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.     

High-temperature electrical properties of magnesiowustite Mg1 − xFexO and spinel Fe3 − x − yMgxCryO4 ceramics

Phase relationships, thermal expansion and electrical properties of Mg_1 − xFe_xO (x = 0.1-0.45) cubic solid solutions and Fe_{3 − x − y}Mg_xCr_yO_4 ± δ (x = 0.7-0.95; y = 0 or 0.5) spinels were studied at 300-1770 K in the oxygen partial pressure range from 10 Pa to 21 kPa. Increasing iron content enlarges the spinel phase stability domain at reduced oxygen pressures and elevated temperatures. The total conductivity of the spinel ceramics is predominantly n-type electronic and is essentially p(O₂)-independent within the stability domain. The computer simulations using molecular dynamics technique confirmed that overall level of ion diffusion remains low even at high temperatures close to the melting point. Temperature dependencies of the total conductivity in air exhibit a complex behavior associated with changing the dominant defect-chemistry mechanism from prevailing formation of the interstitial cations above 1370-1470 K to the generation of cation vacancies at lower temperatures, and with kinetically frozen cation redistribution in spinel lattice below 700-800 K. The average thermal expansion coefficients of the spinel ceramics calculated from dilatometric data in air vary in the range (9.6-10.0) × 10^− 6 K^− 1 at 300-500 K and (13.2-16.1) × 10^− 6 K^− 1 at 1050-1370 K. Mg_1 − xFe_xO solid solutions undergo partial decomposition on heating under oxidizing and mildly reducing conditions, resulting in the segregation of spinel phase and conductivity decrease.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

X-ray photoelectron study of Sn1−xMnxTe semimagnetic semiconductors

X-ray photoelectron (XPS) studies of core-levels in Sn_1−xMn_xTe (x < 0.1) semimagnetic semiconductors have been performed. The spectra were acquired under UHV conditions from the clean (as-cleaved or in-situ scraped) crystal surface. The single-phase NaCl structure of the alloys studied was verified by X-ray diffraction (XRD). The structure of Sn 3d and Te 3d core-levels in SnMnTe was found fully consistent with that of SnTe. Remarkable qualitative similarity of the Mn 2p spectrum of Sn_1−xMn_xTe (x = 0.09) with the case of zinc-blende MnTe [R.J. Iwanowski, M.H. Heinonen, E. Janik, Chem. Phys. Lett. 387 (2004) 110] has been shown: (1) the same binding energies (BEs) of the main contributions to the Mn 2p_3/2 line, related to Mn²⁺ state of the bulk MnTe bond; (2) occurrence of low BE component in the Mn 2p spectrum, indicative of clean-surface species containing reduced-valence Mn ions (i.e. Mn^q+, where 0 < q < 2); (3) strong satellites of the 2p_3/2 (Mn²⁺ related) parent lines. In SnMnTe, the highest intensity ratio of the satellite to main peak (ever reported for Mn 2p photoelectron spectrum) was revealed; this was interpreted in terms of the so-called charge-transfer model.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Ellipsometric investigation of optical constant and energy band gap of Zn1−xMnxSe/GaAs (1 0 0) epilayers

Zn_1−xMn_xSe/GaAs (1 0 0) epilayers were grown using a hot-wall epitaxy method. The spectroscopic ellipsometry was used to determine the optical dielectric constant. The obtained pseudodielectric function spectra revealed the distinct structures at energies of E₀, E₀ + Δ₀, E₁, E₁ + Δ₁, E₂ and  + Δ₀ critical points (CPs) at lower Mn composition range. These critical points were determined by analytical line-shapes fitted to numerically calculated derivatives of their pseudodielectric functions. The peak characteristics were changed with the change in Mn composition. The spectral dependence of pseudodielectric function 〈?〉 was used to obtain the fundamental energy gaps E₀ including a unique relation with Mn composition. Also, the shifting and broadening of the CPs were observed with increasing Mn composition.     

The effect of Mn substitution on thermoelectric properties of Ca3MnxCo4−xO9 at low temperatures

The effects of partial substitution of Mn for Co on the thermoelectric properties of Ca₃Mn_xCo_4−xO₉ (x=0, 0.03, 0.9), prepared by sol-gel process, were investigated at the temperatures from 380 K down to 5 K. The results indicate that the substitution of Mn for Co results in increase in thermopower at temperatures >∼80 K, and substantial (23-31% at 300 K) decrease in lattice thermal conductivity in the whole temperature range investigated. The temperature behavior of ZT suggests that Ca₃Mn_xCo_4−xO₉ with light Mn substitution would be a promising candidate for high-temperature thermoelectric applications.     

Structural and magnetic properties of Cu1−xMnxO nanocrystal prepared by combustion synthesis

Nanoscale Cu_1−xMn_xO powder is prepared by using the combustion synthesis technique with two different fuels. The structural properties of the powder are determined using Rietveld refinement of X-ray diffraction data, high-resolution transmission electron microscopy, and Fourier transform infrared spectroscopy, while its magnetic properties are analyzed by means of hysteresis loop and temperature dependence of magnetization. The results show that (1) the Cu_1−xMn_xO nanocrystal is of monoclinic CuO structure, with grain size of 10-30 nm varying with the type of fuel, the nitrate/fuel ratio (N/F), and the Mn concentration, the doping of Mn has a little influence on the lattice parameters; (2) when the Mn concentration is higher than 7%, a small amount of impurity phase of CuMn₂O₄ appears and annihilates the potential cation vacancies; (3) all of the samples with x≥5% exhibit low-temperature ferromagnetism with the Curie temperature of ∼90 K, which increases slightly by raising the Mn concentration; (4) the paramagnetic moment per Mn ion is around 2-4 bohr magneton above the Curie temperature, which decreases with increasing Mn concentration, implying that the nearest Mn ions are antiferromagnetically coupled and the ferromagnetic order could originate from the super-exchange of next nearest Mn ions along the [1 0 1?] direction.     

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.     

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.     

Nanoscratch study of Zn1−xMnxO heteroepitaxial layers

We investigated the nanotribological properties of Zn_1−xMn_xO epilayers (0 ≤ x ≤ 0.16) grown by molecular beam epitaxy (MBE) on sapphire substrates. The surface roughness and friction coefficient (μ) were analyzed by means of atomic force microscopy (AFM) and hysitron triboscope nanoindenter techniques.The nanoscratch system gave the μ value of the films ranging from 0.17 to 0.07 and the penetration depth value ranging 294-200 nm when the Mn content was increased from x = 0 to 0.16. The results strongly indicate that the scratch wear depth under constant load shows that higher Mn content leads to Zn_1−xMn_xO epilayers with higher shear resistance, which enhances the Mn-O bond. These findings reveal that the role of Mn content on the growth of Zn_1−xMn_xO epilayers can be identified by their nanotribological behavior.     

Local structures and transport properties of K ions in a hollandite superstructure KxMg(8 + x)/3Sb(16 − x)/3O16

Possible local structures of K ions in the tunnel of a hollandite superstructure K_xMg_(8 + x)/3Sb_{(16 − x)/3}O₁₆ (x ≈ 1.76) were presented, and the validity of the models was confirmed by the structure refinement using single-crystal X-ray diffraction data. Additional constraint conditions were introduced in refinements so that the average structure obtained from the refinement is consistent with assumed microscopic pictures. Joint-probability density functions were calculated for specific K ions concerning the hopping process between neighboring cavities, and converted to the one-particle potentials. Three types of the energy barrier for the hopping process were seen, which were uniformly reduced applying the anharmonic atomic displacement parameters.     

Phase and electrical behaviour in the Bi14W1 − xLaxO24 − 3x/2 system

The compositional and thermal dependencies of phase and electrical behaviour of compositions in the system Bi₁₄W_1 − xLa_xO_{24 − 3x/2} (0.00 < x < 1.00) have been studied by X-ray powder diffraction, differential thermal analysis and a.c. impedance spectroscopy. The system exhibits polymorphism and phase separation, which shows both compositional and thermal dependence. Compositions with x = 0.25 and x = 0.50 exhibit a single phase tetragonal structure at room temperature. In contrast, the x = 0.75 composition at room temperature shows a mixture of a cubic phase and a secondary β-Bi₂O₃ related tetragonal phase. A full solid solution is observed at high temperatures, corresponding to the occurrence of a δ-Bi₂O₃ type phase. The appearance of the various phases correlates well with the observed electrical behaviour. The x = 0.75 composition exhibits exceptionally high conductivity at high temperatures (σ₈₀₀ = 1.34 S cm^− 1), but also shows significant phase separation at lower temperatures.     

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 studies of evaporated CoxCr1−x/Si (1 0 0) and CoxCr1−x/glass thin films

Series of Co_xCr_1−x thin films have been evaporated under vacuum onto Si (1 0 0) and glass substrates. Chemical composition and interface properties have been studied by modelling Rutherford backscattering spectra (RBS) using SIMNRA programme. Thickness ranges from 17 to 220 nm, and x from 0.80 to 0.88. Simulation of the energy spectra shows an interdiffusion profile in the thickest films, but no diffusion is seen in thinner ones. Microscopic characterizations of the films are done with X-ray diffraction (XRD) measurements. All the samples are polycrystalline, with an hcp structure and show a 〈0 0 0 1〉 preferred orientation. Atomic force microscopies (AFM) reveal very smooth film surfaces.     

Structural and photoluminescence analysis of Zn1 − xMnxO nanocrystalline powders

This Letter reports on structural and photoluminescence properties of Zn_1 − xMn_xO nanocrystalline powders, which were synthesized by using oxalate precursor decomposition method. From the XRD features, we have noticed that all samples exhibit wurtzite crystal structure. The origin of photoluminescence properties of Mn doped and undoped ZnO have been discussed.     

AlN, GaN, AlxGa1 − xN nanotubes and GaN/AlxGa1 − xN nanotube heterojunctions

Semiconductor optoelectronic devices based on GaN and on InGaN or AlGaN alloys and superlattices can operate in a wide range of wavelengths, from far infrared to near ultraviolet region. The efficiency of these devices could be enhanced by shrinking the size and increasing the density of the semiconductor components. Nanostructured materials are natural candidates to fulfill these requirements. Here we use the density functional theory to study the electronic and structural properties of (10,0) GaN, AlN, Al_xGa_1 − xN nanotubes and GaN/Al_xGa_1 − xN heterojunctions, 0<x<1. The Al_xGa_1 − xN nanotubes exhibit direct band gaps for the whole range of Al compositions, with band gaps varying from 3.45 to 4.85 eV, and a negative band gap bowing coefficient of −0.14 eV. The GaN/Al_xGa_1 − xN nanotube heterojunctions show a type-I band alignment, with the valence band offsets showing a non-linear dependence with the Al content in the nanotube alloy. The results show the possibility of engineering the band gaps and band offsets of these III-nitrides nanotubes by alloying on the cation sites.     

RAIRS studies of CO adsorption on Pd/CeO2−x(1 1 1)/Pt(1 1 1)

Reflection absorption infrared spectroscopy (RAIRS) has been used to investigate the adsorption of CO on CeO_2−x-supported Pd nanoparticles at room temperature. The results show that when CeO_2−x is initially grown on Pt(1 1 1), a small proportion of the surface remains as bare Pt sites. However, when Pd is deposited onto CeO_2−x/Pt(1 1 1), most of the Pd grows directly on top of the CeO_2−x(1 1 1). RAIR spectra of CO adsorption on 1 ML Pd/CeO_2−x/Pt(1 1 1) show a broad CO-Pd band, which is inconsistent with a single crystal Pd surface. However, the 5 ML and 10 ML Pd/CeO_2−x/Pt(1 1 1) spectra show vibrational bands consistent with the presence of Pd(1 1 1) and (1 0 0) faces, suggesting the growth of Pd nanostructures with well defined facets.     

Magnetism in Zn1−xMnxO crystal prepared by hydrothermal method

Crystal Zn_1−xMn_xO magnetic semiconductors have been obtained by using a hydrothermal method for the first time at temperature of 703 K with substituent fraction ranging from x=0 to 0.04. X-ray diffraction and optical absorption measurements provide evidence for the locating at Zn site of Mn ion in ZnO crystals. The non-monotonic variation of band gap indicates the short-ranged interactions of sp-d electrons. However, no evidence of ferromagnetism is found in these systems down to T=2 K. The magnetization is found to be contributed from both free spins and spins associated with antiferromagnetic clusters. The antiferromagnetism is confirmed by fitting a Curie-Weiss function.