High-temperature ferromagnetism in laser-deposited layers of silicon and germanium doped with manganese or iron impurities

The paper reports on the results of a study of the synthesis conditions effects on magnetic and transport properties of nanosized layers of high-T_c diluted magnetic semiconductors (DMS), such as Ge:Mn, Si:Mn and Si:Fe, fabricated by laser-plasma deposition over a wide range of the growth temperature, T_g=(20-550) °C on single-crystal GaAs or Al₂O₃ substrates. Ferromagnetism of the layers was detected by measurement data of the magneto-optical Kerr effect, anomalous Hall effect, negative magnetoresistance and ferromagnetic resonance (FMR) at 5-500 K. The optimum growth temperature, T_g, for Si:Mn/GaAs layers with T_c≈400 K is shown to be about 400 °C. The Si:Mn/Al₂O₃ layers with 35% of Mn have the metal-type of conductivity with manifestation of magnetization up to room temperature. Different types of uniformly doped structures and digital alloys have been investigated. In contrast to GaSb:Mn films, Si-based ferromagnetic layers have strongly different magnetic and electric properties in case of uniformly doped structures and digital alloys. Positive results of the Fermi level variation effect on the improvement of Si- and Ge-based DMS layers have been gained on the use of additional doping with shallow acceptor Al impurity which contributes to the increase of the hole concentration and the RKKY exchange interaction of 3d-ions. The Ge:(Mn, Al)/GaAs or Ge (Mn, Al)/Si layers grown at 20 °C feature surprising extraordinary angular dependence of FMR.     

Theoretical investigations of the (110) interface between the full Heusler alloys and GaAs

The ab initio calculations of the electronic structure and magnetic properties of the (110) interface between Co₂YZ (Y = Cr or Mn and Z = Al, Si, or Ge) and GaAs are carried out by means of the density functional theory depending on the contact configuration. It is revealed that two of four possible atomic interface configurations have high spin polarization. For Co₂MnSi/GaAs(110), one of the contacts has almost 100% spin polarization. Calculations of the adhesion energy on the interfaces allow the most stable contacts to be established.     

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.     

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.     

The radial dependence of the magnetic hyperfine field for Sn atoms in the ferromagnetic Heusler alloys

The magnetic hyperfine fields,B _hf, for impurity¹¹⁹Sn atoms in Z sites of ferromagnetic Heusler alloys Co₂MnZ (Z=Si, Ge) are measured by the Mössbauer effect. At 77 KB _hf=–1.43±0.04 T in Co₂MnSi andB _hf=+1.05±0.05 T in Co₂MnGe. From the comparison between the values ofB _hf for Sn atoms in Co₂MnZ (Z=Si, Ge, Sn), it follows that the negative contribution toB _hf drops as the interatomic distance begins to increase. This radial dependence also manifests itself in the anomalies of the temperature dependences of the hyperfine fields. The temperature anomaly is positive for Sn in Co₂MnGe and negative for Sn in Co₂MnSi.     

Ferromagnets based on diamond-like semiconductors GaSb,InSb, Ge,and Si supersaturated with manganese or iron impurities during laser-plasma deposition

Properties of thin (30–100 nm) layers of diluted magnetic semiconductors based on diamond-like compounds III–V (InSb and GaSb) and elemental semiconductors Ge and Si doped with 3d impurities of manganese and iron up to 15% were measured and discussed. The layers were grown by laser-plasma deposition onto heated single-crystal gallium arsenide or sapphire substrates. The ferromagnetism of layers with the Curie temperature up to 500 K appeared in observations of the ferromagnetic resonance, anomalous Hall effect, and magneto-optic Kerr effect. The carrier mobility of diluted magnetic semiconductors is a hundred times larger than that of the previously known highest temperature magnetic semiconductors, i.e., copper and chromium chalcogenides. The difference between changes in the magnetization with temperature in diluted semiconductors based on III–V, Ge, and Si was discussed. A complex structure of the ferromagnetic resonance spectrum in Si:Mn/GaAs was observed. The results of magnetic-force microscopy showed a weak correlation between the surface relief and magnetic inhomogeneity, which suggests that the ferromagnetism is caused by the 3d-impurity solid solution, rather than ferromagnetic phase inclusions.     

Polarized neutron reflectometry from the interface of the heterostructures SiO2(Co)/Si and SiO2(Co)/GaAs

Polarized neutron reflectometry is used to investigate SiO₂(Co) granular films (70 at% of Co nanoparticles in SiO₂ matrix) deposited on Si and GaAs substrates. The aim of the study is to compare magnetization depth profiles in two systems: in SiO₂(Co)/GaAs heterostructure which shows at room temperature giant injection magnetoresistance (IMR) with the system SiO₂(Co)/Si which reveals almost no IMR effect. We found that at room temperature and at the same value of external magnetic field mean magnetization in the SiO₂(Co)/GaAs sample is much higher than in the case of SiO₂(Co)/Si. We also demonstrate that magnetic scattering length density, and hence, magnetization profile strongly depends on the substrate. We show that SiO₂(Co)/Si heterostructure is ferromagnetically ordered within the temperature range between 120 and 460 K what could explain a weak IMR.     

First-principle study of full Heusler Co2Y Si using PBE0 hybrid functional

First-principle self-consistent full potential linear augmented plane wave calculations based on density functional theory using hybrid functional PBE0 are performed to study magnetic moments, density of states and half-metallicity of L2₁ type full Heusler alloys with formula Co₂Y Si. Y is Ti, V, Mn and Fe. We have compared these results with those of the PBE-GGA exchange correlation functional and the LDA + U method. The results for Co₂FeSi and Co₂MnSi are completely different; using the PBE0 hybrid functional for Co₂FeSi predicts experimental magnetic moment and also predicts this material to be half-metallic ferromagnet, while using PBE-GGA predicts it not to be half-metal. The results of PBE0 are more similar to the ones obtained by LDA + U method.     

Structural characterizations of Co2MnSi/MgO/Co2MnSi magnetic tunnel junctions by transmission electron microscopy

We have investigated the structure of Co₂MnSi/MgO/Co₂MnSi magnetic tunneling junctions with different tunnel magnetoresistance values depending on the in situ annealing temperatures just after the deposition of the upper Co₂MnSi electrodes. The nano-beam diffraction patterns indicated that the degree of order of the upper Co₂MnSi electrode annealed at 550 °C was higher than that of an electrode annealed at 400 °C. Moreover, the degree of the L2₁ order of the upper Co₂MnSi electrode annealed at 550 °C was even lower than that of the lower Co₂MnSi electrode annealed at an almost equal temperature of 600 °C. Atomic-scale observation using a high-angle annular dark-field (HAADF) method distinctly showed the existence of the L2₁-ordered regions in the B2-ordered matrix in the upper Co₂MnSi electrode annealed at 400 °C.     

Growth of magnetic materials and structures on Si(0 0 1) substrates using Co2Si as a template layer

We report in this paper the use of Co₂Si silicide as a template layer for the integration of magnetic materials and structures on silicon substrate. By undertaking Co deposition on silicon at a temperature of about 300 °C, we show that it is possible to obtain a smooth and epitaxial Co₂Si layer, which can act as a template layer preventing the reaction between Co and other transition metals with silicon. Two examples of over-growth of magnetic materials and structures on this template layer will be presented: growth of ferromagnetic Co layers and of magnetic tunnel junctions (Co(Fe)/AlO_x/NiFe).     

第一性原理研究Co2MnSi和Co2MnGe半金属与磁性的稳定性

基于广义梯度近似密度泛函和全势能线性缀加平面波方法,对Co2MnSi和Co2MnGe在晶格常数发生变化的情况下进行电子结构和磁矩的自旋极化计算,得到了它们的自旋态密度分布以及总磁矩和各原子磁矩。计算结果的分析表明：（1）Co2MnSi 和Co2MnGe具有半金属性质;（2）晶格常数的改变分别为-5%~ 4%和-6%~1%时,Co2MnSi 和 Co2MnGe仍保持稳定的半金属质性;（3）Co2MnSi 和Co2MnGe的总磁矩为5.00µB/formula。总磁矩主要来源于Mn和Co的原子磁矩,Si和Ge的原子磁矩对总磁矩的贡献极小而且为负值。（4）Co2MnSi 和 Co2MnGe的晶格常数变化分别为-6% ~ 6%和-7%~ 4%时,虽然各原子磁矩都发生了变化,但是它们总磁矩稳定于5.00µB/formula.     

New diluted ferromagnets based on diamond-like semiconductors GaSb,InSb, InAs,Ge, and Si,supersaturated with manganese or iron impurities during laser epitaxy

The electric, magnetic, and magneto-optical properties of thin (50–100 nm) GaSb:Mn, InSb:Mn, InAs:Mn, Ge:Mn, Ge:Fe, Si:Mn, and Si:Fe layers with a Curie point up to 500 K, obtained by laser plasma deposition in vacuum in the case of strong supersaturation of a solid solution with a 3d impurity, have been experimentally investigated.     

Crystallization of amorphous Co2MnSi thin film

Amorphous Co₂MnSi thin film was deposited using radio-frequency sputtering. The amorphous film crystallized into a single-phased L2₁ structure at 500 °C, which was highly disordered. The structure was meta-stable as the crystallized film decomposed upon further heating. Increasing the annealing temperature to 600 °C precipitated fcc Co together with Co₂MnSi. Magnetic measurements showed that the as-deposited amorphous film was paramagnetic, exhibiting a spin glass state below 44 K. The phase transition at 500 °C produced a ferromagnetic Co₂MnSi thin film whose saturation magnetic moment was considerably lower than reported values due to the disordered structure of the crystallized film.     

Persistent spin splitting of a two-dimensional electron gas in tilted magnetic fields

The effect of atomic disorder on the electron transport and the magnetoresistance (MR) of Co₂CrAl Heusler alloy (HA) films has been investigated. We show that Co₂CrAl films with L2₁ order exhibit a negative value for the temperature coefficient of resistivity (TCR) in a temperature range of 10 < T < 290 K, and the temperature dependence of electric conductivity varies as T ^3/2 similarly to that of the zero-gap semiconductors. The atomic or the site disorder on the way of L2₁ → B2 → A2 → amorphous state in Co₂CrAl HA films causes the deviation from this dependence: reduction in the absolute value of TCR as well as decrease in the resistivity down to ϱ(T = 293 K) ∼ 200 μΩ cm in comparison to ϱ(T = 293 K) ∼ 230 μΩ cm typical for the Co₂CrAl films with L2₁ order. The magnetic-field dependence of MR of the Co₂CrAl films with L2₁ order is determined by two competing contributions: a positive Lorentz scattering and a negative s-d scattering. The atomic disorder in Co₂CrAl films drastically changes MR behavior due to its strong influence on the magnetic properties.     

Nuclear magnetic resonance (NMR) study of 73Ge in Ge[Co2]O4

Nuclear magnetic resonance of ⁷³Ge in Ge[Co₂]O₄ was investigated between 77°K and 290°K. Analysis on resonance shifts showed a presence of considerable everlap between the oxygen and germanium ions, suggesting the long-range superexchange interaction via CoOGeOCo paths.     

Defects-driven appearance of half-metallic ferrimagnetism in Co-Mn-based Heusler alloys

Half-metallic ferromagnetic full-Heusler alloys containing Co and Mn, having the formula Co₂MnZ where Z is a sp element, are among the most studied Heusler alloys due to their stable ferromagnetism and the high Curie temperatures which they present. Using state-of-the-art electronic structure calculations we show that when Mn atoms migrate to sites occupied in the perfect alloys by Co, these Mn atoms have spin moments antiparallel to the other transition metal atoms. The ferrimagnetic compounds, which result from this procedure, keep the half-metallic character of the parent compounds and the large exchange-splitting of the Mn impurities atoms only marginally affects the width of the gap in the minority-spin band. The case of [Co_1−xMn_x]₂MnSi is of particular interest since Mn₃Si is known to crystallize in the Heusler L2₁ lattice structure of Co₂MnZ compounds. Robust half-metallic ferrimagnets are highly desirable for realistic applications since they lead to smaller energy losses due to the lower external magnetic fields created with respect to their ferromagnetic counterparts.     

Structure of precipitates and orientation relationships in Al,Ge, Mo-doped higher manganese silicide crystals

Abstract

The structure of Al, Ge, Mo-doped Higher Manganese Silicide (HMS) crystals with the general formulas Mn(Si_0.99Ge_0.01)_1.75, Mn(Si_0.995Ge_0.005)_1.75 and (Mn_0.98Mo_0.02)[(Si_0.98Ge_0.02)_1.75]_0.99Al_0.01 was investigated by scanning and transmission electron microscopy, electron diffraction and X-ray energy dispersive spectrometry in a wide scale range from a few mm to several Å. Several secondary phases were identified in the Mn₄Si₇ matrix: Ge_1?xSi_x (0.1 < x < 0.9) solid solution precipitates with Ge concentration ranging from 5 at. % up to 93 at.%, MoSi₂ platelets, MnSi and Mn₅Si₃ precipitates. Their morphology, structure and crystallographic relationships with the HMS matrix were determined. Mostly local strains in the matrix and precipitates due to lattice misfits at interfaces derived from crystallographic relationships were found two orders of magnitude higher than deformation induced by thermal expansion mismatch. Only a few exceptions of specific relationships were found when the lattice misfit and thermal mismatch have close values. The largest misfit of about 22% was observed between MnSi and Mn₄Si₇ what led to big and numerous cracks in crystals. Therefore, doping can improve the material performance (1) by preventing the formation of MnSi precipitates with metallic properties and (2) by reduction of cracking and crack propagation because of larger MnSi /Mn₄Si₇ lattice misfit compared to Ge_1?xSi_x /Mn₄Si₇ or MoSi₂/Mn₄Si₇ misfits.     

A non-magnetic Fe probe of multiple magnetic phase transitions in RMn2Si2−x Ge x,R=rare earth

Summary Dilute⁵⁷Fe M?ssbauer-spectroscopy studies of RMn₂X₂ (X=Si and/or Ge, R=La, Ce, Pr, Nd, Sm, Eu and Gd) at 4.2 to 650 K yield the following results: Fe in RMn₂X₂ does not carry a magnetic moment. It reveals the magnetic order in the Mn and R sublattices through transferred hyperfine fields (∼100 kOe). The compounds LaMn₂Si₂, LaMn₂Ge₂, CeMn₂Ge₂, PrMn₂Ge₂, NdMn₂Ge₂ and SmMn₂Ge₂, known to be ferromagnets withT _c=300–350 K, are antiferromagnetically ordered above their correspondingT _c. TherT _N values extend from 385 K (SmMn₂Ge₂) to 470 K (LaMn₂Si₂). At the ferromagnetic-antiferromagnetic phase transition, a sharp reorientation of the Mn magnetic moments relative to the crystalline axes occurs. In RMn₂Si_2−x Ge _x with intermediatex values, the Ge is much more dominant in determining the magnetic properties of the Mn sublattice. While PrMn₂Si₂ is an antiferromagnet (T _N=365 K) and PrMn₂Ge₂ is a ferromagnetantiferromagnet (T _c=328 K,T _N=415 K), we find that in PrMn₂SiGe, the magnetic behaviour is similar to that in pure PrMn₂Ge₂,T _c=305 K andT _N=395 K. Paper presented at ICAME-95, Rimini, 10–16 September 1995.