生长初期Ta膜的表面动态演化行为

用磁控溅射方法在单晶Si衬底上沉积膜厚为15—250nm的Ta膜.基于原子力显微镜获得的薄膜表面形貌，用动力学标度理论量化表征薄膜表面动态演化行为.结果表明：当膜厚d<50nm时，薄膜生长指数β≈0.17，而d>50nm后β≈0.45；随着d增加，粗糙度指数α由0.24逐渐增加到0.69，且在d>50nm后趋于稳定.Ta膜的表面动态演化行为揭示了其由小岛聚合结构向连续膜演化的生长过程.与自阴影等非局域效应引起的非稳定行为不同的是，当d<50nm时，薄膜表面动态演化的非稳定行为来源于生长初期的小岛聚合，表面小岛沿膜面切向的生长优于沿法向的生长.随着d继续增加，薄膜以连续膜形式生长，表面动态演化趋于稳定.     

Self-organization of bimetallic PdAu nanoparticles on SiO<Subscript>2</Subscript> surface

Bimetallic PdAu nanoparticles on SiO₂ substrate were produced by a sequential room-temperature sputtering deposition method. By the atomic force microscopy technique we studied the nanoparticles self-organization mechanisms in various conditions. First, Pd nucleation and growth proceeds at the substrate defects and the Pd nanoparticles density increase rapidly. During the second sputtering deposition, Au atoms adsorb on the SiO₂ and diffuse toward Pd nanoparticles without forming new nuclei. The Au atoms are trapped by the preformed Pd nanoparticles, forming PdAu bimetallic nanoparticles which size increases. Furthermore, fixing the amount of deposited Pd and increasing the amount of deposited Au, we analyzed the evolution of the PdAu film surface morphology: we observe that the PdAu grows initially as three-dimensional islands; then the PdAu film morphology evolves from compact three-dimensional islands to partially coalesced worm-like structures, followed by a percolation morphology and finally to a continuous and rough film. The application of the interrupted coalescence model allowed us to evaluate the critical mean island diameter R _c ≈ 2.8 nm for the partial coalescence process. The application of the dynamic scaling theory of growing interfaces allowed us to evaluate the dynamic growth exponent β = 0.21 ± 0.01 from the evolution of the film surface roughness. Finally, fixing the amount of deposited Pd and Au we studied the self-organization mechanism of the PdAu nanoparticles induced by thermal processes performed in the 973–1173 K temperature range. The observed kinetic growth mechanism is consistent with a surface diffusion-limited ripening of the nanoparticles with a temperature-dependent growth exponent. The dependence of the growth exponent on the temperature is supposed to be linked to the variation with the temperature of the characteristics of the PdAu alloy. The activation energy for the surface diffusion process was evaluated in 0.54 ± 0.03 eV.     

磁控溅射ZnO薄膜的成核机制及表面形貌演化动力学研究

利用原子力显微镜分析了ZnO薄膜在具有本征氧化层的Si(100)和Si(111)基片上的表面形貌 随沉积时间的演化. 通过对薄膜生长形貌的动力学标度表征，研究了射频反应磁控溅射条件 下，ZnO薄膜的成核过程及生长动力学行为. 研究发现，ZnO在基片表面的成核过程可分为初 期成核阶段、低速率成核阶段和二次成核阶段. 对于Si(100)基片，三个成核阶段的生长指 数分别为β₁=1.04，β₂=0.25±0.01，β₃=0.74；对 于Si(11 关键词： ZnO薄膜 磁控溅射 生长动力学 成核机制     

Study of the effect of initial conditions on the scaling properties of CaF2 thin films

The growth of thermally deposited CaF₂ films was studied using three different substrates for deposition: glass, gold and silicon. Each substrate was chosen because of its different topography and used to determine the effect of substrate roughness on the growth of CaF₂ films. After thermally depositing a range of CaF₂ film thicknesses on the substrates, the CaF₂ surfaces were imaged using atomic force microscopy. The images were then used to determine the characteristic exponents which described the surface. In each case the Hurst exponent, H was found to rapidly increase from the initial substrate condition to a constant value (H ≈ 0.85) with increasing CaF₂ film thickness. This rapid crossover is quite remarkable and occurs in films with nominal thicknesses less than ≈20 nm. These data indicate that the roughness of the substrate, or in other words the initial conditions, have little effect on the growth properties of CaF₂ films beyond the crossover at very small values of the film thickness. The scaling of the dynamic exponent, β, is also presented as are measurements of the CaF₂ film porosity.     

Growth morphology of nanoscale sputter-deposited Au films on amorphous soft polymeric substrates

The growth of a room-temperature sputter-deposited thin Au film on two soft polymeric substrates, polystyrene (PS) and poly(methyl methacrylate) (PMMA), from nucleation to formation of a continuous film is investigated by means of atomic force microscopy. In particular, we studied the surface morphology evolution of the film as a function of the deposition time observing an initial Au three-dimensional island-type growth. Then the Au film morphology evolves, with increasing deposition time, from hemispherical islands to partially coalesced worm-like island structures, to percolation, and finally to a continuous and rough film. The overall Au morphology evolution is discussed in the framework of the interrupted coalescence model, allowing us to evaluate the island critical radius for the partial coalescence R _c=8.7±0.9 nm for Au on PS and R _c=7.6±0.8 nm for Au on PMMA. Furthermore, the application of the kinetic freezing model allows us to evaluate the room-temperature surface diffusion coefficient D _s≈1.8×10⁻¹⁸ m²/s for Au on PS and D _s≈1.1×10⁻¹⁸ m²/s for Au on PMMA. The application of the Vincent model allows us, also, to evaluate the critical coverage (at which the percolation occurs) P _c=61% for Au on PS and P _c=56% for Au on PMMA. Finally, the dynamic scaling theory of a growing interface was applied to characterize the kinetic roughening of the Au film on both PMMA and PS. Such analyses allow us to evaluate the dynamic scaling, growth, and roughness exponents z=3.8±0.4, β=0.28±0.03, α=1.06±0.05 for the growth of Au on PS and z=4.3±0.3, β=0.23±0.03, α=1.03±0.05 for the growth of Au on PMMA, in agreement with a non-equilibrium but conservative and linear growth process in which the surface diffusion phenomenon plays a key role.     

Atomic force microscopy study of growth kinetics: Scaling in TiN-TiB2 nanocomposite films on Si(1 0 0)

We used the reactive unbalanced close-field dc-magnetron sputtering growth of TiN-TiB₂ on Si(1 0 0) at room temperature to determine if scaling theory provides insight into the kinetic mechanisms of two-phase nanocomposite thin films. Scaling analyses along with height-difference correlation functions of measured atomic force microscopy (AFM) images have shown that the TiN-TiB₂ nanocomposite films with thickness ranging from 70 to 950 nm exhibit a kinetic surface roughening with the roughness increasing with thickness exponentially. The roughness exponent α and growth exponent β are determined to be ∼0.93 and ∼0.25, respectively. The value of dynamic exponent z, calculated by measurement of the lateral correlation length ξ, is ∼3.70, agreeing well with the ratio of α to β. These results indicate that the surface growth behavior of sputter-deposited TiN-TiB₂ thin films follows the classical Family-Vicseck scaling and can be reasonably described by the noisy Mullins diffusion model, at which surface diffusion serves as the smoothing effect and shot noise as the roughening mechanism.     

Ion beam induced formation and interrogation of Au nanoclusters

Low-energy ion bombardment of a Au thin film by 0.5 keV Ar+ forms self-organized nanoclusters that display quantum size effects. The reduction of Au coverage with sputtering time is quantified with x-ray photoemission spectroscopy, and a decrease of both the rms roughness and correlation length is measured by STM. Neutralization of scattered 3 keV Na+ and K+ alkali-metal ions is used to probe the electronic states of the sputter-induced nanoclusters. The neutral fractions gradually increase as the cluster dimensions decrease, indicating that the electronic structure is similar to that of clusters grown by deposition.     

椭圆偏振光谱实时在线监测与离线分析微晶硅薄膜的生长

采用甚高频等离子体增强化学气相沉积技术高速沉积了有无籽晶层两个系列微晶硅薄膜,通过椭圆偏振光谱、拉曼光谱和XRD对薄膜进行了分析,发现采用籽晶层后,在薄膜沉积初期有促进晶化的作用;由于籽晶层减少了薄膜的诱导成核时间,提高了薄膜的沉积速率,对比了实时在线和离线椭圆偏振光谱两种测量状态对分析微晶硅薄膜的影响,研究发现,当薄膜较薄时,实时在线测量得到的薄膜厚度小于离线下的数值;当薄膜较厚时,两种测量条件下得到的薄膜厚度差异较小;实时在线条件下得到的表面粗糙度要大于离线条件下得到的数值,这是由于薄膜暴露在大气中后表面有硅氧化物生成,对表面有平滑作用.     

Size-controlled Pd nanocluster grown by plasma gas-condensation method

Syntheses of palladium (Pd) nanoclusters by sputtering gas-condensation technique are reported in this work. The Pd nanocluster size distribution and number of nanoclusters are found to depend on several factors which include the inert gas flow rate (f), sputtering discharge power, and growth region length. The discharge power and the length of the growth region are optimized to produce high nanocluster yield. It is found that low f produces small number of large nanoclusters which can be attributed to the formation of nanoclusters via the two-body collision mechanism. For high f, nanocluster size decreases and the number of nanocluster increases with f. This phenomenon can be assigned to nanocluster formation through three-body collision mechanism.     

Crystallization Kinetics of Lamellar Crystals Confined in Polymer Thin Films

We used dynamic Monte Carlo simulations to investigate the crystallization kinetics of flat-on lamellar polymer crystals in variable thickness films. We found that the growth rates linearly reduced with decreasing film thickness for the films thinner than a transition thickness d_t , while they were constant for the films thicker than d_t . Moreover, the mean stem lengths (crystal thickness) we calculated decreased with film thickness in a similar way to the growth rates, and the intramolecular crystallinities we calculated confirmed the film thickness dependence of the crytsal thickness. Besides, the crystal melting rates in thin films were calculated and increased with decreasing film thickness. We proposed a new interpretation on the film thickness dependence of the crystal growth rate in thin films, suggesting that it is dominated by the crystal thickness in terms of the driving force term (l–l _min) expressed by Sadler, rather than the chain mobility based on experiments. The crystal thickness can determine whether a crystal grows or melts in a thin film at a fixed temperature, indicating the reversibility between the crystal growth and melting.     

Elaboration and characterization of crystalline RF-deposited V2O5 positive electrode for thin film batteries

Investigations were realized on the microstructural and morphological evolution of RF-sputtered vanadium pentoxide thin films during growth. V₂O₅ thin films at different stages of growth were studied by spectroscopic ellipsometry, X-ray diffraction, atomic force microscopy and scanning electron microscopy. Film grain orientation, roughness and density were found to have notable evolution during growth. Electrochemical tests in liquid and solid electrolyte state configuration showed non-linear relationship between discharge capacity and V₂O₅ film thickness (<1 μm), which could be attributed in parts to the observed morphological and microstructural changes during growth, mainly the existence of a gradient density through film thickness and the pronounced top surface roughness.     

Thickness effect on stress,structural, electrical and sensing properties of (0 0 2) preferentially oriented undoped ZnO thin films

Preferentially oriented (0 0 2) ZnO thin films with c-axis-oriented wurtzite structure have been grown on Si (1 0 0) and glass substrates using radio frequency magnetron sputtering. The residual stresses have been determined and calculated via the Stoney formalism. The ZnO thin films have been also characterised by X-ray diffraction and scanning electron microscope, and their stoichiometry was verified by Rutherford backscattering spectroscopy. The evolution of the residual stress was studied as a function of film thickness in the 10–1200 nm range. A growth scenario is proposed and a possible correlation between the residual stress, film’s texture and crystallographic orientation is highlighted. The crystalline quality was found to improve, while the stress values decreased with increasing thickness, and as a ramification the thicker films developed better sensing response to gases. The mechanical (stress) and electrical properties of the films were also investigated as a function of the film thickness, which tended to manifestly improve in dependence on thickness as well. We attribute this to the fact that the thinner films are under vehement misfit stress that declines with increasing the film thickness further.     

Mixing length scales: step meandering and island nucleation on vicinal surfaces

Simultaneous island nucleation and step flow growth on vicinal surfaces are studied by Monte Carlo simulations. Step edges experience meandering instability under growth conditions if there is a kink barrier suppressing adatom jumps around kink sites. This instability has a characteristic length scale, with different scaling properties from the island separation scale. We show that there is a coupling between island nucleation and step edge instability. The length scale associated with nucleation begins to couple with the wavelength of the step edge patterns when islands and steps coalesce. Only in the submonolayer regime step meandering is independent of island formation. In this regime the island separation has a cross-over scaling behaviour as terrace width is varied.Received: 9 April 2003, Published online: 19 November 2003PACS: 81.15.Aa Theory and models of film growth - 68.55.Ac Nucleation and growth: microscopic aspects - 81.16.Rf Nanoscale pattern formationM. Rusanen: Present address: Institut Français du Pétrole, Groupe de Modélisation Moléculaire, BP 311, 92852 Rueil-Malmaison, FranceJ. Kallunki: Present address: Laboratory of Physics, PO Box 1100, FIN-02015 HUT, Espoo, Finland     

Ge nanocrystals in magnetron sputtered SiO2

Structural and optical properties of Ge nanocrystals in SiO₂ films created by magnetron sputtering and heat treatment have been investigated. The formation of nanocrystals is found to be influenced by the temperature of heat treatment and the Ge concentration in the films. After heat treatment at 1000 °C nanocrystals are present throughout the film, with the exception of a region close to the surface that does not contain nanocrystals. This effect is assigned to oxidation of Ge in this part of the film. The size distribution of the nanocrystals is analyzed by transmission electron microscopy for a range of deposition and heat-treatment parameters. By analyzing the transmission electron microscopy images, it is possible to estimate the fraction of nanoclusters that are crystalline for a given set of growth parameters. This analysis shows that all the nanoclusters are created in the crystalline state. Raman spectroscopy is employed to probe the Ge–Ge bonds. In combination with transmission electron microscopy, this information can be used to distinguish between growth modes such as nucleation or Ostwald ripening. The photoluminescence spectra exhibit a strong broad line at 625 nm, the presence of which is demonstrated to correlate to the presence of Ge nanocrystals. PACS 61.46.+w; 78.55.-m; 78.67.-n     

Molecular dynamics and experimental studies on deposition mechanisms of ion beam sputtering

Molecular dynamics (MD) simulation and experimental methods are used to study the deposition mechanism of ionic beam sputtering (IBS), including the effects of incident energy, incident angle and deposition temperature on the growth process of nickel nanofilms. According to the simulation, the results showed that increasing the temperature of substrate decreases the surface roughness, average grain size and density. Increasing the incident angle increases the surface roughness and the average grain size of thin film, while decreasing its density. In addition, increasing the incident energy decreases the surface roughness and the average grain size of thin film, while increasing its density. For the cases of simulation, with the substrate temperature of 500 K, normal incident angle and 14.6 × 10⁻¹⁷ J are appropriate, in order to obtain a smoother surface, a small grain size and a higher density of thin film. From the experimental results, the surface roughness of thin film deposited on the substrates of Si(1 0 0) and indium tin oxide (ITO) decreases with the increasing sputtering power, while the thickness of thin film shows an approximately linear increase with the increase of sputtering power.     

Attachment limited versus diffusion limited nucleation of organic molecules: Hexaphenyl on sputter-modified mica

The nucleation and growth of organic molecules is usually discussed in the framework of diffusion limited aggregation (DLA). In this letter we demonstrate for the rod-like organic molecules hexaphenyl (6P) on sputter-modified mica, that under specific experimental conditions the nucleation has to be described by attachment limited aggregation (ALA). The crucial parameter for the growth mode is the roughness of the substrate surface, as induced by ion sputtering. With decreasing surface roughness the diffusion probability of the molecules increases and the growth mode changes from DLA to ALA. This was derived from the deposition rate dependence of the island density. A critical size of i = 7 molecules was determined for the nucleation of 6P on a moderately sputtered mica surface.     

Effective scaling behavior of magnetization and Hamming distance in Ising thin films under a surface field

The recent improvements on the technology for developing high-quality thin magnetic films has renewed the interest in the study of surface effects in both static and dynamic magnetic responses. In this work, we use a Monte-Carlo algorithm with Metropolis dynamics together with a spreading of damage technique to study the interplay between the effects of finite thickness and surface ordering field in thin ferromagnetic Ising (S=1/2) films. We calculate, near the bulk critical temperature and several values of the surface field, the dependence on the film thickness of the average magnetization M and Hamming distance D. We employ a finite size scaling analysis to show that both obey an effective one-parameter scaling but exhibit distinct characteristic surface fields. At their corresponding characteristic surface fields both M and D become roughly thickness independent and we estimate the critical exponent characterizing the behavior of the typical scaling lengths. Received 29 March 1999 and Received in final form 21 April 1999     

Scaling relationship between effective critical exponents throughout the crossover region in thin Ising films

The Monte Carlo (MC) approach is used to check the validity of the scaling relationship for the effective critical exponents in thin Ising films. We investigate this relationship not just in the critical region but throughout the crossover to the expected two-dimensional behavior. Our results indicate that this scaling relationship is very well-fulfilled throughout the entire crossover temperature region, as predicted by a previous renormalization group analysis. The two-dimensional universality class of Ising films is confirmed by means of data collapsing plots for plates with increasing L, up to L=100. The evolution of the maximum value of the effective critical exponents with film thickness is discussed. Received 22 April 1999     

以表面等离子体为媒介的ZnO薄膜发光增强特性研究

采用两步法制备Si基Ag/ZnO双层结构薄膜,研究了Ag覆盖层的厚度和生长温度T对ZnO近带边发光强度的影响.对于厚度为100 nm的ZnO薄膜,发现Ag覆盖层的最佳厚度仅为8 nm,此时双层薄膜相对于单层ZnO薄膜的发光增强因子η达到最大值8.1;同时还发现,在最佳Ag层厚度下,生长温度T≥300 ℃时生长Ag所获Ag/ZnO双层薄膜的ZnO发光强度比生长温度T≤200 ℃时生长的双层薄膜样品大一倍以上,η ≈ 18.结合对双层薄膜表 关键词： 表面等离子体共振 复合薄膜     

Correlation between stress profiles of cubic boron nitride thin films and the phase sequence revealed from infrared data

Cubic boron nitride thin films have been ion-beam-assisted deposited on silicon cantilever structures and subsequently back-etched in order to study the stress evolution and finally the growth mechanisms. After each sputtering step, the film stress, the remaining thickness, and the IR data were examined. In this way, the layered sequence of cBN on top of a hBN base layer, influencing the development of the intrinsic film stress, could be studied in detail. The observed stress distribution can be divided into three regions. First, a non-cubic base layer with a constant stress value is formed, followed by a linear increase in the stress after cBN nucleation as a result of the coalescence of cBN nanocrystals. Finally, the stress reaches a second plateau characteristic of the cBN top layer. In addition, the layered sequence was verified by the evolution of the FTIR spectra. Furthermore, the fraction of the sp²-bonded material of the cBN top layer was determined from the IR data. For various deposition conditions, a linear relationship between the stress of the nanocrystalline cBN top layer and the amount of sp³-bonded material was observed. From this, it can be concluded that stress relaxation occurs at the sp²-bonded grain boundary material. No evidence for stress relaxation after cBN nucleation was found. Received: 27 August 1999 / Accepted: 31 August 1999 / Published online: 3 November 1999