet-semiconductor (Ga,Mn)As/GaAs structures

The effect of ferromagnetic layers on the spin polarization of holes and electrons in ferromagnet-semiconductor superlattices with a fixed Mn δ-layer thickness of 0.11 nm and different GaAs interlayer thicknesses varying in the range from 2.5 to 14.4 nm and a fixed number of periods (40) is studied by means of hot-electron photoluminescence (HPL). Here, our study of the HPL demonstrates that the holes in δ-layers of (Ga,Mn)As DMS occupy predominantly the Mn acceptor impurity band. The width of the impurity band decreases with the increase of the interlayer distance. We also found that an increase in the GaAs interlayer thickness softens the magnetic properties of the ferromagnetic layers as well as reduces the carrier polarization. It is demonstrated that the hole spin polarization in the DMS layers and spin polarization of electrons in nonmagnetic GaAs are proportional to the sample magnetization.     

FMR studies in the TbFeCo/GdFeCoSi bilayers

Bilayers, TbFeCo/GdFeCoSi, made by sputtering on glass substrate with buffer and capping layers were studied by measuring the hysteresis loop and by ferromagnetic resonance (FMR). When the field H was applied along the film normal, a double H_C hysteresis loop related to the two sublayers was observed. In ferromagnetic resonance measurements, a peculiar out-of-plane angular dependence of FMR spectrum was obtained. When scanning field H was 0-637 kA/m less than the anisotropy field of TbFeCo sublayer, two FMR peaks were observed. One peak was characteristic of uniaxial and unidirectional anisotropy. The anisotropy constants were obtained by fitting the data with the theory of FMR, and this peak was considered to be related to the low anisotropy GdFeCoSi layer. The second peak appeared only when the dc field H was orientated in a limited angular range around 180°. This peak was considered to be related to an uncoupled interfacial GdFeCoSi sublayer near Al capping layer. However, when H was scanned between 0-1114 kA/m, only one peak is observed due to magnetization reversal of TbFeCo layer with uniaxial anisotropy.     

Analysis of magnetic field dependent mobility in ferromagnetic Ga1−xMnxAs layers

The magneto-transport properties of ferromagnetic Ga_1−xMn_xAs epilayers with Mn mole fractions in the range of x≈2.2-4.4% were investigated through Hall effect measurements. The magnetic field-dependent Hall mobility for a metallic sample with x≈2.2% in the temperature range of T=0-300 K was analyzed by magnetic field-dependent mobility model including an activation energy of Mn acceptor level. This model provides outstanding fits to the measured data up to T=300 K. It was found that the acceptor levels with activation energies of 112 meV at B=0 Oe decreased to 99 meV at B=5 kOe in the ferromagnetic region. The decrease in acceptor activation energy was due to the spin splitting of the Mn acceptor level in the ferromagnetic region, and was responsible for increase in carrier concentration.     

Fabrication of ferromagnetic (Ga,Mn)As by ion irradiation

Using Mn⁺ implantation following ion beam-induced epitaxial crystallization (IBIEC) annealing, high Curie temperature ferromagnetic (Ga,Mn)As thin film was fabricated. The crystalline quality of the Mn⁺ implanted layer was identified by X-ray diffraction (XRD) and transmission electron microscopy (TEM). A clear ferromagnetic transition at T_c 253 K was observed by magnetization vs. temperature measurement. We infer that IBIEC treatment is a useful method not only for the low-temperature annealing of (Ga,Mn)As thin films but also for other dilute magnetic semiconductor (DMS) samples.     

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.     

Low temperature formation of multi-layered structures of ferromagnetic silicide Fe3Si and Ge

Low-temperature (<300 °C) molecular beam epitaxy of Fe₃Si/Ge was investigated. By optimizing growth conditions, Fe₃Si layers with a flat interface and good crystallinity were epitaxially grown on Ge(1 1 1) substrates. In addition, double heteroepitaxial growth of Fe₃Si/Ge on high quality Fe₃Si/Ge substrates was investigated. Reflective high-energy electron diffraction measurements suggested Fe₃Si and Ge layers were epitaxially grown on Fe₃Si/Ge substrates. However, transmission electron microscopy measurements indicated stacking faults formed in the intermediate Ge and top Fe₃Si layers. Improved crystallinity of the intermediate Ge layer is essential to realize high quality [Fe₃Si/Ge]₂ multi-layered structures.     

Magnetic phases in lanthanum-strontium manganite-cobaltite La1.25Sr0.75MnCoO6

Two methods—the solid-phase high-temperature (1300 °C) and the liquid-phase low-temperature (750 °C) routes—were used to synthesize the complex oxide La_1.25Sr_0.75MnCoO₆, which has the structure of rhombohedral perovskite and is characterized by a disordered distribution of Mn and Co in structural sites. It was found by means of X-ray absorption near edge spectroscopy (XANES) at the K-edge that mixed valence states of Co²⁺/Co³⁺ and Mn³⁺/Mn⁴⁺, exist in both phases. Measurements of dc magnetization and real (χ′) and imaginary (χ″) parts of the ac susceptibility showed that the magnetic properties of these oxides are determined by a ferromagnetic transition at T_C=217 K and a frequency-dependent transition at T_g<100 K. The high frequency dependence of T_g is indicative of the cluster-glass behavior of La_1.25Sr_0.75MnCoO₆ (7 5 0) at T<T_C within the ferromagnetic state.     

Ferromagnetic semiconductor Ge1−x−ySnxMnyTe with phase transformation of ferroelectric type

It is expected that joint existence of ferromagnetic properties and ferroelectric structural phase transition in diluted magnetic semiconductors IV-VI leads to new possibilities of these materials. Temperature of ferroelectric transition for such crystals can be tuned by the change of Sn/Ge ratio. Magnetic susceptibility, Hall effect, resistivity and thermoelectric power of Ge_1−x−ySn_xMn_yTe single crystals grown by Bridgeman method (x=0.083-0.115; y=0.025-0.124) were investigated within 4.2-300 K. An existence of FM ordering at T_C∼50 K probably due to indirect exchange interaction between Mn ions via degenerated hole gas was revealed. A divergence of magnetic moment temperature dependences at T?T_C in field-cooled and zero-field-cooled regimes is obliged to magnetic clusters which are responsible for superparamagnetism at T>T_C≈T_f (freezing temperature) and become ferromagnetic at T_C arranging spin glass state at T<T_f≈T_C. Phase transition of ferroelectric type at T≈46 K was revealed. Anomalous Hall effect which allows to determine magnetic moment was observed.     

Effect of electron-beam irradiation on the magnetic properties of Ga1−xMnxAs thin films grown on GaAs (100) substrates

The effect of electron-beam irradiation on the magnetic properties of (Ga_1−xMn_x)As thin films grown on GaAs (100) substrates by using molecular beam epitaxy was investigated. The ferromagnetic transition temperature (T_c) of the annealed (Ga_0.933Mn_0.067)As thin films was 160 K. The T_c value for the as-grown (Ga_0.933Mn_0.067)As thin films drastically decreased with increasing electron-beam current. This significant decrease in the T_c value due to electron-beam irradiation originated from the transformation of Mn substituted atoms, which contributed to the ferromagnetism, into Mn interstitials or Mn-related clusters. These results indicate that the magnetic properties of (Ga_1−xMn_x)As thin films grown on GaAs (100) substrates are significantly affected by electron-beam irradiation.     

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 of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.