Mössbauer Studies of Electrodeposited and Ion Beam Mixed Alloy Coatings

CEMS, XMS, XRD and electron microprobe analysis were applied to study electrodeposited and ion beam mixed Fe–Cr–Ni as well as electrodeposited and ball-milled Sn–Cr alloys. In Fe–Cr–Ni alloys with composition 40% Cr and 20–30% Ni a metastable ferromagnetic phase has been found beside a metastable paramagnetic and an equilibrium phase in all deposits. The relative occurrence of the ferromagnetic phase exhibits an increase in the plating temperature range: 30–40°C. With plating temperature an increase of the short-range order in the ferromagnetic phase was observed. The highenergy heavy ion irradiation of Fe–Ni–Cr multilayer produces ferromagnetic and paramagnetic metastable phases. The electrodeposition of Sn–Cr alloys results in metastable Sn–Cr phases. In the case of ball-milling preparation the equilibrium Sn₃Cr₂ phase (=2.3 mm/s, =1.2 mm/s) appears in Sn–Cr alloys. The quantity of the Sn₃Cr₂ phase increases with the milling time.     

Surface morphology of metal films deposited on mica at various temperatures observed by atomic force microscopy

Thin films of eight metals with a thickness of 150 nm were deposited on mica substrates by thermal evaporation at various temperatures in a high vacuum. The surface morphology of the metal films was observed by atomic force microscopy (AFM) and the images were characterized quantitatively by a roughness analysis and a bearing analysis (surface height analysis). The films of Au, Ag, Cu, and Al with the high melting points were prepared at homologous temperatures T/T_m = 0.22-0.32, 0.40, and 0.56. The films of In, Sn, Bi, and Pb with the low melting points were prepared at T/T_m = 0.55-0.70, where T and T_m are the absolute temperatures of the mica substrate and the melting point of the metal, respectively. The surface morphology of these metal films was studied based on a structure zone model. The film surfaces of Au, Ag, and Cu prepared at the low temperatures (T/T_m = 0.22-0.24) consist of small round grains with diameters of 30-60 nm and heights of 2-7 nm. The surface heights of these metal films distribute randomly around the surface height at 0 nm and the morphology is caused by self-shadowing during the deposition. The grain size becomes large due to surface diffusion of adatoms and the film surfaces have individual characteristic morphology and roughnesses as T increases. The surface of the Al film becomes very smooth as T increases and the atomically smooth surface is obtained at T/T_m = 0.56-0.67 (250-350 °C). On the other hand, the atomically smooth surface of the Au film is obtained at T/T_m = 0.56 (473 ± 3 °C). The films of In, Sn, Bi, and Pb prepared at T/T_m = 0.55-0.70 also show the individual characteristic surface morphology.     

On the superconductivity of the tin-hydrogen system

Conductivity and superconductivity studies of amorphous [Sn_1–y Cu _y–]_1–x H _x samples in connection with¹¹⁹Sn Mössbauer effect experiments on¹¹⁹Sn_1–x H _x give strong evidence that the observed increase of the superconducting transition temperatureT _c in the Sn–H-system is caused by the stabilization of an amorphous structure. Thus the Sn–H-system is very similar to the Sn–Cu-system and no H-specific effect is needed to explain the increase ofT _c.     

High-T c superconducting Bi−Sr−Ca−Cu−O thin films prepared by laser-induced plasma deposition

High-T _c superconducting thin films of Bi–Sr–Ca–Cu oxides were prepared by laser-induced plasma deposition of high-T _c superconducting Bi₂Sr₂Ca₁Cu₂O_x and Bi₂Sr₂Ca₂Cu₃O_x targets in vacuum and a short post-annealing in air at 875°C. Thin films (thickness <500 nm) with a critical temperatureT _c -onset of 95 K can be prepared on silicon substrate material with a SrTiO₃ interface layer. The thin films were completely superconducting between 80 and 90 K. The stoichiometry transfer of superconducting target material by laser-induced plasma deposition was investigated.     

Thickness dependence of superconductivity for In/Mo thin films

We report on the superconducting characteristics of the Indium thin films on molybdenum under-layer as a function of the In film thickness. Our molybdenum under-layer with thickness of 50 Å does not cause the occurrence of superconductivity until 1.5 K and the sheet resistance has logarithmic temperature dependence observed in the present investigation. As thickness of In increased, the oscillation phenomenon of T_C was observed at early stage of deposition and the value of T_C is higher than the that for bulk of In. Furthermore, it is found that with increase of the In thickness, there are large differences of the strengths of the upper critical magnetic field H_C2(T), resistivity and T_C between films with thickness below and above 100 Å. On the other hand, the T_C decreases monotonously as sheet resistance increases, when the T_C is plotted against sheet resistance. To clarify the relation of superconducting characteristics and the surface structure of the films with different thickness, we have performed surface observation by atomic force microscope. As a result, we have found that the surface changes from homogeneous structure to inhomogeneous (or percolative) structure, when the thickness of in films pass through about 100 Å. Superconductivity of In/Mo films with relatively thick-inhomogeneous films cannot be explained in terms of the simple percolation theory. Therefore, we analysis the experimental data of H_C2(T) near T_C, using a extended Landau–Ginzburg model. It is found out that our In/Mo films must consider some factors; such as, grain size, the distance of grain space, and the strength of couplings between grains.     

Melting and Recrystallization of Nylon-6,10 Thin Films

The melting and recrystallization of nylon-6,10 thin films immersed in an aqueous solution of calcium chloride were investigated by DSC measurements. The crystal length, ζ, was determined as a function of the melting peak temperature, T _m . The end surface free energy of nylon-6,10 crystals used for the ζ–T _m conversion was derived thermodynamically. For films of 0.01 mm thickness, the original length of ζ (=7.6 structural units) at T _m decreased step by step with increasing immersion time by the length near the structural unit (2.24 nm) per step. However, the suppression of the recrystallization after melting of the original crystals formed during the first cooling by the adsorbed calcium ions did not occur completely, even for films immersed for 30～60 min at 50°C.     

Aluminium diffusion in titanium nitride films. Efficiency of TiN barrier layers

Two kinds of reactively evaporated titanium nitride films with columnar (B ₀ films) and fine-grained (B ₊ films) film structures, respectively, have been examined as diffusion barriers for preventing aluminium diffusion. The aluminium diffusion profiles have been investigated by 2 MeV ⁴He⁺ Rutherford backscattering spectrometry (RBS) at temperatures up to 550° C. The diffusivity from 300° C to 550° C is: D[m²s^–1]=3×10^–18 exp[–30/(RT)] in B ₀ layers and D[m²s^–1]=1.4×10^–16 exp[–48/(RT)] in B ₊ TiN layers. The activation-energy values determined indicate a grain boundary diffusion mechanism. The difference between the diffusion values is determined implicitly by the microstructure of the layers. Thus, the porous B ₀ layers contain a considerable amount of oxygen absorbed in the intercolumnar voids and distributed throughout the film thickness. As found by AES depth profiling, this oxygen supply allows the formation of Al₂O₃ during annealing the latter preventing the subsequent diffusion of the aluminium atoms.     

Diffusion of silicon in titanium nitride films. Efficiency of TiN barrier layers

Two kinds of reactively evaporated titanium nitride films with columnar (B ₀ films) and fine-grained film structure (B ₊ films) have been examined as diffusion barriers, preventing the silicon diffusion in silicon devices. The silicon diffusion profiles have been investigated by 2 MeV ⁴He⁺ Rutherford backscattering spectrometry (RBS) after annealing at temperatures up to 900° C, in view of application of high-temperature processes. The diffusivity from 400 to 900° C: D (m² s^–1)=2.5×10^–18 exp[–31 kJ/mol/(RT)] in B ₀ layers and D (m² s^–1)=3×10^–19 exp[–26 kJ/mol/(RT) in B ₊ TiN layers. The diffusivities determined correspond to grain boundary diffusion, the difference being due to the different microstructure. The very low diffusivity of silicon in B ₊ TiN layer makes it an excellent high-temperature barrier preventing silicon diffusion.     

Effect of substrate interactions on the melting behavior of thin polyethylene films

Polymer films have been known to change their physical properties when film thickness is decreased below a certain value. The cause of this phenomenon is still unclear but it has been suggested that interactions and/or chain free-volume changes at the surface of the films are largely responsible for this behavior. In this paper, the effect of substrate interactions on the behavior of polymer thin films is evaluated quantitatively. The infrared spectra of nanothin polyethylene (PE) films were recorded as a function of temperature and amount of substrate covering the surface of the film. The evolution of specific bands in the CH₂ rocking region of the spectra was used to determine the melting temperature (T _m ) of the material. Results show different variations in T _m depending on the nature of the substrate, indicating that interactions dominate free-volume considerations in PE thin films. By varying the amount of surface coverage, a quantitative estimate of the heat of interaction was determined, which confirmed the importance of surface interactions.     

Effect of oxygen segregation on the surface structure of single-crystalline niobium films on sapphire

Single-crystalline Nb films are grown on (1120) oriented sapphire substrates by electron-beam evaporation in ultra-high vacuum. The films are studied in-situ by RHEED and Auger analysis. At a substrate temperature T _S=750° C the RHEED pattern shows a smooth growth of bcc-Nb in the [110] direction. In addition to the fundamental streaks, we observe superlattice streaks of fractional order in several azimuthal directions. The reciprocal lattice of the surface is determined. The basic vectors of the superlattice in real space are given by b ₁=2a ₁, b ₂=–a ₁+3a ₂ where a ₁ and a ₂ are the basic vectors of the Nb (110) surface. Auger analysis shows that the surface of these films is contaminated with oxygen. Therefore, the superstructure is attributed to a modified surface structure due to segregated oxygen, possibly having diffused from the sapphire to the film surface. The superstructure dissappears during further evaporation of Nb at T _S<450° C with a concomitant decrease of the oxygen signal. Nb films on sapphire with a clean, oxygen-free surface can only be prepared at lower temperatures in an island-growth mode.     

Y1Ba2Cu3O7-δ thin films from KrF laser ablation with substrate heating and in situ patterning by CO2 laser radiation

Y₁Ba₂Cu₃O_7– thin films were deposited by KrF laser ablation while replacing conventional contact heating by cw CO₂ laser irradiation of the substrate front surface. The HTSC films obtained on (100)ZrO₂ showed T _c(R=0)=90 K, T(90–10%)=0.5 K, j _c=2.5 × 10⁶ A/cm², a sharp transition in the ac susceptibility X(T), and pure c-axis orientation. Micrographs of thin films (< 0.5 m) showed a smooth morphology while thick films (>1 m) contained many crystallites sticking in the bulk material. Furthermore, in situ patterning was achieved during deposition by local laser heating of a selected substrate surface area. The resulting planar films contained amorphous, semiconducting parts only 1 mm or less apart from crystalline material showing the above HTSC quality.Presented at LASERION '91, June 12–14, 1991, München (Germany)     

Crystallization temperatures of thin Co−Zr amorphous alloy films from electron diffraction

The transformation of amorphous thin alloy films of Co–Zr to the crystalline state was observed with an electron microscope in the diffraction mode. This investigation elucidates the crystallization temperatures,T _x , of thin films as opposed to theT _x presented for thicker samples; usually melt-quenched in the thickness range of 20–50 m. TheT _x of the thin films are compared also with theT _x for sputtered alloys of Co–Zr at 5 m.     

Concentration dependence of nickel diffusion in nickel-cobalt alloys

In the present paper the results of measuring the self-diffusion coefficients for Ni in Ni-Co alloy in the composition interval 0–100 at.% Co, and in the temperature range 1065–1290 °C are given. The measurements have been carried out by the Gruzin method using the radioisotope Ni-63. The curves indicating the concentration dependence of the diffusion coefficients calculated for differentaT _m vaules (T _m is the melting point at a given concentration,a is a number from the interval (0, 1)) are straight lines; this feature has been found in other solid solutions which slightly deviate from regularity as well. It results in simple equations for the concentration dependence of self-diffusion characteristicsD ₀ andH.     

多晶薄膜表面粗化与生长方式转变

采用原子力显微镜研究了磁控溅射多晶薄膜表面粗化行为对归一化沉积温度T_s/T_m(T_s是沉积温度，T_m是材料熔点)的依赖性与薄膜生长方式转变行为.随着T_s/T_m增加，薄膜表面粗糙度增加，而表征粗糙度随时间演化特征的生长指数β历经了先减小再增加的过程.β对T_s/T_m的依赖关系反映了薄膜生长方式的转变行为，即薄膜生长依次由随机生长方式向表面扩散驱动生长方式与异常标度行为生长方式转变.在低于体扩散控制薄膜生长的温度时，晶界扩散机理导致多晶薄膜的表面粗化的异常标度行为. 关键词： 多晶薄膜 表面粗化 温度 生长     

Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides

The Fe²⁺/Fe³⁺ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3–1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species –O–Fe(OH)₂ and (Si–O–)₂–FeOH forming the surface monolayer are not reduced at 400–600°C because of their covalent bonding to the silica surface, as demonstrated by Mössbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T 500°C with formation of metallic iron in the form of -Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T 600°C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves.     

Influence of magnetic field on cesium thermionic energy converter

This article deals with the calculation of the influence of the magnetic field upon the electric current of a thermionic converter presupposing the approach to conditions in a low-pressure cesium converter. The distribution of the starting velocities of the emitted electrons is considered firstly as independent of the angle from the perpendicular to the emitter plane, and secondly according to the cosine law.The magnetic field effect from the converter current is calculated and compared with the calculations in the papers by Schock [1] and Block [2]; the effect of the external magnetic field is verified by measurements on a solar thermionic converter prototype.Symbols F=I/I ₀ factor of current reduction from magnetic field effect - ¯F value of factorF (when the magnetic field is not constant) - I [A/m²] density of collector current (real current influenced by magnetic field) - I ₀ [A/m²] theoretical density of collector current (in ideal case equals electron emission current) - T _e [°K] electron gas temperature; assumed equal to emitter temperatureT _E [°K] - B[Wb/m²] magnetic induction (field) - D[m] distance from emitter to collector - R[m] radius of electrodes, emitter and collector - r[m] variable radius in the limits 0 toR - V [m/s] random velocity of electron - v _xz [m/s] component of the vectorV inx-z plane - v _m =2kT _E /m most probable velocity in the velocity distribution according to Maxwell and Boltzmann - w-v _xz /v _m relatively expressed electron velocityv _xz - the angle of any vectorV - [m] radius of circular electron path - n [m^–3] number (density) of electrons with certain value of random velocity - n ₀ [m^–3] total electron number (density) - n ₁ [m^–3] number of electrons returned to emitter by means of magnetic field - N ₀ [m^–2s^–1] total flow of thermionic electrons emitted from a unit surface - N ₁ [m^–2s^–1] partial flow of electrons returned to emitter - P=N ₁/N₀ relatively expressed flow of electrons returned to emitter (whenB = const.) - ¯P mean value ofP (whenB const.) - F _cos, ,P _cos, values asF,¯F,P,¯P in case of velocity distribution according to cosine law - m=9·107×10^–31 [gk] electron mass - e=1·60×10^–19 [C] electron charge - k×1·38×10^–23 [J/grad] Boltzmann's constant - ₀ 1·257×10^–6 [H/Vs] permeability of vacuum     

The magnetic susceptibility of p-type CdSb

The paper gives the measurements of the magnetic susceptibility of p-type CdSb at 77°K on samples crystallographically oriented and cut from single crystals having an acceptor concentration of 2.3×10¹⁵cm^–3, 2.4×10¹⁶ cm^–3 and 1.5×10¹⁷ cm^–3. The anisotropy of the lattice and hole gas contribution was found and the ratio of the hole effective mass obtained from measurement of the transversal magnetoresistivity in p-type CdSb at 77°K [3] was used to determine their absolute values:m _a=0.48m ₀=m _b=0.44m ₀,m _c=0.17m ₀.     

An X-ray diffraction and Mössbauer spectroscopic study on thec-axis texture YBa2(Cu1−x Fe x )3O7−y thick films

YBa₂(Cu_1–x Fe _x )₃O_7–y thick films (x=0, 0.01, 0.02, 0.03) on ceramic substrate were prepared. X-ray diffraction determinations show the formation of partialc-axis texture perpendicular to the surface of the ceramic substrate in the preparation process. The⁵⁷Fe Mössbauer spectra were measured at 300 K, where the angle between the incidence-ray beam and the surface of the film is 90° and 36°, respectively. The⁵⁷Fe Mössbauer spectra with=90° possess four sets of asymmetrical doublets.     

Temperature accelerated dielectric breakdown of PECVD low-k carbon doped silicon dioxide dielectric thin films

The dielectric breakdown strength of carbon doped silicon dioxide thin films with thickness d from 32 nm to 153 nm is determined at 25 °C, 50 °C, 100 °C, 150 °C and 200 °C, using I–V measurements with metal-insulator-semiconductor (MIS) structures. It is found that the dielectric breakdown strength, E_B, decreases with increasing temperature for a given film thickness. In addition, a film thickness dependence of breakdown is also observed, which is argued to show an inverse relation to thickness d in the form of E_B∝(d-d_c)^-n. The exponential parameter n and critical thickness limit d_c also exhibit temperature dependent behavior, suggesting a temperature accelerated electron trapping process. The activation energy for the temperature acceleration was shown to be thickness dependent, indicating a thickness dependent conduction mechanism. It is thereafter demonstrated that for relatively thick films (thickness >50 nm), the conduction mechanism is Schottky emission. For relatively thin films (thickness <50 nm), the Schottky conduction mechanism was obeyed at low field region while FN tunnelling was observed as a prevail one in the high field region. PACS 73.40.Qv     

Silicide formation by furnace annealing of thin Si films on large-grained Ni substrates

Si films with a thickness of approximately 250 nm have been electron-beam evaporated on thick, large-grained Ni substrates (grain size a few mm to 1 cm in diameter). An in situ sputter cleaning procedure has been used to clean the Ni surface before the Si deposition. Thermal annealings have been performed in a vacuum furnace. Ni₂Si is the first phase that grows at temperatures between 240 °C and 300 °C as a laterally uniform interfacial layer with a diffusion-controlled kinetics. The layer thicknessx follows the growth lawx ²=kt, withk=k ₀ exp(-E _a k _B T), wherek ₀=6.3 × 10^–4cm 2/s andE _a=(1-1±0.1) eV. Because of the virtually infinite supply of Ni, annealing at 800 °C for 130min yields a Ni-based solid solution as the final phase. The results are compared with those reported in the literature on suicide formation by the reaction of a thin Ni film on Si substrates, as well as with those for interfacial phase formation in Ni/Zr bilayers.