STRESS ANALYSIS IN CUBIC BORON NITRIDE FILMS BY X-RAY DIFFRACTION USING sin2 ψ METHOD

The boron nitride (BN) films containing cubic boron nitride (c-BN) and hexagonal boron nitride (h-BN) were prepared by radio frequency a ssisted thermal filament chemical vapor deposition. The stress and strain in BN films were investigated by X-ray diffraction analysis using the sin² ψ method. The results showed that both c-BN and h-BN in the same film have similar values of elastic strain, however, the compressive stress in c-BN is much greater than that in h-BN for the same film. Both stress and strain gradually decre ased with the increase of substrate temperature (T_s). The effective stress in the films calculated by the effective stress model increased with the increase of T_s. Furthermore, the dependence of effective stress in the films on T_s was also investigated.     

Secondary ion emission from clean and K-covered Ni surfaces near threshold impact energies

Clean and K-covered Ni surfaces are bombarded with low energy (10–500 eV) beams of He⁺, Ne⁺, Ar²⁺, and Kr⁺ ions, and the emitted ion yield is measured as a function of beam energy. The apparent threshold energies for K⁺ and Ni⁺ emission are proportional to the ionic binding energies of K⁺ and Ni⁺ to the Ni surface. From comparison of the ion and neutral yield curves, it is suggested that these ions are emitted via momentum transfer collisions similar to neutral sputtering.     

Thick c-BN films deposited by radio frequency magnetron sputtering in argon/nitrogen gas mixture with additional hydrogen gas

The excellent physical and chemical properties of cubic boron nitride(c-BN) film make it a promising candidate for various industry applications. However, the c-BN film thickness restricts its practical applications in many cases. Thus, it is indispensable to develop an economic, simple and environment-friend way to synthesize high-quality thick, stable c-BN films. High-cubic-content BN films are prepared on silicon(100) substrates by radio frequency(RF) magnetron sputtering from an h-BN target at low substrate temperature. Adhesions of the c-BN films are greatly improved by adding hydrogen to the argon/nitrogen gas mixture, allowing the deposition of a film up to 5-μm thick. The compositions and the microstructure morphologies of the c-BN films grown at different substrate temperatures are systematically investigated with respect to the ratio of H_2 gas content to total working gas. In addition, a primary mechanism for the deposition of thick c-BN film is proposed.     

Relative sputtering yields from close-packed directions in nickel under low-energy Ar bombardment

A new approach to low-energy sputtering was developed wherein a monoenergetic Ar⁺ ion beam of the order of 10⁻⁹ A impinged onto a crystalline nickel target. Target preparation consisted of plating about 100 monolayers of high specific activity Ni-63 onto a coldrolled nickel substrate and then heating the target above its recrystallization temperature under ultra-high vacuum. The result was a highly ordered polycrystalline structure which, when sputtered, behaved like the (100) surface of a nickel single crystal. Approximately 25 percent of the surface atoms were Ni-63. Sputtered material was collected on a molybdenum foil which was subsequently analyzed by radiotracer techniques.

Experimental results concerning sputtering from [110] and [100] close-packed directions in nickel under bombardment by Ar⁺ ions of energy 25 eV to 600 eV are reported. The relative sputtering yields from [110] directions are presented as a function of incident ion energy for 75° and 15° ion incidence measured with respect to the [110] directions, and the extrapolated thresholds are compared with theoretical predictions.

In addition to the expected deposits on the foil due to sputtering from individual closepacked directions, secondary deposits occurred which are attributed to specular reflection of sputtered nickel atoms from the molybdenum foil.     

Dependence of Auger depth resolution and surface texturing on primary ion species

The dependence of Auger depth resolution and surface texturing on primary ion species was systematically investigated for polycrystalline Al, Mo, Ag and Ta films deposited on Si wafers, using 3 keV Ne⁺, Ar⁺ and Xe⁺ ions as projectiles. The resolution was found to depend strongly on ion species; the higher the ion mass, the better the resolution. The resolution improvement attained with Xe⁺ ions was dramatic for Al, becoming less pronounced for higher mass targets. As revealed by high-resolution scanning electron microscopy, Xe⁺ sputtering led to less-developed topographical structures of sputtered areas, which allowed us to conclude that ion sputtering with heavier ions roughens the surface less, resulting in a marked improvement in resolution.     

Investigation of relative sputtering yields during ionoluminescence of Si

Atomic line emissions resulting from sputtered atoms and ions are investigated on Si(100) bombarded by 60 keV Ne⁺, 300 keV Xe⁺ and 300 keV SF₅⁺ ions. It has been observed that the presence of oxygen enhances light emission due to radiative de-excitation. Relative sputtering yields of Si for 60 keV Ne⁺, 300 keV Xe⁺ and 300 keV SF₅⁺ are estimated from the photon yields. The estimates of sputtering yields of adsorbed oxygen on Si for the above projectiles are also made from the transients of Si I 251.6 nm line. A non-linearity in the sputtering yield for SF₅⁺ ions was observed in comparison with the yields for Ne⁺ and Xe⁺ ions. The results are discussed with the model of overlapping of individual collision cascades.     

Three-dimensional spatiokinetic distributions of sputtered andscattered products of Ar+ and Cu+ impacts onto theCu surface: molecular dynamics simulations

Energy and angular distributions of reflections and sputtered atoms are essential inputs for feature profile evolution simulations. Molecular dynamics simulations are used to compute the three-dimensional energy and angular distributions for reflected and sputtered products when both Ar⁺ and Cu⁺ ions bombard a copper surface. We term these “spatiokinetic” distribution functions (SKDF's). We show by example that SKDF's for reflected Ar⁺ ions focus as the incident angle &thetas;_i (normal=0°) is increased from 60-75° and broaden as the incident energy E_i is increased from 55-175 eV. We show that the SKDF's for glancing-angle reflected Cu⁺ ions focus when E_i is increased from 55-175 eV. We show that the SKDF's for copper atoms sputtered by 175 eV Ar⁺ are insensitive to &thetas;_i;. We report total sputter yields for Ar⁺ and Cu⁺ ions at 55 and 175 eV for incident angles between 0° and 85°, and sticking probabilities for Cu⁺ ions for these energies and angles. Comparison to representative experimental results (Doughty et al., 1997) is given     

Computer simulation of two-component target sputtering

The TRIM SP computer simulation program, which is based on the binary collision approximation, is applied to sputtering of two component targets. The topics discussed in this paper are: contribution of different processes leading to sputtering, total and partial sputtering yields, surface compositions at stationary conditions, sputtering of isotopic mixtures, angular and energy distributions and the escape depth of sputtered particles. Targets investigated are TaC, WC, TiC, TiD₂, and B (as an isotope mixture), bombarded by the noble gas ions and D (in the case of TiD₂). Comparison with experimental data and calculated results show good agreement demonstrating that collisional effects are sufficient to describe the experimental data in the examples investigated.     

Modeling of ion-assisted deposition using BCA computer simulation

Abstract

TRIM type binary collision approximation event store codes have employed to simulate collisional effects which occur during ion-beam or plasma assisted deposition of thin films.

Calculations can been performed using simplifying rate equation models, into which yields obtained from static TRIM simulations are inserted. Alternatively, the dynamic-composition code TRIDYN allows direct and complete simulations of the time-dependent processes.

Results are shown for different processes of ion-beam assisted deposition (IBAD), ion-beam mixing (IBM) post-treatment, and plasma-enhanced chemical vapour deposition (PECVD). Simulations of the formation of boron nitride films deposited from evaporated boron and energetic nitrogen show an excellent agreement with experimental results for nitrogen concentrations below the stoichiometric limit. For high N/B flux ratios, non-collisional mechanisms (ion-induced outdiffusion, surface trapping of outdiffusing nitrogen) have been included in the simulations, again producing good agreement with the experimental results. The ion-induced interface mixing of boron films on iron substrates is compared to experimental adhesion studies both for Ar⁺ post-treatment and Ar⁺ bombardment during deposition, demonstrating that the final adhesion is also influenced by other than purely collisional mechanisms. A special version of TRIDYN is used to treat the ion-induced densification of carbon films grown during simultaneous Ne⁺ bombardment, with reasonable agreement with experimental results. Finally, simple models are evaluated for the growth, composition and structure of C:H films grown in methane plasmas. The hydrogen content of the films decreases with increasing ion energy due to ion-induced release of hydrogen. Attempts to understand their bonding structure, in terms of the sp³/sp² ratio, on the basis of ion-induced preferential displacement, fail with respect to the energy dependence.     

Phase transformation in BN films by nitrogen-protected annealing at atmospheric pressure

Two groups of RF-sputtered BN films (pure hexagonal phase and approximately 27.5% cubic content, respectively) were annealed at 600 to 1000 °C under nitrogen at atmospheric pressure after deposition. FTIR spectroscopy indicates a reversible transformation from hexagonal phase to cubic phase, and again hexagonal phase. The most effective temperature for h-BN converting to cubic zincblende (c-BN) is 900 °C. Further, the indirectly stepwise transformation from hexagonal (h-BN) to explosive BN (E-BN) and then to c-BN employing metastable E-BN as an intermedium was observed. In addition, we tentatively put forward that the existence of defective h-BN and the N defects plays a key role on h-BN to c-BN transformation.     

Interactions of HCOOH with stoichiometric and defective TiO2(110) surfaces

Interactions of HCOOH with stoichiometric (nearly defect-free) and defective TiO₂(110) surfaces have been studied experimentally using X-ray photoelectron spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and theoretically using electronic structure calculations. The HCOOH saturation coverages were 0.58 ML, 0.77 ML, and 0.92 ML (1 ML ≈ 5.2 × 10¹⁴ cm⁻²) for nearly defect-free surfaces, for electron-beam exposed surfaces, and for Ar⁺ ion bombarded surfaces, respectively. The excess formic acid adsorption quantitatively corresponds to the number of newly exposed sites created by electron-beam exposure. Electronic structure calculations show a strong adsorptive interaction for formate on cation sites on both stoichiometric and defective TiO₂ surfaces, consistent with the experimental observations. In spite of adsorption at defect sites, little or no defect healing (defect healing means a reduction in defect signal observed by the photoemission measurements) was observed for either electron-beam exposed or Ar⁺ bombarded surfaces by HCOOH exposure up to 10⁴L at room temperature. However, some healing will occur if extra energy provided by electrons is introduced to breakdown formate species. In contrast to water adsorption, electronic structure calculations on defective TiO₂ have found that formate is located in an asymmetric position with respect to the Ti³⁺ sites with a potential additional interaction with the Ti⁴⁺ site.     

不同离子激发Au靶的多电离效应

重离子与固体表面相互作用时,会引起靶原子内壳层的电离,相应空穴退激过程中发射的X射线对研究重离子与固体表面的相互作用有着重要意义,可为相关研究提供基础数据.目前,在K和L壳层电离方面做了一些工作,而M壳层的研究较少,本文依托兰州重离子加速器国家实验室320 kV高电荷态离子综合研究平台,测量了不同能量的H~+, Ar~(8+), Ar~(12+), Kr~(13+)和Eu~(20+)离子与Au表面作用产生的特征X射线谱及其能移,计算了X射线的产额比值.结果表明:重离子引起了靶原子内壳层的多电离,多电离效应使Au的MX射线有不同程度的能移;多电离程度取决于入射离子能量、离子的原子序数和其外壳层的空穴数量.     

立方氮化硼薄膜沉积过程的相变研究

从能量和结构两个角度分析了BN四种相的转变过程，以及杂质和缺陷对立方氮化硼(c-BN)薄膜制备的影响.研究了从六角氮化硼(h-BN)到c-BN转变的一个可能的过程，即h-BN→菱形氮化硼(r-BN)→c-BN过程.对纯的h-BN到r-BN的转变需要克服一个很高的能量势垒，在实验室条件下很难能够提供能量来越过这个势垒.而从r-BN到c-BN的转变只需要克服一个很低的能量势垒.这个能量势垒要低于从h-BN到纤锌矿氮化硼(w-BN)转变所需要克服的能量势垒.c-BN薄膜的制备过程中，薄膜在高能粒子轰击下，会产生大量的缺陷，这些缺陷对立方相的形成起到了重要的作用，缺陷和杂质的存在大大降低了从h-BN到r-BN转变的能量势垒.根据这个理论模型，在两步法制备c-BN薄膜的基础上，调整实验参数，形成三步法制备高质量c-BN薄膜.主要研究了三步法中第一步的时间和衬底负偏压对c-BN薄膜制备的影响，找到合适的沉积时间和衬底负偏压分别为5min和-180V.采用三步法制备薄膜，可以重复得到高立方相体积分数(立方相体积分数超过80%)的BN薄膜，并且实验重复性达到70%以上. 关键词： 立方氮化硼 能量势垒 缺陷 衬底偏压     

Sputtering studies with the Monte Carlo Program TRIM.SP

The Monte Carlo Program TRIM.SP (sputtering version of TRIM) was used to determine sputtering yields and energy and angular distributions of sputtered particles in physical (collisional) sputtering processes. The output is set up to distinguish between the contributions of primary and secondary knock-on atoms as caused by in- and outgoing incident ions, in order to get a better understanding of the sputtering mechanisms and to check on previous theoretical models. The influence of the interatomic potential and the inelastic energy loss model as well as the surface binding energy on the sputtering yield is investigated. Further results are sputtering yields versus incident energy and angle as well as total angular distributions of sputtered particles and energy distributions in specific solid angles for non-normal incidence. The calculated data are compared with experimental results as far as possible. From this comparison it turns out that the TRIM.SP is able to reproduce experimental results even in very special details of angular and energy distributions.     

Preferential sputtering and radiation enhanced segregation in palladium-platinum alloys

Five palladium-platinum alloys of different compositions ranging from 10 to 90 at% Pd were sputtered with 1 keV Ar⁺ ions. The surface concentrations were then determined with Auger electron spectroscopy (AES) and low energy ion scattering spectroscopy (ISS). The observed concentrations differed largely from bulk values. This difference is explained in terms of the difference in sputtering yields for platinum and palladium and the radiation enhanced segregation of palladium. The surface was then mechanically cleaned in situ. The surface concentrations measured subsequently corresponded excellently with the bulk values confirming the calibration procedure for the calculation of the surface concentrations. A recently developed model for surface segregation was used to fit the experimental data. Values for the surface segregation energy ΔG and the radiation enhanced diffusion coefficient D were obtained in the range 2000–8000 J/mol and (1.2–8.0)×10⁻²⁰ m²/s, respectively.     

Evidence for atomic recondensation on ion-bombarded solid surfaces

Direct evidence is presented that vapor-phase crystal growth is induced on solid surfaces bombarded with inert-gas ions. Surface cones formed on AlGaAs/GaAs superlattice targets exposed to a few keV Ar⁺ ions were characterized as polycrystalline cone tips protruding beyond the original target surface. Fine particles were also found to grow in close vicinity to the cone evolution sites, thus demonstrating that target atoms ejected from the impact area condensed into polycrystalline cone tips and particles, as a result of an enhanced particle supply to the projected areas. Since this finding is not within the current knowledge of ion-solid interactions, a new theoretical approach is required for its interpretation.     

H+和Ar11+激发Si的K壳层X射线发射研究

测量了50–250 keV H⁺和1.0–3.0 MeV Ar¹¹⁺ 轰击Si表面过程中辐射的X射线. 结果表明, 在Ar¹¹⁺入射的情况下, 引起了Si的L壳层上3, 4个电子的多电离.计算了Si的K壳层X射线产生截面, 并将两体碰撞近似(BEA), 平面波恩近似, ECPSSR理论计算与实验值进行了对比. ECPSSR理论与质子产生的截面数据能够很好地符合; 而考虑多电离后, BEA理论与Ar¹¹⁺的实验结果符合较好. 关键词： X射线 高电荷态重离子 多电离     

Arq+入射金表面激发靶原子Mα-X射线的动能和势能的阈值

在兰州重离子加速器国家实验室 用动能150 keV和1.2 MeV的Ar^q+束流分别入射Au表面, 测量了离子与表面相互作用过程中辐射的X射线谱. 结果表明, 多电荷态Ar^q+激发Au原子的M_α-X射线至少需要2 keV的势能. 本文采用半经典两体碰撞近似, 估算了炮弹离子通过碰撞激发靶原子辐射X射线的动能阈值.