Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

The effect of Co ion implantation on Ge1−xMnx films

Ge_1−xMn_x (x = 0, 0.013, 0.0226, 0.0339, 0.0565, 0.0678, 0.0904, 0.113) films prepared by magnetron sputtering at 773 K had a Ge cubic structure except for x = 0.1130. Co ion implantation into these films can effectively prevent the formation of a second phase. Both single-doped and co-doped samples were ferromagnetic at room temperature. The d-d exchange interaction between the interstitial Mn (MnT) and the substituted Mn (Mn_Ge) resulted in ferromagnetism in the sputtered films. Since Co ion implantation destroyed the Mn_T-Mn_Ge-Mn_T complex, the saturated magnetization decreased. Hall measurements revealed that the Co ion implanted films were n-type semiconductors, and the anomalous Hall Effect (AHE) suggested the ferromagnetism was carrier-mediated in the implanted films.     

MnxGe1−x thin layers studied by TEM, X-ray absorption spectroscopy and SQUID magnetometry

Mn_0.06Ge_0.94 samples have been grown by molecular-beam epitaxy on Ge(0 0 1)2 × 1. High-resolution transmission electron microscopy shows the coexistence of an ordered diluted Mn_0.06Ge_0.94 film and of nanoscopic crystallites, which were identified as Mn₅Ge₃ by electron diffraction. The magnetic properties of the Mn_0.06Ge_0.94 samples show a superposition of a paramagnetic behavior, due to the interaction of Mn atoms diluted in the Ge host, and a ferromagnetic behavior attributed to the Mn₅Ge₃ crystallites dispersed into the films. The Mn L_2,3 X-ray absorption spectra of the Mn_0.06Ge_0.94 films exhibit a lineshape typical of metallic Mn, with considerably reduced multiplet structure.     

Structural, magnetic and electronic transport properties of MnxGe1−x/Ge(0 0 1) films grown by MBE at 350 °C

We report on the structural, magnetic and electronic transport properties of thin Mn_xGe_1−x films grown at 350 °C. Isolated Mn₅Ge₃ nanoclusters, about 100 nm in size, were formed at the top surface of the film, dominating the magnetic properties of the whole film. Electronic transport properties show Mn doping effect indicating the presence of substitutional Mn ions dispersed in the Ge host, contributing to the formation of a Mn_xGe_1−x diluted phase. Electrical behaviour indicates a saturation effect with the raise of the nominal Mn concentration in the film, above x ≅ 0.03.     

Structural and surface properties of Si1−xGex thin films obtained by reduced pressure CVD

This paper investigates the structure and surface characteristics, and electrical properties of the polycrystalline silicon-germanium (poly-Si_1−xGe_x) alloy thin films, deposited by vertical reduced pressure CVD (RPCVD) in the temperature range between 500 and 750 °C and a total pressure of 5 or 10 Torr. The samples exhibited a very uniform good quality films formation, with smooth surface with rms roughness as low as 7 nm for all temperature range, Ge mole fraction up to 32% (at 600 °C), textures of 〈2 2 0〉 preferred orientation at lower temperatures and strong 〈1 1 1〉 at 750 °C, for both 5 and 10 Torr deposition pressures. The ³¹P⁺ and ¹¹B⁺ doped poly-Si_1−xGe_x films exhibited always lower electrical resistivity values in comparison to similar poly-Si films, regardless of the employed anneal temperature or implantat dose. The results indicated also that poly-Si_1−xGe_x films require much lower temperature and ion implant dose than poly-Si to achieve the same film resistivity. These characteristics indicate a high quality of obtained poly-Si_1−xGe_x films, suitable as a gate electrode material for submicron CMOS devices.     

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.     

Photoluminescence investigation of ferromagnetic Ga1−xMnxN layers with GaN templates grown on sapphire (0 0 0 1) substrates

We have investigated the temperature and composition dependent photoluminescence (PL) spectra in Ga_1−xMn_xN layers (where x ≈ 0.1-0.8%) grown on sapphire (0 0 0 1) substrates using the plasma-enhanced molecular beam epitaxy technique. The efficient PL is peaked in the red (1.86 eV), yellow (2.34 eV), and blue (3.29 eV) spectral range. The band-gap energy of the Ga_1−xMn_xN layers decreased with increasing temperature and manganese composition. The band-gap energy of the Ga_1−xMn_xN layers was modeled by the Varshni equation and the parameters were determined to be α = 2.3 × 10⁻⁴, 2.7 × 10⁻⁴, 3.4 × 10⁻⁴ eV/K and β = 210, 210, and 230 K for the manganese composition x = 0.1%, 0.2%, and 0.8%, respectively. As the Mn concentration in the Ga_1−xMn_xN layers increased, the temperature dependence of the band-gap energy was clearly reduced.     

Band-edge exciton transitions in (Ga1−xMnx)N diluted magnetic semiconductor films with above room temperature ferromagnetic transition

(Ga_1−xMn_x)N thin films grown on GaN buffer layers by using molecular beam epitaxy were investigated with the goal of producing diluted magnetic semiconductors (DMSs) with band-edge exciton transitions for applications in optomagnetic devices. The magnetization curve as a function of the magnetic field at 5 K indicated that ferromagnetism existed in the (Ga_1−xMn_x)N thin films, and the magnetization curve as a function of the temperature showed that the ferromagnetic transition temperature of the (Ga_1−xMn_x)N thin film was above room temperature. Photoluminescence and photoluminescence excitation spectra showed that band-edge exciton transitions in (Ga_1−xMn_x)N thin films appeared. These results indicate that the (Ga_1−xMn_x)N DMSs with a magnetic single phase hold promise for potential applications in spin optoelectronic devices in the blue region of the spectrum.     

Analysis of the Ge1−xCx films deposited by MFMST

Ge_1−xC_x films deposited by using a medium frequency magnetron sputtering technique (MFMST) were analyzed with X-ray photoelectron and Raman spectroscopy. The deposited Ge_1−xC_x films consist of C, Ge, GeC and GeO_y. The GeC content in the Ge_1−xC_x films linearly decreases, and the C content linearly increases with increasing deposition temperature from 150 to 350 °C. The GeC content decreases from 11.6% at a substrate bias of 250 V to a lowest value of 9.6% at 350 V, then increases again to 10.4% at 450 V. While the C content increases from 49.0% at the bias of 250 V to a largest value of 58.0% at 350 V and then maintains this level at 450 V. It is found that selecting a bias parameter seems more effective than deposition temperature if we want to obtain a higher content of GeC in the deposited films. In addition, a new method is presented in this paper to estimate the changes of GeC content in the Ge_1−xC_x films by observing the shifts of Ge-Ge LO phonon peak in Raman spectra for the Ge_1−xC_x films. The related mechanism is also discussed in this paper.     

Elemental depth profiling of a-Si1−xGex:H films by elastic recoil detection analysis and secondary ion mass spectrometry

The hydrogen content in a-Si_1−xGe_x:H thin films is an important factor deciding the density and the optical band gap. We measured the elemental depth profiles of hydrogen together with Si and Ge by elastic recoil detection analysis (ERDA) combined with Rutherford backscattering (RBS) using MeV He²⁺ ions. In order to determine the hydrogen depth profiles precisely, the energy- and angle-dependent recoil cross-sections were measured in advance for the standard sample of a CH₃⁺-implanted Si substrate. The cross-sections obtained here are reproduced well by a simple expression based on the partial wave analysis assuming a square well potential (width: r₀ = 2.67 × 10⁻¹³ cm, depth: V₀ = −36.9 MeV) within 1%. For the a-Si_1−xGe_x:H films whose elemental compositions were determined by ERDA/RBS, we measured the secondary ions yields of HCs₂⁺, SiCs₂⁺, H⁻, Si⁻ and Ge⁻ as a function of Ge concentration x. As a result, it is found that the useful yield ratios of HCs₂⁺/SiCs₂⁺, H⁻/Si⁻ and Ge⁻/Si⁻ are almost constant and thus the elemental depth profiles of the a-Si_1−xGe_x:H films can be also determined by secondary ion mass spectrometry (SIMS) within 10% free from a matrix effect.     

Annealing of thin Zr films on Si1−xGex(0≤x≤1): X-ray diffraction and Raman studies

X-ray diffraction experiments have been combined with Raman scattering and transmission electron microscopy data to analyze the result of rapid thermal annealing (RTA) applied to Zr films, 16 or 80 nm thick, sputtered on Si_1−xGe_x epilayers (0≤x≤1). The C49 Zr(Si_1−xGe_x)₂ is the unique phase obtained after complete reaction. ZrSi_1−xGe_x is formed as an intermediate phase. The C49 formation temperature T_f is lowered by the addition of Ge in the structure. Above a critical Ge composition close to x=0.33, a film microstructure change was observed. Films annealed at temperatures close to T_f are continuous and relaxed. Annealing at T>T_f leads to discontinuous films: surface roughening resulting from SiGe diffusion at film grain boundaries occurred. Grains are ultimately partially embedded in a SiGe matrix. A reduction in the lattice parameters as well as a shift of Raman lines are observed as T exceeds T_f. Both Ge non-stoichiometry and residual stress have been considered as possible origins for these changes. However, as Ge segregation has never been detected, even by using very efficient techniques, it is thought that the changes originate merely from residual stress. The C49 grains are expected to be strained under the SiGe matrix effect and shift of the Raman lines would indicate the stress is compressive. Some simple evaluations of the stress values indicate that it varies between −0.3 and −3.5 GPa for 0≤x≤1 which corresponds to a strain in the range (−0.11, −1.15%). X-ray and Raman determinations are in good agreement.     

Structural and magnetic properties of Mg(In2−xMnx)O4 system

We synthesized the Mn-doped Mg(In_2−xMn_x)O₄ oxides with 0.03?x?0.55 using a solid-state reaction method. The X-ray diffraction patterns of the samples were in a good agreement with that of a distorted orthorhombic spinel phase. Their lattice parameters and unit-cell volumes decrease with x due to the substitution of the smaller Mn³⁺ ions to the larger In³⁺ ions. The undoped MgIn₂O₄ oxide presents diamagnetic signals for 5 K?T?300 K. The M(H) at T=300 K reveals a fairly negative-sloped linear relationship. Neither magnetic hysteresis nor saturation behavior was observed in this parent sample. For the Mn-doped samples, however, positive magnetization were observed between 5 and 300 K even if the x value is as low as 0.03. The mass susceptibility enhances with Mn content and it reaches the highest value of 1.4×10⁻³ emu/g Oe (at T=300 K) at x=0.45. Furthermore, the Mn-doped oxides with x=0.06 and 0.2, respectively, exhibit nonlinear magnetization curves and small hysteretic loops in low magnetic fields. Susceptibilities of the Mn-doped samples are much higher than those of MnO₂, Mn₂O₃ oxides, and Mn metals. These results show that the oxides have potential to be magnetic semiconductors.     

A Hall coefficient investigation of ferromagnetic Ga1−xMnxAs layers on (100) GaAs substrates

Ferromagnetic Ga_1−xMn_xAs epilayers with Mn mole fraction in the range of x≈2.2-4.4% were grown on semi-insulating (100) GaAs substrates using the molecular beam epitaxy technique. The transport properties of these epilayers were investigated through Hall effect measurements. The measured hole concentration of Ga_1−xMn_xAs layers varied from 4.4×10¹⁹ to 3.4×10¹⁹ cm⁻³ in the range of x≈2.2-4.4% at room temperature. From temperature dependent resisitivity data, the sample with x≈4.4% shows typical behavior for insulator Ga_1−xMn_xAs and the samples with x≈2.2 and 3.7% show typical behavior for metallic Ga_1−xMn_xAs. The Hall coefficient for the samples with x≈2.2 and 4.4% was fitted assuming a magnetic susceptibility given by Curie-Weiss law in a paramagnetic region. This model provides good fits to the measured data up to and the Curie temperature T_c was estimated to be 65, 83 K and hole concentration p was estimated to be 5.1×10¹⁹, 4.6×10¹⁹ cm⁻³ for the samples with x≈2.2 and 4.4%, respectively, confirming the existence of an anomalous Hall effect for metallic and insulating samples.     

Role of carbon in the formation of hard Ge1−xCx thin films by reactive magnetron sputtering

We have deposited germanium carbide (Ge_1−xC_x) films on Si(1 0 0) substrate via radio-frequency (RF) reactive magnetron sputtering in a CH₄/Ar mixture discharge, and explored the effects of carbon content (x) on the chemical bonding and hardness for the obtained films. We find that x significantly influences the chemical bonding, which leads to a pronounced change in the hardness of the film. To reveal the relationship between the chemical bonding and hardness, first-principles calculations have been carried out. It is shown that as x increases from 0 to 0.33, the fraction of sp³ C-Ge bonds in the film increases at the expense of Ge-Ge bonds, which promotes formation of a strong covalently bonded network, and thus enhances the hardness of the film. However, as x further increases from 0.33 to 0.59, the fraction of sp³ C-Ge bonds in the film gradually reduces, while that of sp³ C-H and graphite-like sp² C-C bonds increases, which damages the compact network structure, resulting in a sharp decrease in the hardness. This investigation suggests that the medium x (0.17<x<0.40) is most favorable to the preparation of hard Ge_1−xC_x films due to the formation of dominant sp³ C-Ge bonds.     

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.     

Synthesis and magnetic properties of Zn1−xMnxO films prepared by the sol-gel method

We report on the ferromagnetic characteristics of Zn_1−xMn_xO films (x=0.1-0.3) prepared by the sol-gel method on silicon substrates using transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffractometry (XRD) and superconducting quantum interference device (SQUID) magnetometry at various temperatures. Magnetic measurement show that the Curie temperature (T_C) and the coercive field (H_C) were ∼39 K and ∼2100 Oe for the film of x=0.2, respectively. EDS and TEM measurements indicate that Mn content at the interface is significantly higher than that at the center of the Zn_0.8Mn_0.2O film showing the ratio, Zn:Mn:O≅1:12:15. This experimental evidence suggests that ferromagnetic precipitates containing manganese oxide may be responsible for the observed ferromagnetic behavior of the film.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

Structural and photoluminescence properties of thermally evaporated Cd1−xMnxS nano-crystalline films

Thin films of Cd_1−xMn_xS (0≤x≤0.5) were formed on glass substrates by resistive vacuum thermal evaporation. All the films were deposited at 300 K and the films were annealed at 373, 473 and 573 K for 1 h in a vacuum of 10⁻⁶ mbar. Atomic force microscopy (AFM) studies showed that all the films investigated were in nano-crystalline form with a grain size in the range 36-82 nm. All the films exhibited a wurtzite structure of the host material. The lattice parameters varied linearly with composition following Vegard’s law in the entire composition range. Photoluminescence studies showed that two distinct emission bands were observed for each Cd_1−xMn_xS compound. One corresponds to internal transition and the other one is due to the transition of Mn²⁺ ions in interstitial sites or in small ‘Mn’ chalcogenic clusters.     

Structural and magnetic phase diagram and room temperature CMR effect of La1−xAgxMnO3

The study of the structural and magnetic phase diagram of the manganites La_1−xAg_xMnO₃ shows similarity with the La_1−x′Sr_x′MnO₃ series, involving a metallic ferromagnetic domain at relatively high temperature (≈300 K). The Ag-system differs from the Sr-one by a much smaller homogeneity range (x≤1/6) and the absence of charge ordering. But the most important feature of the Ag-manganites deals with the exceptionally high magnetoresistance (−25%) at room temperature under 1.2 T, that appears for the composition x=1/6. The latter is interpreted as the coincidence of the optimal double exchange condition (Mn³⁺:Mn⁴⁺=2) with T_max=300 K (maximum of the ρ(T) curve in zero field).     

Optical properties of bulk Zn1−xCoxO magnetic semiconductors

Polycrystalline Zn_1−xCo_xO (x=0, 0.02, 0.05, 0.10 and 0.15) oxides have been synthesized by solid state reaction via sintering ZnO and Co powders in open air. X-ray diffraction analyses using Rietveld refinement indicate that a stoichiometric single phase with a wurtzite-like structure was found in Zn_1−xCo_xO samples with x up to 0.10. The elemental mapping using energy dispersive X-ray spectroscopic analyses presents a uniform distribution of Co. Optical transmittance measurements show that several extra absorption bands appear in the Co-doped ZnO, which is due to the transitions between the crystal-field-split 3d levels of tetrahedral Co²⁺ substituting Zn²⁺ ions. Raman measurements show that limited host lattice defects are induced by Co doping. Magnetization measurements reveal that the Co-doped ZnO samples are paramagnetic due to the absence of free carriers and in low temperature the dominant magnetic interaction is nearest-neighbor antiferromagnetic.