Ab-initio calculation of magnetic properties of Mn-doped ZnGeN2

We have performed a density functional theory within a generalized gradient approximation study of Mn-doped zinc germanium dinitride (ZnGeN₂) semiconductor. Our results show Mn-doped ZnGeN₂ to be antiferromagnetic for Mn_Zn (Mn substitutes Zn site) and ferromagnetic for Mn_Ge (Mn substitutes Ge site). Ferromagnetic state is also preferred if Mn atoms substitute both Zn and Ge sites. Formation of half-metallic ferromagnetism is possible in this type of material.     

EPR study of the impurity paramagnetic centres in (CaO−Ga2O3−GeO2) glasses

The X-band EPR spectra of Cr³⁺, Mn²⁺, and Fe³⁺ impurity ions in glasses of (CaO?Ga₂O₃?GeO₂) system are investigated in the 77÷300 K temperature range. The experimental data analysis yields the following results: (i) Impurity chromium ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glasses network in Cr³⁺ (3d³,⁴F_3/2) paramagnetic valence state only and occupy the strong distorted oxygen coordinated octahedral sites. (ii) For all activated and non-activated (CaO?Ga₂O₃?GeO₂) glasses the iron impurity is present at concentration roughly 0.01 wt.%. Isotropic EPR signals atg _eff=4.29 andg _eff=2.00 are assigned to Fe³⁺ (3d⁵,⁶S_5/2) ions in the sites with strong rhombic distortion and in the sites with nearly cubic symmetry respectively. (iii) The manganese EPR spectrum in (CaO?Ga₂O₃?GeO₂) glasses is weakly dependent on temperature, doping procedure as well as manganese concentration. EPR spectra of impurity manganese ions in glasses with Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ compositions are virtually identical and belong to Mn²⁺ (3d⁵,⁶S_5/2) ions. Impurity manganese ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glass network as isolated Mn²⁺ centres and clusters of Mn²⁺ ions.     

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.     

Vapor–solid–solid growth of Ge nanowires from GeMn solid cluster seeds

We describe the fabrication of Ge nanowires during a single co-deposition step of Ge and Mn at high temperature. In these experimental conditions, a phase separation occurs and two different phases Ge and Ge_1 ? xMn_x are formed with Ge_1 ? xMn_x in the shape of small clusters distributed randomly in the Ge matrix. Because of the high deposition temperature, a new Ge_1 ? xMn_x phase with low eutectic point is stabilized; this phase is different from the one (commonly Ge₃Mn₅) stabilized at lower temperature. During the growth process at 350 °C, the crystalline clusters remain solid but they are highly mobile and can float at the surface, serving as seeds to direct the growth of crystalline Ge nanowires from the vapor. The sketch steps of NWs formation are first the phase separation with formation of specific Ge_1 ? xMn_x critical nuclei with low eutectic point and second the growth of Ge NWs directed by the Ge_1 ? xMn_x solid cluster seeds. Ge NWs growth is forced along particular crystalline axis by the cluster seeds that lower the interfacial energy Ge/Ge_1 ? xMn_x and the energy formation of the germanium crystal stabilizes the cluster position at the tip of the NWs. The density of NWs can be tuned by varying the nominal Mn concentration since this density is related to the number of clusters with the specific Ge_1 ? xMn_x phase (with low eutectic point). The single step MBE process presented here has the main advantage to fully avoid any incorporation of unintentional impurity into Ge nanowires (apart from Mn atoms) and could be applied to several other systems. This work also provides new insights into the vapor–solid–solid growth mechanisms of Ge NWs.     

Silicon-germanium nanostructures with high germanium concentration

The impact of nucleation conditions on the quality of epitaxial layers of germanium and GeSi alloys containing a high Ge mole fraction grown on (100) silicon substrates using electron-beam epitaxy is considered. The Ge_xS_{1 -x}/Ge superlattices are grown on a Ge_ySi_{1 -y} (x > y) relaxed buffer layer. X-ray diffractometry, atomic force microscopy and Auger spectroscopy are the main techniques used to study the properties of the grown structures.     

Degradation of La0.8Ca0.2MnO3 single crystal surface: Electron spectroscopy studies

The electronic structure of degraded (as grown and chemically polished) and ion-sputtered La_0.8Ca_0.2MnO₃ single crystal surfaces has been studied by X-ray photoemission and Auger electron spectroscopy techniques. XPS spectra of deep core levels (Mn2p, O1s, La3d, La4d) were taken from as grown, chemically polished and cleaned in UHV by Ar⁺ ion-bombardment surfaces. XPS data show different oxidation state of Mn and La ions on the degraded and ion-sputtered surfaces of the manganite crystal. Mn2p_3/2 line width and energy position suggest mixed valence state of the manganese ions at the degraded and ion-sputtered crystal surfaces.     

X-ray photoelectron spectroscopy study of the electronic structure of La<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3+δ</Subscript> solid solutions

The electronic structure of La_1–x Ga _x MnO_3+δ. solid solutions is studied by X-ray photoelectron spectroscopy (XPS). The valence state of the manganese is estimated by various methods: by analyzing the difference in the binding energies of the Mn2p_3/2 and O1s electronic levels, analyzing exchange splitting in the spectrum of Mn3s, and from the dependence of the binding energy of the XPS spectrum of Mn2p_3/2 on the calcium concentration. The state of oxidation of the manganese in the compositions containing calcium lies between Mn³⁺ and Mn⁴⁺. The efficacies of these methods are compared. A correlation is found between the type of crystalline structure of La_1–x Ga _x MnO_3+δ. (0 ≤ x < 1) and the binding energy of the Mn2p_3/2 peak. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 419–427, May–June, 2009.     

Optical and EPR spectroscopy of manganese ions in Sr3Ga2Ge4O14 crystals

Results of investigations of the spectroscopic properties of manganese-activated single crystals of Sr₃Ga₂Ge₄O₁₄ by the methods of optical and EPR spectroscopy are reported. It is shown that magnagese activator ions form substitutional centers Mn³⁺ and Mn²⁺ in 1a-octahedral positions of the Sr₃Ga₂Ge₄O₁₄ lattice. Changes in the opticla properties of Sr₃Ga₂Ge₄O₁₄: Mn after vacuum thermal annealing are attributed to charge transfer of some of the manganese ions (Mn³⁺→Mn²⁺). The relationship between the spectroscopical properties of Mn²⁺ ions and the crystallochemical structure of the system are discussed. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 779–783, November–December, 1997.     

Study of the component distribution in Si/GexSi1−x /Si heterostructures grown by molecular beam epitaxy

This paper reports on a study of the depth profile of components in GeSi heterostructures grown on low-temperature silicon (LTSi: T _gr ～ 350–400° C) and porous silicon by molecular-beam epitaxy. An excess Ge concentration was found by Auger electron spectroscopy depth profiling at the Ge_xSi_1?x /LTSi interface, which decreased in all samples subjected to annealing. The Ge diffusion activation energy was calculated to be E _a ≈ 1.6 eV in this case. An enhanced Ge concentration was also detected by x-ray photoelectron spectroscopy at the Si cap surface. Possible reasons for the surface enrichment of the silicon layer and of the Ge_xSi_1?x film interface by germanium are considered, and the relation between the component distribution and the structural features of plastically strain-relieved layers are discussed.     

MnxGe1－x稀磁半导体薄膜的结构研究

利用X 射线衍射(XRD)和X射线吸收精细结构(XAFS)方法研究了磁控共溅射方法制备的Mn_xGe_1-x薄膜样品的结构随掺杂磁性原子Mn含量的变化规律.XRD结果表明，在Mn的含量较低(7.0%)的Mn_0.07Ge_0.93样品中，只能观察到对应于多晶Ge的XRD衍射峰，而对Mn含量较高(25.0%, 36.0%)的Mn_0.25Ge_0.75和Mn关键词： 磁控溅射 XRD XAFS xGe_1-x稀磁半导体薄膜')" href="#">Mn_xGe_1-x稀磁半导体薄膜     

Ferromagnetism in MnxGe1−x films prepared by magnetron sputtering

Mn_xGe_1−x thin films were prepared by magnetron sputtering with a substrate temperature of 673 K and subsequently annealed at 873 K. The X-ray diffraction (XRD) measurements showed that all samples had a single Ge cubic structure. No films showed clear magnetic domain structure under a magnetic force microscope (MFM). Atom force microscope (AFM) measurements showed that the films had an uniform particle size distribution, and a columnar growth pattern. X-ray photoelectron spectroscopy (XPS) measurements indicated that the valences of both Mn and Ge atoms increase with the Mn concentration. The resistance decreased with increasing temperature, suggesting that the films were typical semiconductors. Magnetic measurements carried out using a Physical Property Measurement System (PPMS) showed that all samples exhibited ferromagnetism at room temperature. There was a small concentration of Mn₁₁Ge₈ in the films, but the ferromagnetism was mainly induced by Mn substitution for Ge site.     

Nanometer-scale spatial inhomogeneities of the chemical and electronic properties of an ion implanted Mn-Ge alloy

Electron energy loss spectroscopy maps using a transmission electron microscope were used to investigate with nanometer spatial resolution the Mn distribution of a Mn_xGe_1−x ion implanted alloy (x ? 4%). Mn is fully diluted in the Ge matrix in a subsurface implanted layer, showing concentration inhomogeneities at the nm scale. In the deep implanted layers the presence of Mn rich clusters—either amorphous or in the Mn₅Ge₃ phase—is directly evidenced. Scanning Tunneling Microscopy/Spectroscopy directly shows that the Mn₅Ge₃ clusters are metallic, while those smaller and amorphous are semiconducting with 0.45 ± 0.05 eV band gap. The Ge matrix with Mn dilution is semiconducting with 0.60 ± 0.05 eV gap. Electronic structure results are compared with ab-initio calculations.     

Electronic properties of LiMn2?xTixO4

Ti-substituted LiMn₂O₄ (LiMn_2−x Ti _x O₄, x=0, 0.15, 0.30, 0.45, 0.60, and 0.75) has been synthesized using solid-state reactions. Their crystal and electronic structures were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). XRD data suggested that the lattice parameters of LiMn_2−x Ti _x O₄ increase due to the replacement of Mn by Ti ions. XPS results indicated that the substituted Ti ions were in +4 oxidation state; consequently, the normal oxidation state of Mn ions has been detected by measuring the binding energy splitting of Mn 3s states, which decreases with the content of substituted Ti. The valence band spectra suggested that the intensity of e _g level of Mn 3d orbitals increased due to the increase of the Mn³⁺/Mn⁴⁺ ratio.     

Determination par diffraction des neutrons de la structure antiferromagnetique du grenat Mn3Al2Ge3O12

The magnetic structure of the antiferromagnet Mn₃Al₂Ge₃O₁₂ with Mn²⁺ on dodecahedral site is determined by neutron diffraction. At the difference of the magnetic structures of isomorphous rare earth garnets, the observed structure is rhombohedral. The importance of super-superexchange interactions of the type MnOOMn or MnOGeO is pointed out.     

Preparation of thin films of the ternary heavy fermion system CeNi2Ge2

2 Ge₂ layers on W(110). In order to produce well-ordered and atomically clean surfaces of the Ce-based intermetallic system the growth was performed under UHV conditions (p<2×10^-11 mbar). Both the polycrystalline CeNi₂Ge₂ compound and the individual elements Ce, Ni, and Ge were used as evaporants. The characterisation of the layers was made with LEED, SEM, and XPS. We find a significant influence of the substrate temperature and the evaporation power on the growth characteristics. The compound material CeNi₂Ge₂ exhibits complicated behaviour when evaporated. Under carefully selected growth conditions we obtain well-ordered films with a stoichiometry of Ce:Ni:Ge=1:2:2 and a (001) oriented surface of the body-centered tetragonal ThCr₂Si₂-type structure. The k_∥ dispersion and binding energies of the valence bands of these layers were determined with ARUPS. Received: 26 October 1997/Accepted: 27 October 1997     

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.     

Chemical characterization by XPS of Cu/Ge ohmic contacts to n-GaAs

Chemical composition of Cu/Ge layers deposited on a 1 μm thick n-type GaAs epitaxial layer (doped with Te to a concentration of 5 × 10¹⁸ cm⁻³) and its interface were examined ex situ by XPS combined with Ar⁺ sputtering. These measurements indicate a diffusion of Cu and Ge from the Cu/Ge layer towards GaAs and, also, an out-diffusion of Ga and As from the GaAs layer to the metallic films. The Auger parameter corrected Auger spectra and XPS spectra show only Cu and Ge metals in the in the Cu/Ge layer and in the interface.     

Phase transformations in the Mn-Ge system and in Ge x Mn1 ? x diluted semiconductors

Results of an X-ray diffraction study as well as magnetic and electrical measurements of the solid-state reactions in Ge/Mn polycrystalline films of an 80/20 atomic composition have been presented. It has been shown that the ferromagnetic Mn₅Ge₃ phase is formed first on the Ge/Mn interface after annealing at ??120°C. The further increase in the annealing temperature to 300°C leads to the beginning of the synthesis of the Mn₁₁Ge₈ phase, which becomes dominating at 400°C. The existence of new structural transitions in the Mn-Ge system in the region of ??120 and ??300°C has been predicted on the basis of the presented results and results obtained earlier when studying solid-state reactions in different film structures. The supposition about the general chemical mechanisms of the synthesis of the Mn₅Ge₃ and Mn₁₁Ge₈ phases during the solid-state reactions in the Ge/Mn films of the 80/20 atomic composition and the phase separation in Ge _x Mn_{1 ? x} (x > 0.95) diluted semiconductors has been substantiated.     

Microwave magnetoresistance and electron spin resonance in Ge:Mn thin films and nanowires

Resonant and nonresonant absorption of microwave radiation is found to occur in germanium films implanted with manganese at concentrations of 2, 4, and 8 at %. Electron spin resonance is observed in two temperature ranges: (i) in the vicinity of the phase transition of Mn₅Ge₃ clusters to the ferromagnetic state at T = 295 K; and (ii) in the range of temperatures below 60 K, at which collective ordering of Mn spins in the crystal lattice and spin-wave resonance take place. The dependence of the nonresonant signal of the microwave magnetoresistance on the magnetic field exhibits a nonmonotonic behavior identical for the X and K microwave bands. An analysis of the field dependence of the microwave magnetoresistance makes it possible to separate two components of the derivative of the magnetoresistance: the quasi-linear Lorentzian component observed in strong fields and the negative exponential anisotropic component determined by spin-dependent scattering of charge carriers from magnetic impurities. The length of the phase relaxation of charge carriers is estimated to be 350 nm at T = 2 K and exceeds the thickness of the film (120 nm) and the sizes of clusters and precipitates (3–5 nm). In quasi-one-dimensional nanowires of the composition Ge:Mn at the same impurity concentrations, microwave magnetoresistance is absent. These facts suggest that conduction in thin films has a quasi-two-dimensional character and that the measured microwave magnetoresistance is associated with charge carriers in the crystal lattice rather than with impurity clusters.     

ZnO:Mn as a member of II-VI:Mn family

ZnO:Mn thin films are grown by the metal organic chemical vapor deposition technique. Mn (x) varies in the 0<x<0.44 range. Vegard’s law has been verified for the lattice parameters. Electron paramagnetic resonance (EPR) measurements prove the substitutional incorporation of Mn²⁺ on zinc sites. The behavior of the EPR line width regarding temperature is discussed. All ZnO:Mn layers show antiferromagnetic interaction and a J₁/k_B=-15 K effective exchange constant. The optical band gap of ZnO:Mn increases with the manganese concentration. Raman spectroscopy reveals a Mn-related scattering band. PACS 71.55.Gs; 75.50.Pp; 61.10.Nz; 76.30.Fc; 75.30.Et; 78.40.-q