Possible origin of room-temperature ferromagnetism in undoped GaN epilayers implanted with Mn ions

Manganese ions were implanted into unintentionally doped GaN epilayers grown by metal organic chemical vapor deposition (MOCVD). The (Ga,Mn)N and Ga_xMn_y phases were formed after Mn-implanted undoped GaN epilayers annealed at 700 and 800 °C. The samples showed ferromagnetic behavior at room temperature with the highest magnetization obtained in the sample annealed at 800 °C. Ferromagnetic signal reduces as annealing temperature increased above 900 °C. It is believed that the room-temperature ferromagnetic property of Mn-implanted undoped GaN epilayers are mainly from (Ga_,Mn)N. The Ga_xMn_y phases play a critical role in providing holes and also contribute to increasing the ferromagnetic property.     

Enhanced ferromagnetism by preventing antiferromagnetic MnO2 in InP:Be/Mn/InP:Be triple layers fabricated using molecular beam epitaxy

The p-type InP:Be/Mn/InMnP:Be triple epilayers were prepared using MBE to increase T_c (>300 K) by preventing MnO₂. After milling 1–3 nm of epilayers thickness from the top surface, the transmission electron microscopy (TEM) and X-ray diffraction (XRD) revealed no MnO₂ and precipitates, and TEM and XRD results coincide with results of ferromagnetism. The enhanced ferromagnetic transition at >300 K corresponds to InMnP:Be. The increased ferromagnetic coupling without MnO₂ is considered to originate from the increased p–d hybridation. These results demonstrate that InP-based ferromagnetic semiconductor layers having enhanced ferromagnetism can be formed by above process.     

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.     

High temperature annealing effect on structure, optical property and laser-induced damage threshold of Ta2O5 films

Ta₂O₅ films were deposited by conventional electron beam evaporation method and then annealed in air at different temperature from 873 to 1273 K. It was found that the film structure changed from amorphous phase to hexagonal phase when annealed at 1073 K, then transformed to orthorhombic phase after annealed at 1273 K. The transmittance was improved after annealed at 873 K, and it decreased as the annealing temperature increased further. The total integrated scattering (TIS) tests and AFM results showed that both scattering and root mean square (RMS) roughness of films increased with the annealing temperature increasing. X-ray photoelectron spectroscopy (XPS) analysis showed that the film obtained better stoichiometry and the O/Ta ratio increased to 2.50 after annealing. It was found that the laser-induced damage threshold (LIDT) increased to the maximum when annealed at 873 K, while it decreased when the annealing temperature increased further. Detailed damaged models dominated by different parameters during annealing were discussed.     

Characterization of chemically deposited ZnSe/SnO2/glass films: Influence of annealing in Ar atmosphere on physical properties

The Zinc Selenide (ZnSe) thin films have been deposited on SnO₂/glass substrates by a simple and inexpensive chemical bath deposition (CBD). The structural, optical and electrical properties of ZnSe films have been characterized by X-ray diffraction (XRD), Energy Dispersive X-ray Analysis (EDAX), optical absorption spectroscopy, and four point probe techniques, respectively. The films have been subjected to different annealing temperature in Argon (Ar) atmosphere. An increase in annealing temperature does not cause a complete phase transformation whereas it affects the crystallite size, dislocation density and strain. The optical band gap (E_g) of the as-deposited film is estimated to be 3.08 eV and decreases with increasing annealing temperature down to 2.43 eV at 773 K. The as-deposited and annealed films show typical semiconducting behaviour, dρ/dT > 0. Interestingly, the films annealed at 373 K, 473 K, and 573 K show two distinct temperature dependent regions of electrical resistivity; exponential region at high temperature, linear region at low temperature. The temperature at which the transition takes place from exponential to linear region strongly depends on the annealing temperature.     

Magnetic behavior of nanocrystalline powders of Co-doped ZnO diluted magnetic semiconductors synthesized by polymerizable precursor method

This paper reports the first synthesis of nanocrystalline powders of Co-doped ZnO (i.e. Zn_0.9Co_0.1O) diluted magnetic semiconductor by a polymerizable precursor method using nitrate salts of Zn and Co and a mixed solution of citric acid and ethylene glycol as a chelating agent and reaction medium, respectively. The polymeric precursors were characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at 723 K. The precursors were calcined at different temperatures of 773, 873, 973, and 1073 K for 1 h to obtain nanocrystalline powders. The morphology and crystalline size of the calcined particles were evaluated by SEM, TEM and Scherrer's equation. The average particle sizes calcined at 773, 873, 973, and 1073 K for 1 h were, respectively, 20, 60, 80, 150 nm, obtained from TEM. The XRD and Fourier transmission infrared (FT-IR) results indicated that the synthesized Zn_0.9Co_0.1O powders have the pure wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. Room temperature magnetization results revealed a ferromagnetic behavior for the Zn_0.9Co_0.1O powders. Although the specific magnetization seemed to change with the particle size but there was no clear dependency since the largest magnetization was observed in the powders calcined at 873 K (60 nm). Instead, the specific magnetization appeared to show a trend of dependency on the lattice constant c of the wurtzite unit cell.     

Thermal stability of titanium nitride coatings prepared by the mixing technology with laser and plasma

Titanium samples were treated by the mixing technology with laser and plasma (LPN) using different laser power densities. These nitrided samples were then annealed at 473 K, 673 K, 873 K, and 1073 K for 2 h in vacuum, respectively. The samples before and after annealing were characterized at room temperature and compared in terms of microstructure. X-ray diffraction and cross-sectional optical microscopy studies showed that the layer structure of the titanium nitride coating is preserved after annealing at 1073 K when the coating is formed using a laser power density of 8.0 × 10⁵ W/cm². Therefore, titanium nitride coatings produced by LPN demonstrate excellent thermal stability and are potential candidates for high temperature tribological applications.     

Annealing effects on the structural and electrical transport properties of n-type Bi2Te2.7Se0.3 thin films deposited by flash evaporation

N-type Bi₂Te_2.7Se_0.3 thermoelectric thin films with thickness 800 nm have been deposited on glass substrates by flash evaporation method at 473 K. Annealing effects on the thermoelectric properties of Bi₂Te_2.7Se_0.3 thin films were examined in the temperature range 373-573 K. The structures, morphology and chemical composition of the thin films were characterized by X-ray diffraction, field emission scanning electron microscope and energy dispersive X-ray spectroscopy, respectively. Thermoelectric properties of the thin films have been evaluated by measurements of the electrical resistivity and Seebeck coefficient at 300 K. The Hall coefficients were measured at room temperature by the Van der Pauw method. The carrier concentration and mobility were calculated from the Hall coefficient. The films thickness of the annealed samples was measured by ellipsometer. When annealed at 473 K, the electrical resistivity and Seebeck coefficient are 2.7 mΩ cm and −180 μV/K, respectively. The maximum of thermoelectric power factor is enhanced to 12 μW/cm K².     

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.     

Intense and broad photoluminescence at room temperature in structurally disordered Ba[Zr0.25Ti0.75]O3 powders: An experimental/theoretical correlation

Intense and broad photoluminescence (PL) emission at room temperature was observed on structurally disordered Ba[Zr_0.25Ti_0.75]O₃ (BZT) powders synthesized by the polymeric precursor method. BZT powders were annealed at 573 K for different times and at 973 K for 2 h in oxygen atmosphere. The single-phase cubic perovskite structure of the powder annealed at 973 K for 2 h was identified by X-ray diffraction and Fourier transform Raman techniques. PL emission increased with the increase of annealing time, which reached its maximum value in the powder annealed at 573 K for 192 h. First principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered models. The theoretical calculations and experimental measurements of Ultraviolet-visible absorption spectroscopy indicate that the presence of intermediary energy levels in the band gap is favorable for the intense and broad PL emission at room temperature in disordered BZT powders. The PL behavior is probably due the existence of a charge gradient on the disordered structure, denoted by means of a charge transfer process from [TiO₅]-[ZrO₆] or [TiO₆]-[ZrO₅] clusters to [TiO₆]-[ZrO₆] clusters.     

Reversible wettability of nanostructured ZnO thin films by sol-gel method

Nanostructured ZnO thin films were deposited on Si(1 1 1) and quartz substrate by sol-gel method. The thin films were annealed at 673 K, 873 K, and 1073 K for 60 min. Microstructure, surface topography, and water contact angle of the thin films have been measured by X-ray diffractometer, atomic force microscopy, and water contact angle apparatus. XRD results showed that the ZnO thin films are polycrystalline with hexagonal wurtzite structure. AFM studies revealed that rms roughness changes from 2.3 nm to 7.4 nm and the grain size grow up continuously with increasing annealing temperature. Wettability results indicated that hydrophobicity of the un-irradiated ZnO thin films enhances with annealing temperature increase. The hydrophobic ZnO surfaces could be reversibly switched to hydrophilic by alternation of UV illumination and dark storage (thermal treatment). By studying the magnitude and the contact angle reduction rate of the light-induced process, the contribution of surface roughness is discussed.     

Effect of annealing temperature for Si0.8Ge0.2 epitaxial thin films

This study investigates the effect of annealing temperature on the Si_0.8Ge_0.2 epitaxial layers. The Si_0.8Ge_0.2 epitaxial layers were deposited by using ultrahigh vacuum chemical vapor deposition (UHVCVD) with different annealing temperatures (400-1000 °C). Various measurement technologies, including high-resolution X-ray diffraction (HRXRD), atomic force microscopy (AFM) and interfacial adhesion tester, were used to characterize the materials properties of the SiGe epilayers. The experimental results showed that the SiGe epilayers gradually reduced lattice-mismatch to the underlying substrate as annealing temperature increased (from 400 to 800 °C), which resulted from a high temperature enhancing interdiffusion between the epilayers and the underlying substrate. In addition, the average grain size of the SiGe films increased from 53.3 to 58 nm with increasing annealing temperature. The surface roughness in thin film annealed at 800 °C was 0.46 nm. Moreover, the interfacial adhesion strength increased from 476 ± 9 to 578 ± 12 kg/cm² with increasing the annealing temperature.     

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.     

Growth instability and surface phase transition of Ti thin film on Si(1 1 1): An atomic force microscopy study

Evolution of surface structure during the annealing of e-beam evaporated Ti films is studied by means of atomic force microscopy (AFM). Image variography and power spectral density analysis are used to study scaling properties of the films, ranging from 50 nm to 20 μm length scale. No particular grain size is observed up to 473 K. At 673 K, grain size of ∼250 nm are formed and coalesced to form bigger grain size upon further annealing. At 473 K, RMS roughness dropped at all length scale and became rougher at 673 K with an increasing trend up to 873 K. Clustering at 673 K indicates Kosterlitz-Thaouless [J.M. Kosterlitz, D.J. Thaouless, J. Phys. Chem. 6 (1973) 1181] type phase transition at the surface. The observed transition is also consistent with existing scaling laws.     

FINEMET type alloy without Si: Structural and magnetic properties

Magnetic and structural properties of a Finemet type alloy (Fe_73.5Ge_15.5Nb₃B₇Cu₁) without Si and high Ge content were studied. Amorphous material was obtained by the melt spinning technique and was heat treated at different temperatures for 1 h under high vacuum to induce the nanocrystallization of the sample. The softest magnetic properties were obtained between 673 and 873 K. The role of Ge on the ferromagnetic paramagnetic transition of the as-quenched alloys and its influence on the crystallization process were studied using a calorimetric technique. Mössbauer spectroscopy was employed in the nanocrystallized alloy annealed at 823 K to obtain the composition of the nanocrystals and the amorphous phase fraction. Using this data and magnetic measurements of the as-quenched alloy, the magnetic contribution of nanocrystals to the alloy annealed at 823 K was estimated via a linear model.     

Optical properties of In2O3 oxidized from InN deposited by reactive magnetron sputtering

Unintentionally doped and zinc-doped indium nitride (U-InN and InN:Zn) films were deposited on (0 0 0 1) sapphire substrates by radio-frequency reactive magnetron sputtering, and all samples were then treated by annealing to form In₂O₃ films. U-InN and InN:Zn films have similar photon absorption characteristics. The as-deposited U-InN and InN:Zn film show the absorption edge, ∼1.8-1.9 eV. After the annealing process at 500 °C for 20 min, the absorption coefficient at the visible range apparently decreases, and the absorption edge is about 3.5 eV. Two emission peaks at 3.342 eV (371 nm) and 3.238 eV (383 nm) in the 20 K photoluminescence (PL) spectrum of In₂O₃:Zn films were identified as the free-exciton (FE) or the near band-to-band (B-B) and conduction-band-to-acceptor (C-A) recombination, respectively.     

The effect of different temperature annealing on phase relation of LaFe11.5Si1.5 and the magnetocaloric effects of La0.8Ce0.2Fe11.5−xCoxSi1.5 alloys

The phase relation of LaFe_11.5Si_1.5 alloys annealed at different high-temperature from 1223 K (5 h) to 1673 K (0.5 h) has been studied. The powder X-ray diffraction (XRD) patterns show that large amount of 1:13 phase begins to form in the matrix alloy consisting of α-Fe and LaFeSi phases when the annealing temperature is 1423 K. In the temperature range from 1423  to 1523 K, α-Fe and LaFeSi phases rapidly decrease to form 1:13 phase, and LaFeSi phase is rarely observed in the XRD pattern of LaFe_11.5Si_1.5 alloy annealed at 1523 K. With annealing temperature increasing from 1573  to 1673 K, the LaFeSi phase is detected again in the LaFe_11.5Si_1.5 alloy, and there is La₅Si₃ phase when the annealing temperature reaches 1673 K. There almost is no change in the XRD patterns of LaFe_11.5Si_1.5 alloys annealed at 1523 K for 3-5 h. According to this result, the La_0.8Ce_0.2Fe_11.5−xCo_xSi_1.5 (0≤×≤0.7) alloys are annealed at 1523 K (3 h). The analysis of XRD patterns shows that La_0.8Ce_0.2Fe_11.5xCo_xSi_1.5 alloys consist of the NaZn₁₃-type main phase and α-Fe impurity phase. With the increase of Co content from x=0 to 0.7, the Curie temperature T_C increases from 180 to 266 K. Because the increase of Co content can weaken the itinerant electron metamagnetic transition, the order of the magnetic transition at T_C changes from first to second-order between x=0.3 and 0.5. Although the magnetic entropy change decreases from 34.9 to 6.8 J/kg K with increasing Co concentration at a low magnetic field of 0-2 T, the thermal and magnetic hysteresis loss reduces remarkably, which is very important for the magnetic refrigerant near room temperature.     

Investigations on co-evaporated Cu2SnSe3 and Cu2SnSe3-ZnSe thin films

Cu₂SnSe₃ is an important precursor material for the growth of Cu₂ZnSnSe₄, an emerging solar cell absorber layer via solid state reaction of Cu₂SnSe₃ and ZnSe. In this study, we have grown Cu₂SnSe₃ (CTSe) and Cu₂SnSe₃-ZnSe (20%) films onto soda-lime glass substrates held at 573 K by co-evaporation technique. The effect of annealing of these films at 723 K for an hour in selenium atmosphere is also investigated. XRD studies of as-deposited Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films indicated SnSe as secondary phase which disappeared on annealing. The direct optical band gap of annealed Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films were found to be 0.90 eV and 0.94 eV respectively. Raman spectroscopy studies were used to understand the effect of ZnSe on the properties of Cu₂SnSe₃.     

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.     

Effect of nanoscale thin films of Dy2Fe14B on the magnetic hysteresis characteristics of melt-spun ribbons of Nd2Fe14B

The effectiveness of nanoscale Dy₂Fe₁₄B thin films on coercivity and energy product of melt-spun ribbons of Nd₂Fe₁₄B at high temperatures was investigated. It is hypothesized that the nanoscale Dy-thin film will act as an obstacle for the nucleation of reverse domains and also maximize the energy of domain walls and thereby improve the magnetic performance at high temperatures. Pulsed laser deposition (PLD) of amorphous Dy₂Fe₁₄B layers on Nd₂Fe₁₄B melt-spun ribbons was performed for a nominal thickness of 40 nm. The coated ribbons were then annealed in environmentally controlled quartz furnace at two different cycles (750 °C for 15 min and 900 °C for 2 h) to cause crystallization. Magnetic hysteresis tests conducted at 300 and 400 K revealed that there is small but consistent improvement in the magnetic properties of the coated ribbons annealed at 750 °C for 15 min. However, higher temperature annealing (900 °C for 2 h) drastically reduced the magnetic properties. The incomplete recrystallization of amorphous structure at 750 °C for 15 min and large grain growth and formation of non-magnetic phases at 900 °C for 2 h are believed to be responsible for not meeting the expected magnetic performance.