Origins of growth stresses in amorphous semiconductor thin films

Stress evolution during deposition of amorphous Si and Ge thin films is remarkably similar to that observed for polycrystalline films. Amorphous semiconductors were used as model materials to study the origins of deposition stresses in continuous films, where suppression of both strain relaxation and epitaxial strain inheritance provides considerable simplification. Our data show that bulk compression is established by surface stress, while a subsequent return to tensile stress arises from elastic coalescence processes occurring on the kinetically roughened surface.     

In situ measurement of the surface stress evolution during magnetron sputter-deposition of Ag thin film

We measured the evolution of in situ surface stress of Ag thin film during the magnetron sputter deposition. The measurement of force per width of Ag thin film showed that both the surface state and surface stress of Ag layer can be controlled through the variation of the deposition conditions such as the deposition temperature and rate. At room temperature, the force per width curve of Ag film deposited to 1 Å/s showed a typical curve consisting of three stages of surface stress. A brief presence of initial compressive stage and broad tensile maximum resulting in a compressive state had a tendency to disappear with increasing the deposition temperature. Meanwhile, a development of final compressive stage was more at higher temperature. Similar effect was observed but less obvious on increasing the deposition rate.     

X-ray diffraction study of effect of deposition conditions on α--β phase transition and stress evolution in sputter-deposited W coatings

Pure W and W-Cu-W trilayer coatings were deposited on an Fe substrate by d.c. magnetron sputtering. The α-β phase evolution, intragranular stress evolution in sputter-deposited W layer were investigated by x-ray diffraction. They are directly related to the film microstructure, density and adhesion. Therefore, control of the film stress and phase component transition is essential for its applications. The phase component transition from β-W to α-W and intragranular stress evolution from tensile to compressive strongly depend on the deposition parameters and can be induced by lowering Ar pressure and rising target power. The compressively stressed films with α-W phase have a dense microstructure and high adhesion to Fe substrate.     

Origin of compressive residual stress in polycrystalline thin films

We present a model for compressive stress generation during thin film growth in which the driving force is an increase in the surface chemical potential caused by the deposition of atoms from the vapor. The increase in surface chemical potential induces atoms to flow into the grain boundary, creating a compressive stress in the film. We develop kinetic equations to describe the stress evolution and dependence on growth parameters. The model is used to explain measurements of relaxation when growth is terminated and the dependence of the steady-state stress on growth rate.     

磁控溅射硅基薄膜应力演化实时研究

采用多光束应力实时测量装置监控并分析了磁控溅射Si和SiNx薄膜的总力及应力演化过程。在两种膜层中均观察到了应力释放及恢复现象。Si膜中应力是可逆的,而SiNx膜中应力是部分可逆的。物理吸附和解吸附分别是应力释放和恢复的主要原因。不可逆的应力分量来源于化学吸附,基于吸附机制建立了一个应力释放模型。     

Biaxial stresses, surface roughness and microstructure in evaporated TiO2 films with different deposition geometries

The residual stresses, surface roughness and microstructure in titanium oxide films prepared by electron-beam evaporation and deposited with different geometries were investigated, with particular focus on the in-plane anisotropy of the biaxial stresses and microstructures. Thin films were deposited with various deposition angles on B270 glass substrates and silicon wafers. Two different types of deposition geometries were studied. The residual stress in the thin films was examined by a phase-shifting Twyman-Green interferometer. The optical constants, biaxial stress and surface roughness were found to be related to the evolution of the anisotropic microstructures in the films. The results revealed that the anisotropic stresses that developed in the evaporated titanium oxide films were dependent upon the deposition geometry and microstructure of the films.     

Molecular dynamics study of roughness and stress evolution using a Lennard–Jones potential

A three-dimensional molecular dynamics (MD) simulation is proposed to study the film growth, roughness and stress evolution during atom deposition on the (100) plane of a fcc regular crystal. We use the cubic system with an x–y periodic boundary condition. At the bottom we have an atomic surface and at the top a reflecting wall. The model uses the Lennard-Jones potential to describe the interatomic forces. The simulation results show that the film grows with the Volmer–Weber mode and exhibits specific curve shape of the stress evolution. The mean biaxial stress obtained during the simulation attains a local tension maximum at a coverage of two monolayers. The stress in the normal direction is smaller than the biaxial stress. The main contribution to the stress in the film arises from the first monolayer. The curves describing roughness possess maximum values at the same substrate coverage. The dependence of the roughness on the temperature is examined.     

In-situ surface stress and magnetic property of CoCrX(X = Pt, Ta)/CrTi bilayer during sputter-deposition

The measurement of the force per width of CoCrX(X = Pt, Ta)/CrTi bilayer showed that both the surface structure state and surface stress of CoCrX magnetic layer can be controlled by regulating the average film stress of CrTi underlayer through a variation of deposition conditions such as deposition rate and temperature as well as underlayer thickness. As the tensile surface stress of CoCrX magnetic layer was more, its coercivity was also more. This was because not a dynamic phase decomposition with a compressive ledge due to high adatoms mobility but an epitaxial film growth with a tensile ledge due to low adatoms mobility. Thus, the development of the crystallographic texture of CoCrX alloy can largely improved its coercivity. It is believed that the principal mechanism determining the coercivity of CoCrX/CrTi film is the optimized development of the crystallographic texture through an evolution of the surface stress of CrTi underlayer.     

Intrinsic stress analysis of sputtered carbon film

Intrinsic stresses of carbon films deposited by direct current （DC） magnetron sputtering were investigated. The bombardments of energetic particles during the growth of films were considered to be the main reason for compressive intrinsic stresses. The values of intrinsic stresses were determined by measuring the radius of curvature of substrates before and after film deposition. By varying argon pressure and target-substrate distance, energies of neutral carbon atoms impinging on the growing films were optimized to control the intrinsic stresses level. The stress evolution in carbon films as a function of film thickness was investigated and a void-related stress relief mechanism was proposed to interpret this evolution.     

In situ measurements of InAs and InP (0 0 1) surface stress changes induced by surface reconstruction transitions

The anisotropic surface stress changes associated with the transition between different surface reconstructions of InAs and InP (0 0 1) surfaces are measured in situ and in real time in a molecular beam epitaxy (MBE) system. Reflectivity anisotropy of the surface measured at 1.96 eV, together with reflection high energy electron diffraction (RHEED) pattern, are used in order to identify the surface reconstructions, and the monitoring of the substrate curvature evolution to determine the variations in surface stress. Our results show the important contribution to the surface stress of the dimers present in these reconstructed surfaces. Furthermore, we provide for the first time quantitative values of the surface stress changes due to the transition between surface reconstructions for these III-V semiconductors compounds. We obtain values for these changes up to 0.7 Nm⁻¹, that is, of the same magnitude as the stress induced by deposition of one monolayer during growth of lattice-mismatched III-V semiconductor heteroepitaxial systems. This points out the great importance of surface stress evolution in this kind of processes.     

Residual stress of physical vapor-deposited polycrystalline multilayers

An extended one-dimensional stress model for the deposition of multilayer films is built based on the existing stress model by considering the influence of deposition conditions. Both thermal stress and intrinsic stress are considered to constitute the final residual stress in the model. The deposition process conditions such as deposition temperature, oxygen pressure, and film growth rate are correlated to the full stress model to analyze the final residual stress distribution, and thus the deformation of the deposited multilayer system under different process conditions. Also, the model is numerically realized with in-house built code. A deposition of Ag-Cu multilayer system is simulated with the as-built extended stress model, and the final residual stresses under different deposition conditions are discussed with part of the results compared with experiment from other literature.     

Effects of deposition temperature on the structure of amorphous carbon nitride films

Amorphous carbon nitride films (a-CN_x) were deposited on Si(100) under different rf power and at different substrate temperature T_S using rf magnetron sputtering of a high-purity graphite target in pure nitrogen. IR absorption, Raman spectra, and residual stress measurements are used to characterise the films in the as deposited state. The differences in the microstructure of the a-CN_x films is related to differences in the deposition mechanism. The T_S contribution can operate to increase the connectivity of the C-C network. The stress evolution is the result of the densification, i.e. a structural transformation within of the films that accompanies the nitrogen evolution, due to the C-N and C-C evolution when T_S is increased.     

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     

沉积参量及时效时间对 SiO2薄膜残余应力的影响

SiO2 薄膜由电子束蒸发方法沉积而成。用GPI数字波面光学干涉仪测量了不同沉积条件下玻璃基底镀膜前后曲率半径的变化,并确定了 SiO2 薄膜中的残余应力。在其他条件相同的情况下,当沉积温度由 190 ℃升高到350 ℃时,SiO2 薄膜中的压应力由-156 MPa增大为-289 MPa。氧分压由3.0×10-3 Pa升高到13.0×10-3 Pa时,SiO2 薄膜中的应力由-223.5 MPa变为20.4 MPa。通过对薄膜折射率的测量,发现薄膜的堆积密度随沉积条件的改变也发生了规律性的变化。应力的变化主要是由于沉积时蒸发粒子的动能不同,导致薄膜结构不同引起的。同时,在样品的存放过程中,发现随着存放时间的延长,薄膜中的应力表现出了由压应力状态向张应力状态演变的趋势。     

Molecular dynamics simulation of stress and grain evolution

A three-dimensional molecular dynamics simulation is carried out to study the evolution of grains and stresses during the deposition of atoms on the (100) plane of a fcc regular crystal, using the cubic system with x–y periodic boundary conditions. At the bottom an atomic surface and at the top a reflecting wall are assumed. Atoms in the system interact via the Lennard–Jones potential. During simulation the films grow according to the Volmer–Weber mode and exhibit specific shape of the stress curves. When the film becomes continuous, the stress during the growth possesses a maximum value, but later new grain boundaries are formed. Individual atoms in the grain boundaries generate compressive stress in the films.     

力和扩散机理下外延形貌的演化分析

本文提出了一个新的基于扩散界面的相场模型来描述外延生长中岛的形核、生长及熟化过程. 该模型同时考虑了弹性场、表面能、沉积、扩散、解吸和能量势垒等热力学及动力学过程对表面纳米形貌的影响. 采用经典的BCF模型来描述生长中的扩散形核过程, 而采用一个新的包含弹性应变能的自由能函数, 通过变分得到一个描述多层岛生长的相场方程, 该方法可以有效地描述外延生长中复杂的外延形貌. 采用有限差分格式对非线性耦合方程组进行求解. 数值结果显示, 该模型可以真实地再现外延生长中多层岛结构(即山丘状形貌)的演化过程, 模拟结果与已有实验结果一致. 同时模拟了生长过程中随外延形貌演化而形成的复杂生长应力, 研究表明, 在生长过程中, 岛中存在着复杂的应力分布, 且在岛边界处应力达到局部最大, 这与实验结果定性一致. 此外, 本文的重要发现是, 外延生长中的应力演化明显地影响原子的扩散过程, 当应力存在时, 外延结构变化较无弹性场时变快. 该项研究对理解外延生长中各物理机理的协同作用有重要的指导意义.     

离子辅助沉积法制备SiO2介质薄膜的应力研究

在高功率垂直腔面发射激光器制作工艺中,生长出低应力、高质量、高稳定性的SiO₂介质层非常关键。我们使用高效率LaB₆离子源辅助,在低放电电流条件下,在GaAs衬底上沉积了SiO₂,并对退火的应力影响进行了测试。在有离子辅助沉积时,对不同生长速率、不同厚度的应力影响进行了研究,对沉积过程进行了分析。结果表明:离子辅助沉积的SiO₂薄膜的应力远小于常规工艺条件下沉积的薄膜的应力,且退火后应力变化小。     

FTIR法研究BCN薄膜的内应力

采用射频磁控溅射技术,用六角氮化硼和石墨为溅射靶,以氩气(Ar)和氮气(N₂)为工作气体,在Si(100)衬底上制备出硼碳氮(BCN)薄膜。利用傅里叶变换红外光谱(FTIR)考察了不同沉积参数(溅射功率为80～130 W、衬底温度为300～500 ℃、沉积时间为1～4 h)条件下制备的薄膜样品。实验结果表明,所制备薄膜均实现了原子级化合。并且沉积参数对BCN薄膜的生长和内应力有很大影响,适当改变沉积参数能有效释放BCN薄膜的内应力。在固定其他条件只改变一个沉积参数的情况下,得到制备具有较小内应力的硼碳氮薄膜的最佳沉积条件：溅射功率为80 W、衬底温度为400 ℃、沉积时间为2 h。     

ZrO2薄膜残余应力实验研究

采用ZYGO MarkⅢ-GPI数字波面干涉仪对电子束蒸发方法制备的ZrO2薄膜中的残余应力进行了研究,讨论了沉积温度、沉积速率等工艺参量对ZrO2薄膜残余应力的影响。实验结果表明：随着沉积温度及沉积速率的升高,ZrO2薄膜中残余应力状态由张应力变为压应力,且压应力值随着沉积温度升高而增大。同时用X射线衍射技术测量分析了不同沉积条件下ZrO2薄膜的微结构组织,探讨了ZrO2薄膜微结构与其应力的对应关系。     

Film growth mechanisms in pulsed laser deposition

This paper reviews our recent studies of the fundamentals of growth morphology evolution in Pulsed Laser Deposition in two prototypical growth modes: metal-on-insulator island growth and semiconductor homoepitaxy. By comparing morphology evolution for pulsed laser deposition and thermal deposition in the same dual-use chamber under identical thermal, background, and surface preparation conditions, and varying the kinetic energy by varying the laser fluence or using an inert background gas, we have isolated the effect of kinetic energy from that of flux pulsing in determining the differences between morphology evolution in these growth methods. In each growth mode analytical growth models and Kinetic Monte Carlo simulations for thermal deposition, modified to include kinetic energy effects, are successful at explaining much of what we observe experimentally.