非晶Ni88P12合金薄膜的表面形貌特征与晶化行为的研究

采用化学镀的方法在363K和p型Si（100）衬底上制得非晶Ni₈₈P₁₂合金薄膜．利用X射线衍射、X射线光电子能谱、扫描隧道显微镜和原子力显微镜对非晶合金薄膜及其经处理后形成的氧化态、还原态和晶态的结构、组分和表面的形貌特征作了研究，并对它的晶化行为作了初步探讨．结果表明，非晶合金薄膜是由纳米级微粒聚集成微米级颗粒组成；在低于晶化温度条件下经氧化和还原处理后的薄膜表面晶化；在晶化过程中，合金薄膜的非晶纳米微粒转变为微晶后长大成晶粒，其表面结构光滑平坦，几何边界 关键词：     

Surface properties of Fe76Mo8Cu1B15 alloy after annealing

NANOPERM-type alloy Fe₇₆Mo₈Cu₁B₁₅ is investigated in amorphous and in partially crystallized state. Samples were prepared by 1 h isothermal annealing in vacuum at temperatures ranging from 330°C up to 700°C. Bulk and surface microstructural characteristics were studied using transmission and conversion electron Mössbauer effect techniques, respectively. Surface features were checked by the help of atomic force microscopy. Presence of nanocrystalline bcc-Fe phase was detected during the first crystallization stage. The crystallization process starts at 450°C and it is more pronounced in surface regions than in the bulk. With progressing crystallization, hyperfine parameters especially of the amorphous residual phase are altered. Distinctions in surface morphology are revealed between wheel and air side of the ribbon-shaped samples.     

Crystallization of the Fe84-xVxB16 amorphous alloys

Resistometric and Mössbauer measurements of the isothermal crystallization of nearly eutectic Fe-V-B amorphous alloys containing up to 8 at.%V were performed. The concentration dependence of the hyperfine fields of the crystallization products was found. The α-Fe-V and tetragonal mixed boride were detected and their contents in the course of crystallization estimated. The crystallization kinetics corresponds to the growth of α-phase nuclei proved by CEMS at the contact surface.     

Mössbauer study on surface crystallization behavior of amorphous Fe90Zr10 alloy ribbon

The precipitous drop of crystallization temperature at the surface of amorphous Fe₉₀Zr₁₀ ribbon is confirmed by TMS and CEMS. The deficiency in Zr at the surface amorphous phase, caused by the absorption and the diffusion of oxygen, is found to be responsible for it. The final crystalline products are assigned to α-Fe, Fe₃Zr and Fe₂Zr, whereas only α-Fe precipitates at the surfaces. Moreover, it is indicated that the crystallization behavior of the bulk is influenced by the ambient gases during annealing and quite different between in vacuum and in air.     

A STUDY OF THE CRYSTALLIZATION OF AMORPHOUS Cu60Zr40 ALLOY

The crystallization of the amorphous Cu₆₀Zr₄₀ alloy has been studied by differential scanning calorimetry (DSC), scanning Auger microprobe (SAM) and transmission electron microscopy (TEM). The DSC trace showed that the sample exhibited a glass transition at 750 K and a strong exothermic effect beginning from 782 K. An enrichment of the element Zr and significant oxygen contamination in a zone near the surface to a depth of about 10 nm were revealed by SAM in the analysis of surface competition and depth profiles of the Cu₆₀Zr₄₀ sample. Also, the change of concentration ratio of Ca to Zr in amorphous matrix at the clean Cu₆₀Zr₄₀ surface as a function of annealing temperature was examined in detail, and it was found that the concentration of Zr at the surface is slightly higher than that in the bulk until 780K and that the concentration ratio of Cu to Zr in matrix has an abrupt increase in the temperature range of 780-800K. The observations by high resolution TEM revealed the appearance of cluster-like regions of approximately 1.5-2.0 nm in size just before crystallization and they distributed randomly throughout the sample. This phenomenon is analogous to the results obtained using field ion microscopy (FIM) by the present authors. The microstructural changes of the sample daring heating show the gradual crystallization of the amorphous matrix.     

Mössbauer study of surface crystallization in metallic glasses

Mössbauer spectroscopy has been used to study the kinetics of surface crystallization in amorphous Fe₄₀Ni₄₀B₂₀. The activation energy for the surface crystallization is found to be about 230 kJ/mol, which is much lower than that for the bulk crystallization. Change in the surface composition due to aging can be a possible cause of this reduced surface stability.     

A STUDY OF THE CRYSTALLIZATION OF AMORPHOUS Cu60Zr40 ALLOY

The crystallization of the amorphous Cu₆₀Zr₄₀ alloy has been studied by differential scanning calorimetry (DSC), scanning Auger microprobe (SAM) and transmission electron microscopy (TEM). The DSC trace showed that the sample exhibited a glass transition at 750 K and a strong exothermic effect beginning from 782 K. An enrichment of the element Zr and significant oxygen contamination in a zone near the surface to a depth of about 10 nm were revealed by SAM in the analysis of surface competition and depth profiles of the Cu₆₀Zr₄₀ sample. Also, the change of concentration ratio of Ca to Zr in amorphous matrix at the clean Cu₆₀Zr₄₀ surface as a function of annealing temperature was examined in detail, and it was found that the concentration of Zr at the surface is slightly higher than that in the bulk until 780K and that the concentration ratio of Cu to Zr in matrix has an abrupt increase in the temperature range of 780-800K. The observations by high resolution TEM revealed the appearance of cluster-like regions of approximately 1.5-2.0 nm in size just before crystallization and they distributed randomly throughout the sample. This phenomenon is analogous to the results obtained using field ion microscopy (FIM) by the present authors. The microstructural changes of the sample daring heating show the gradual crystallization of the amorphous matrix.     

Surface and bulk crystallization of amorphous alloys Ni-Si-B probed by electrical resistivity

Electrical resistivity measurements are tested as a sensitive probe of the crystallization processes in amorphous metallic alloys of Ni₇₈Si₇B₁₅, rendering the determination of nucleation rates at the surface and in bulk. It is shown that the increase in the electrical resistivity just below the crystallization temperature is mainly due to nucleation phenomena. Moreover, the Avrami coefficient, calculated from resistivity data, provides information about types of crystallization mechanisms, dimensionality of the crystallite growth and the sequence of crystallization stages.     

Effect of hydrogen on surface texturing and crystallization of a-Si:H thin film irradiated by excimer laser

Hydrogenated amorphous silicon (a-Si:H) thin films have been considered for use in solar cell applications because of their significantly reduced cost compared to crystalline bulk silicon. However, their overall efficiency and stability are lower than that of their bulk crystalline counterpart. Limited work has been performed on simultaneously solving the efficiency and stability issues of a-Si:H. Previous work has shown that surface texturing and crystallization on a-Si:H thin film can be achieved through a single-step laser processing, which can potentially alleviate the disadvantages of a-Si:H in solar cell applications. In this study, hydrogenated and dehydrogenated amorphous silicon thin films deposited on glass substrates were irradiated by KrF excimer laser pulses and the effect of hydrogen on surface morphologies and microstructures is discussed. Sharp spikes are focused only on hydrogenated films, and the large-grained and fine-grained regions caused by two crystallization processes are also induced by presence of hydrogen. Enhanced light absorptance is observed due to light trapping based on surface geometry changes of a-Si:H films, while the formation of a mixture of nanocrystalline silicon and original amorphous silicon after crystallization suggests that the overall material stability can potentially improve. The relationship between crystallinity, fluence and number of pulses is also investigated. Furthermore, a step-by-step crystallization process is introduced to prevent the hydrogen from diffusing out in order to reduce the defect density, and the relationship between residue hydrogen concentration, fluence and step width is discussed. Finally, the combined effects show that the single-step process of surface texturing and step-by-step crystallization induced by excimer laser processing are promising for a-Si:H thin-film solar cell applications.     

The effect of femtosecond laser micromachining on the surface characteristics and subsurface microstructure of amorphous FeCuNbSiB alloy

Detailed studies on the effects of femtosecond laser ablation on surface characteristics and subsurface microstructure of amorphous FeCuNbSiB alloy are reported. Three types of ripple structures were observed on the material surface in the gentle ablated (damaged) zone. As observed with X-ray diffraction (XRD), amorphous form is kept in the damaged zone, and there is few crystallization form in ablation zone.     

Crystallization of D2O thin films on Ru(0 0 1) surfaces

The phase conversion of amorphous solid water (ASW) to crystalline ice (CI) has been investigated in the very thin (∼10 monolayers) film regime on a Ru(0 0 1) surface. We analyze the converted CI fraction with the Avrami model, and recognize that one-dimensional CI growth occurs, which can be contrasted to the three-dimensional CI growth generally established in the thick (≥50 monolayers) film regime. We evaluate activation energy for the ASW crystallization to be about 1.0 eV. We suggest that the ASW crystallization is not influenced by the substrate even near the substrate-ice interface.     

Heterogeneous crystallization of amorphous silicon expedited by external force fields: a molecular dynamics study

Applying a molecular dynamics simulation technique with the Tersoff potential, we investigate the isothermal crystallization processes of amorphous silicon (a-Si). To obtain a realistic amorphous structure, a rapid quenching process from liquid-phase at 3500 K to solid-phase at 500 K is simulated at a rate of 10¹² K/s and the Voronoi analysis is conducted to observe atomic structural changes during this cooling process. This amorphous structure is utilized to simulate the crystallization processes at various process temperatures with and without external force fields. While homogeneous crystallization of a-Si could not be achieved readily, it is shown that the heterogeneous crystallization can be significantly accelerated by external force fields. This enhancement is owing to increased molecular jumping frequencies associated with the molecular potential energies being increased by external excitations, rather than due to thermal mechanisms normally found in conventional solid-phase crystallization processes.     

Influence of surface on the nanocrystalline structure formation

In contrast to the common Fe-B-base amorphous alloys, Mössbauer transmission and CEMS studies of the early stages of the nanocrystalline structure formation in the new magnetically soft FeCuNbSiB alloys produced via the amorphous way, revealed that the primary crystallization of the Fe₃Si-like phase is inhibited by the surface. This result supports the role of copper as nucleation agent in the amorphous structure.     

Crystallization over the liquid layer

In this article, a new phenomenon of high-speed crystallization of metals in a low-temperature plasma formed as a result of the effect of a short laser pulse is considered. The mechanism of the way the reaction occurs on the surface of the melt formed under the effect of the laser pulse on an amorphous substrate is described. The main factors affecting the crystallization process are described. Primary attention is paid to laminar convection and the latent heat of crystallization.     

The influence of a poly-Si intermediate layer on the crystallization behaviour of Ni-Ti SMA magnetron sputtered thin films

Shape memory alloy Ni-Ti thin films as sputtered are amorphous if the substrate is not intentionally heated during deposition. Therefore, these films have to be heat treated to induce crystallization in order to exhibit the shape-memory effect. Several films have been prepared by dc magnetron sputtering and then studied concerning the influence of the type of substrate (single-crystal Si, polycrystalline Si) on the crystallization kinetics and the final structure. The structural development of the films during crystallization (at a constant temperature of 430 °C) has been studied by X-ray diffraction in grazing incidence geometry off-plane (GIXD) at a synchrotron-radiation beamline. These experiments allow us to establish a correlation between the deposition conditions and the kinetics of crystallization. For films deposited at an electrode distance of 70 mm on a Si(100) substrate, a longer crystallization time is needed compared with films obtained at 40 mm, for otherwise fixed deposition parameters. The analysis of the nucleation kinetics by using the Johnson–Mehl–Avrami equation leads to exponents between 2.6 and 3. The presence of an intermediate layer of poly-Si drastically enhances the crystallization process. Additionally, ex situ annealing of identical samples at 500 °C during 1 h and complementary characterization of the structure and morphology of the films by cross-sectional transmission electron microscopy and selected-area electron diffraction were performed. The temperature dependence of the electrical resistivity was measured, identifying the phase transformation temperature ranges. An increase of the overall resistivity with the precipitation of Ni₄Ti₃ has been detected. Results obtained by X-ray reflectometry and GIXD suggest that during crystallization excess nickel is driven into an amorphous region ahead of the crystal/amorphous interface, thus leading to a higher concentration of Ni at the surface and further precipitation of Ni₄Ti₃. PACS 81.15.Cd; 61.10.Nz; 68.55.Jk     

Crystallization of glassy metal surfaces in Mg–Zn alloy determined by resonant photoacoustic detection

Amorphous layers in a Mg-based alloy are studied by a resonant photoacoustic technique. The technique is shown to provide information on the crystallization temperature of a thin amorphous layer when the sample is heated. This determination provides crucial information regarding thermal stability of the treated surface, not accessible by standard calorimetric techniques. The layer analyzed is tens of micrometers thick, produced by rapid melting by a pulsed electron gun and subsequent rapid cooling towards the substrate. It is shown that the signal from the photoacoustic detection arises mainly from the volume change during crystallization at about 390 K. The volume change due to the structural relaxation of the glass before crystallization is also detected. PACS 64.70.Pf; 78.20.Nv; 81.70.Cv     

Boundary-driven colloidal crystallization in simple shear flow

Using confocal microscopy, we directly observe that simple shear flow induces transient crystallization of colloids by wall-normal propagation of crystallization fronts from each shearing surface. The initial rate of the front propagation was 1.75±0.07 colloidal layers per unit of applied strain. The rate slowed to 0.29±0.04 colloidal layers per unit of applied strain as the two fronts approached each other at the midplane. The retardation of the front propagation is caused by self-concentration of shear strain in the growing bands of the lower-viscosity crystal, an effect that leads to a progressive reduction of the shear rate in the remaining amorphous material. These findings differ significantly from previous hypotheses for flow-induced colloidal crystallization by homogeneous mechanisms.     

Phase and structural transformations in a molecular dynamics model of iron under ultrafast heating and cooling

It is shown that a system of classical particles considered in a molecular dynamics model with Pak-Doyama pairwise interatomic potential adequately describes not only the various structural states of iron (melt, bcc crystal, metal glass) but also the complex self-organization processes occurring in first-and second-order phase transitions (crystallization and vitrification, respectively). When the temperature is varied at a constant rate of 6.6×10¹¹ K/s, crystallization sets in from both the amorphous and the liquid state; at a rate of 1.9×10¹² K/s, crystallization is observed only in the amorphous state; and when heated at a rate of 4.4×10¹² K/s, the model amorphous iron transfers to the liquid state without crystallization. The energy of homogeneous formation of a crystal nucleus in the bulk of the amorphous phase of iron is calculated to be ～0.71 eV under the assumption that there is a spectrum of activation energies.     

Structural separation of amorphous Fe40Ni40P14B6 alloy during natural ageing

Both the transmission and depth selective conversion electron Mössbauer spectroscopy (DCEMS) were applied usefully to study structural transformations in the bulk and in the surface layer ～50 and 100 nm thick during three years natural ageing of an amorphous alloy. The primary crystallization was revealed in the surface layer ～100 nm thick on the rough side of amorphous ribbon.     

Glass transition and intermixing of amorphous water and methanol

The diffusion of molecules in amorphous water and methanol films has been investigated on the basis of time-of-flight secondary ion mass spectrometry as a function of temperature. The glass-liquid transition of the amorphous water film occurs at 130-145 K as confirmed from the surface segregation of embedded methanol molecules. The morphology of the pure amorphous water film changes drastically at 160 K as a consequence of dewetting induced by the surface tension and the strongly decreased viscosity of the film. The morphology of the amorphous methanol film changes at 115 K following the self-diffusion onset at 80 K. The binary films of water and heavy methanol are intermixed completely at 136 K as evidenced by the occurrence of the H/D exchange.