Heteroepitaxial film growth of layered compounds with the ZrCuSiAs-type and ThCr2Si2-type structures: From Cu-based semiconductors to Fe-based superconductors

FeAs-based layered superconductors such as F-doped LaFeAsO have recently been investigated intensively because of their high superconducting transition temperatures. Epitaxial films of these compounds are important to examine their intrinsic materials properties as well as to transfer them to device applications. In this review, we first present our research route from transparent p-type oxides semiconductors to the Fe-based superconductors. Then we review growth of epitaxial thin films for the layered oxychalcogenides and oxypnictides. Reactive solid-phase epitaxy technique was inevitable to prepare epitaxial thin films of the oxychalcogenides and Zn-based oxypnictides. On the other hand, epitaxial thin films of Mn-based oxypnictides were grown by standard pulsed laser deposition. These techniques, however, did not grow epitaxial thin films for LaFeAsO. Thus, we developed a modified pulsed laser deposition process and succeeded in obtaining epitaxial thin films of FeAs-based superconductors, LaFeAsO and cobalt-doped SrFe₂As₂.     

Magnetism of Fe in SrFe2As2: Local investigation by time differential perturbed angular distribution (TDPAD) spectroscopy

Employing the γ-ray perturbed angular distribution technique, we have measured the magnetic hyperfine field of ⁵⁴Fe in tetragonal and orthorhombic structural phases of SrFe₂As₂. In the tetragonal phase, the magnetic response of ⁵⁴Fe shows Curie-Weiss type local susceptibility, indicating the presence of localized moment on Fe. The temperature dependence of the hyperfine field of ⁵⁴Fe reflects quasi-two dimensional first order magnetic transition at 200 K. Our data indicate that Fe moments in the magnetically ordered phase of SrFe₂As₂ may be canted out of the ab-plane.     

Structure, magnetic and optical properties of polycrystalline Co-doped TiO2 films

Co-doped TiO₂ films were fabricated under different conditions using reactive facing-target magnetron sputtering. Co doping improves the transformation of TiO₂ from anatase phase to rutile phase. The chemical valence of doped Co in the films is +2. All the films are ferromagnetic with a Curie temperature above 340 K. The average room-temperature moment per Co of the Co-doped TiO₂ films fabricated at 1.86 Pa decreases from 0.74 μ_B at x=0.03 to 0.02 μ_B at x=0.312, and decreases from 0.54 to 0.04 μ_B as x increases from 0.026 to 0.169 for the Co-doped TiO₂ films fabricated at 0.27 Pa. The ferromagnetism originates from the oxygen vacancies created by Co²⁺ dopants at Ti⁴⁺ cations. The optical band gaps value (E_g) of the Co-doped TiO₂ films fabricated at 1.86 Pa decreases linearly from 3.35 to 2.62 eV with the increasing x from 0 to 0.312. For the Co-doped TiO₂ films fabricated at 1.86 Pa, the E_g decreases linearly from 3.26 to 2.53 eV with increasing x from 0 to 0.350.     

Epitaxial Properties of Co-Doped ZnO Thin Films Grown by Plasma Assisted Molecular Beam Epitaxy

High quality Co-doped ZnO thin films are grown on single crystalline Al2O3（0001） and ZnO（0001） substrates by oxygen plasma assisted molecular beam epitaxy at a relatively lower substrate temperature of 450℃. The epitaxial conditions are examined with in-situ reflection high energy electron diffraction （RHEED） and ex-situ high resolution x-ray diffraction （HRXRD）. The epitaxial thin films are single crystal at film thickness smaller than 500nm and nominal concentration of Co dopant up to 20%. It is indicated that the Co cation is incorporated into the ZnO matrix as Co^2＋ substituting Zn^2＋ ions. Atomic force microscopy shows smooth surfaces with rms roughness of 1.9 nm. Room-temperature magnetization measurements reveal that the Co-doped ZnO thin films are ferromagnetic with Curie temperatures Tc above room temperature.     

Growth,electronic and magnetic properties of doped ZnO epitaxial and nanocrystalline films

We have used oxygen plasma assisted metal organic chemical vapor deposition along with wet chemical synthesis and spin coating to prepare Co_xZn_1-xO and Mn_xZn_1-xO epitaxial and nanoparticle films. Co(II) and Mn(II) substitute for Zn(II) in the wurtzite lattice in materials synthesized by both methods. Room-temperature ferromagnetism in epitaxial Co:ZnO films can be reversibly activated by diffusing in Zn, which occupies interstitial sites and makes the material n-type. O-capped Co:ZnO nanoparticles, which are paramagnetic as grown, become ferromagnetic upon being spin coated in air at elevated temperature. Likewise, spin-coated N-capped Mn:ZnO nanoparticle films also exhibit room-temperature ferromagnetism. However, the inverse systems, N-capped Co:ZnO and O-capped Mn:ZnO, are entirely paramagnetic when spin coated into films in the same way. Analysis of optical absorption spectra reveals that the resonances Co(I)↔Co(II)+e^- _CB and Mn(III)↔Mn(II)+h⁺ _VB are energetically favorable, consistent with strong hybridization of Co (Mn) with the conduction (valence) band of ZnO. In contrast, the resonances Mn(I)↔Mn(II)+e^- _CB and Co(III)↔Co(II)+h⁺ _VB are not energetically favorable. These results strongly suggest that the observed ferromagnetism in Co:ZnO (Mn:ZnO) is mediated by electrons (holes). PACS 75.50.Pp     

BaT2As2 single crystals (T = Fe,Co, Ni) and superconductivity upon Co-doping

The crystal structure and physical properties of BaFe₂As₂, BaCo₂As₂, and BaNi₂As₂ single crystals are surveyed. BaFe₂As₂ gives a magnetic and structural transition at T_N = 132(1) K, BaCo₂As₂ is a paramagnetic metal, while BaNi₂As₂ has a structural phase transition at T₀ = 131 K, followed by superconductivity below T_c = 0.69 K. The bulk superconductivity in Co-doped BaFe₂As₂ below T_c = 22 K is demonstrated by resistivity, magnetic susceptibility, and specific heat data. In contrast to the cuprates, the Fe-based system appears to tolerate considerable disorder in the transition metal layers. First principles calculations for BaFe_1.84Co_0.16As₂ indicate the inter-band scattering due to Co is weak.     

Epitaxial growth of CeO2 on (100) InP using reactive r.f. magnetron sputtering

The epitaxial growth of CeO₂ thin films has been realized on (100) InP substrates using reactive r.f. magnetron sputtering. Oxide films were nucleated in the presence of molecular hydrogen (4% H₂/Ar sputtering gas) in order to reduce the native oxide formation on the InP surface, which interferes with CeO₂ epitaxy. A metal cerium target was used as the cation source, with water vapor serving as the oxidizing species. Epitaxial films were sputter-deposited at a substrate temperature of 550 °C in a H₂O vapor pressure of approximately 10^-3 Torr. Crystallinity of the oxide films was examined using θ–2θ X-ray diffraction, ω-rocking curves, and in-plane φ-scans. The best results were obtained when the initial nucleation layer was deposited with P(H₂O)<10^-5 Torr, followed by deposition at P(H₂O)=10^-3 Torr. The epitaxial growth of CeO₂ on InP could prove enabling in efforts to integrate functional oxides with InP-based optoelectronic and microwave technologies. Received: 20 February 20002 / Accepted: 21 February 2002 / Published online: 19 July 2002     

Anisotropic thermal expansion of AEFe2As2 (AE = Ba,Sr, Ca) single crystals

We report anisotropic thermal expansion of the parent, AEFe₂As₂ (AE = Ba, Sr, and Ca), compounds. Above the structural/antiferromagnetic phase transition anisotropy of the thermal expansion coefficients is observed, with the coefficient along the a-axis being significantly smaller than the coefficient for the c-axis. The high temperature (200 K ≤ T ≤ 300 K) coefficients themselves have similar values for the compounds studied. The sharp anomalies associated with the structural/antiferromagnetic phase transitions are clearly seen in the thermal expansion measurements. For all three pure compounds, the ‘average’ a-value increases and the c-lattice parameter decreases on warming through the transition, with the smallest change in the lattice parameters observed for SrFe₂As₂. The data are in general agreement with the literature data from X-ray and neutron diffraction experiments.     

Room-temperature epitaxial growth of V2O3 films

Herein we report the room-temperature epitaxial growth of V2O3 films by laser molecule beam epitaxy. X-ray diffraction profiles show the room-temperature epitaxial V2O3 films orient in the [110] direction on α-Al2O3(0001) substrates. Atomic force microscopy measurements reveal that the ultra-smooth surfaces with root-mean-square surface roughness of 0.11 nm and 0.28 nm for 10-nm-thick and 35-nm-thick V+2O3 film, respectively. X-ray photoelectron spectroscopy results indicate the V3 oxidation state in the films. Typical metal-insulator transition is observed in films at about 135 K. The resistivities at 300 K are approximately 0.8 mΩ cm and 0.5 mΩ cm for 10-nm-thick and 35-nm-thick V2O3 film, respectively.     

Nitrogen doping-mediated room-temperature ferromagnetism in insulating Co-doped SnO2 films

Co-doped SnO₂ films codoped with nitrogen (N) have been prepared by magnetron sputtering to investigate the effect of p-type defects on magnetic properties. The incorporation of N modifies the preferential growth orientation of the films. Multiple characterization techniques reveal that the incorporated Co²⁺ and N³⁻ ions substitute for Sn⁴⁺ and O²⁻ sites in SnO₂ lattice, respectively. As N concentration increases, the band gap of the films decreases because of the formation of Sn-N bond. Room-temperature ferromagnetism is observed in (Co, N)-codoped SnO₂ films, and the saturated magnetic moment is sensitive to the incorporated N concentration. The variations in the magnetic properties as a function of N concentration are discussed on the basis of bound magnetic polaron model.     

Study of the structure of a superconducting state of Co-doped BaFe2As2 multiband compounds

The terahertz and infrared spectra of the complex dynamic conductivity, as well as the temperature dependences of the density of a superconducting condensate and the electronic specific heat of superconducting Ba(Fe_{1 ? x} Co _x )₂As₂ compounds, have been analyzed within a Bardeen-Cooper-Schrieffer-like model of a multiband superconductor with strong coupling. It has been shown that the superconducting state of these compounds is determined by three (one electronic and two hole) weakly interacting condensates. The order parameters of the condensates are: Δ₁ ≈ 15 cm^?1, Δ₂ ≈ 21 cm^?1, and Δ₃ ≈ 30–35 cm^?1. The results significantly refine the existing notions on the structure of the superconducting state of Co-doped BaFe₂As₂ multiband compounds.     

Co-doped In2O3 thin films: Room temperature ferromagnets

Laser-ablated Co-doped In₂O₃ thin films were fabricated under various growth conditions on R-cut Al₂O₃ and MgO substrates. All Co:In₂O₃ films are well-crystallized, single phase, and room temperature ferromagnetic. Co atoms were well substituted for In atoms, and their distribution is greatly uniform over the whole thickness of the films. Films grown at 550 °C showed the largest magnetic moment of about 0.5 μ_B/Co, while films grown at higher temperatures have magnetic moments of one order smaller. The observed ferromagnetism above room temperature in Co:In₂O₃ thin films has confirmed that doping few percent of magnetic elements such as Co into In₂O₃ could result in a promising magnetic material.     

Distribution and magnetization of Co near the rutile TiO2 (110) surface: A first-principles study

The room-temperature ferromagnetism demonstrated by Co-doped TiO₂ films remains a challenge to our understanding, notwithstanding intensive experimental and theoretical investigations. We have calculated the binding energy and spin-polarization of Co atoms doped in the rutile TiO₂ (110) surface using first-principles method, aiming to elucidate the relationship between structure and magnetism of Co-doped TiO₂ films. In a defect-free surface the binding energy of Co substituting for Ti reduces slightly with the depth into the surface, suggesting a very minor Co depletion near the surface. More interestingly, the stability of ferromagnetic coupling over anti-ferromagnetic coupling of Co atoms decreases rapidly when it goes from surface to the bulk region. The residual ferromagnetism in the surface will give rise to a non-vanishing average magnetic moment of the thin film. The calculated pairing energy of Co is 0.12 eV/Co in the surface layer and 0.20 eV/Co in the middle layer of the film, an indication that Co atoms have a tendency to aggregate in both regions and that pairing will not modify the Co concentration in the direction vertical to the surface.     

Co掺杂MgF2电子结构和光学特性的第一性原理研究

基于密度泛函理论（DFT）的第一性原理平面波超软赝势方法,计算了Co掺杂MgF₂晶体的几何结构、电子结构和光学性质.结果表明,Co掺杂导致MgF₂晶体结构畸变,可能发生一种类四方和斜方型结构相变.由于Co原子的加入,体系的禁带宽度减小,可观察到半导体—金属性转变.计算也表明,Co掺杂对静态介电常数和光吸收系数有重要调制作用,所得结果与最近实验测量很好相符,揭示了Co:MgF₂体系在光学元器件方面的潜在应用. 关键词： 密度泛函理论（DFT） 第一性原理 超软赝势 2')" href="#">Co掺杂MgF₂     

Critical current densities and vortex dynamics in FeTexSe1−x single crystals

The critical current density and the normalized relaxation rate are reported in FeTe_0.59Se_0.41 single crystal. Critical current density is of order of 10⁵ A/cm², which is comparable to that in Co-doped BaFe₂As₂. In low temperature and low field region, the vortex dynamics of this system is well defined by the collective creep theory, which is quite similar to Co-doped BaFe₂As₂ reported before. We also discuss the origin of the anomaly in the field dependence of the relaxation rate.     

Raman scattering investigations on Co-doped ZnO epitaxial films: Local vibration modes and defect associated ferromagnetism

Raman scattering spectroscopy has been performed on high quality Co-doped ZnO epitaxial films, which were grown on Al₂O₃ (0001) by oxygen-plasma assisted molecular beam epitaxy. Raman measurements revealed two local vibration modes (LVMs) at 723 and 699 cm⁻¹ due to the substitution of Co²⁺ in wurtzite ZnO lattice. The LVM at 723 cm⁻¹ is found to be an elemental sensitive vibration mode for Co substitution. The LVM at 699 cm⁻¹ can be attributed to enrichment of Co²⁺ bound with oxygen vacancy, the cobalt–oxygen vacancy–cobalt complexes, in Zn_1−xCo_xO films associated with ferromagnetism. The intensity of LVM at 699 cm⁻¹, as well as saturated magnetization, enhanced after the vacuum annealing and depressed after oxygen annealing.     

On the origin of ferromagnetism in semiconducting TiO2−δ:Co oxide

In Co-doped TiO_2?δ oxide films deposited on SrTiO₃(100) substrates, a room-temperature ferromagnetism is found to occur only in a limited charge-carrier concentration interval from 2×10¹⁸? 5×10²² cm^?3. This indirectly testifies that ferromagnetism in the aforementioned n-type semiconductor is associated with the exchange interaction of magnetic ions via conduction electrons rather than with the formation of Co clusters in the material. The magnetic moment per Co atom is 0.8μ_B in the TiO cubic phase and 0.5μ_B in the anatase tetragonal phase of TiO₂.     

Scanning tunneling microscopy observation of ultrathin epitaxial CoSi<Subscript>2</Subscript>(111) films grown at a high temperature

Scanning tunneling microscopy (STM) is used to study the basic laws of growth of ultrathin epitaxial CoSi₂(111) films with Co coverages up to 4 ML formed upon sequential deposition of Co and Si atoms taken in a stoichiometric ratio onto the Co–Si(111) surface at room temperature and subsequent annealing at 600–700°C. When the coverage of Co atoms is lower than ~2.7 ML, flat CoSi₂ islands up to ~3 nm high with surface structure 2 × 2 or 1 × 1 grow. It is shown that continuous epitaxial CoSi₂ films containing 3–4 triple Si–Co–Si layers grow provided precise control of deposition. CoSi₂ films can contain inclusions of the local regions with (2 × 1)Si reconstruction. At a temperature above 700°C, a multilevel CoSi₂ film with pinholes grows because of vertical growth caused by the difference between the free energies of the CoSi₂(111) and Si(111) surfaces. According to theoretical calculations, structures of A or B type with a coordination number of 8 of Co atoms are most favorable for the CoSi₂(111)2 × 2 interface.     

稀掺杂GaNxAs1－x(x≤0.03)薄膜的调制光谱研究

利用室温下压电调制反射光(PzR)谱技术系统测量了N掺杂浓度为0.0%—3%的分子束外延生长GaN_xAs_1-x薄膜，并对图谱中所观察的光学跃迁进行了指认.在GaN_0.005As_0.995和GaN_0.01As_0.99薄膜的PzR谱中观察到此前只在椭圆偏振谱中才看到的N掺杂相关能态E₁+Δ₁+Δ_N.当N掺杂浓度达到 关键词： 压电调制反射光谱(PzR) xAs_1-x薄膜')" href="#">GaN_xAs_1-x薄膜 分子束外延(MBE)     

Development of high sensitivity ethanol gas sensor based on Co-doped SnO2 nanoparticles by microwave irradiation technique

We have successfully synthesized Co doped SnO₂ nanoparticles by a simple microwave irradiation technique. Powder X-ray diffraction results reveal that the SnO₂ doped with cobalt concentration from 0 to 5 wt % crystallizes in tetragonal rutile-type structure. The products were annealed at 600 °C for 5 h in ambient atmosphere in order to improve crystallinity and structural perfection. Transmission electron microscopy (TEM) studies illustrate that both the undoped and Co doped SnO₂ crystallites form in spherical shapes with an average diameter of 30–15 nm, which is in good agreement with the average crystallite sizes calculated by Scherrer's formula. A considerable red shift in the absorbing band edge was observed with increasing of Co content (0–5 wt %) by using UV–Vis diffuse reflectance spectroscopy (DRS). Oxygen-vacancies, tin interstitial and structural defects were analyzed using photoluminescence (PL) spectroscopy. Electron paramagnetic resonance (EPR) spectroscopic studies clearly showed that the Co²⁺ was incorporated into the SnO₂ host lattice. Ethanol gas sensitivity of pure and Co-doped (5 wt %) SnO₂ nanoparticles were experimented at ambient temperature using optical fiber based on clad-modified method. By modifying the clad exposure to ethanol vapor, the sensitivities were estimated to be 18 and 30 counts/100 ppm for undoped and Co-doped SnO₂ nanoparticles, respectively. These results show that the Co doping into SnO₂ enhances its ethanol gas sensitivity significantly.