不同能量密度下脉冲激光烧蚀制备纳米Si晶粒成核生长动力学研究

在室温、10 Pa氩气环境下,采用脉冲激光烧蚀(PLA)技术,通过改变激光能量密度,在烧蚀点正下方、与烧蚀羽辉轴线平行放置的衬底上沉积制备了一系列纳米Si晶薄膜.采用SEM、Raman散射谱和XRD对纳米Si晶薄膜进行了表征.结果表明:沉积在衬底上的纳米Si晶粒分布在距靶一定的范围内,晶粒尺寸随与靶面距离的增加先增大后减小;随着激光能量密度的增加,晶粒在衬底上的沉积范围双向展宽,但沉积所得最大晶粒尺寸基本保持不变,只是沉积位置随激光能量密度的增加相应后移.结合流体力学模型、成核分区模型和热动力学方程,通过模拟激光烧蚀靶材的动力学过程,对纳米Si晶粒的成核生长动力学过程进行了研究.     

低压环境中外加氩气流对激光沉积纳米硅晶粒尺寸及分布的影响

采用脉冲激光沉积(PLD)技术,在烧蚀点正上方0.35 cm、距靶0.7 cm处引入Ar气流,保持环境气压0.3 Pa,烧蚀高阻抗单晶硅(Si)靶.在烧蚀点正下方0.35 cm,距靶0.5 cm、0.7 cm、1.4 cm、2.1 cm、2.8 cm、3.0 cm和3.5cm处水平放置衬底来收集纳米Si晶粒.利用原子力显微镜(AFM)、X射线衍射(XRD)、Raman散射对样品表面形貌和微观结构进行分析表征.结果表明:在引入气流前后,纳米Si晶粒的尺寸均随着与靶距离的增加而逐渐减小;在同一位置,引入气流比不引入气流晶粒尺寸小,面密度大;在3.0～3.5 cm处,不引入气流时的样品不再有纳米Si晶粒,而引入气流的还存在纳米Si晶粒.     

脉冲激光烧蚀制备纳米硅晶粒成核生长的热力学条件研究

文中利用蒙特卡洛方法,引入成核生长模型,研究了纳米硅晶粒成核生长过程.结合宏观阻力模型,计算了纳米硅成核和生长所对应的过饱和度范围.结果显示,衬底的二次溅射,造成成核次数增多,生成小尺寸纳米晶粒的数量增加;晶粒成核过程和生长过程所需要的过饱和度范围不同,过饱和度较大(>2600)时成核次数多生长次数少;而过饱和度在250～2600时生长次数多成核次数少.     

真空中脉冲激光烧蚀制备银纳米晶粒在水平衬底上的分布特性

在室温、真空环境中,通过XeCl准分子脉冲激光烧蚀银靶,烧蚀产物沉积在水平放置的Si(111)衬底上.利用扫描电子显微镜(SEM)、X射线衍射(XRD)仪、探针式表面轮廓(PTSP)仪和选区电子衍射(SAED)对沉积所得的样品进行表征.结果表明,样品主要由具有不同尺寸的银纳米晶粒组成;随着衬底与靶面水平距离的增加,样品厚度和晶粒尺寸逐渐减小;样品的(111)和(200)晶面的XRD特征谱线强度,随着衬底位置的改变而变化.在增加激光能量密度、衬底与烧蚀焦点垂直距离的情况下,晶粒尺寸及样品XRD特征谱线变化规律并未发生明显变化.结合银纳米晶粒传输特性和沉积样品沿不同晶面生长所需表面能的差异,对实验结果进行了分析.     

基于朗缪尔探针的硅离子空间分布特性及纳米晶粒生长过程研究

在室温、10 Pa氩气环境气体中,采用脉冲激光烧蚀技术,在以烧蚀点为圆心、半径为2 cm的玻璃弧形支架的不同角度处放置衬底,沉积了纳米Si晶薄膜.通过扫描电子显微镜、拉曼散射仪对制备样品的形貌和特性进行分析.结果表明:纳米Si晶粒以羽辉轴线为轴呈对称分布,在轴线处平均尺寸最大,随着衬底同轴线夹角的增加,晶粒尺寸逐渐减小.结合朗缪尔探针对空间不同位置羽辉中Si离子密度和热运动温度分布的诊断情况,从晶粒生长过程的角度对其尺寸随空间位置变化的结果进行了研究,得到了晶粒尺寸正比于烧蚀粒子密度和热运动温度的结论.     

混合环境气体配比对纳米硅晶粒角度分布的影响

为了研究混合环境气体配比对脉冲激光烧蚀制备纳米硅(Si)晶粒角度分布的影响,采用XeCl准分子激光器,烧蚀高阻抗单晶Si靶,改变混合环境气体配比(He/Ar =41、1∶10、1∶1、1∶4、1∶2),在半圆环衬底上成功制备了一系列纳米Si晶薄膜.使用扫描电子显微镜(SEM)图像、X射线衍射谱(XRD)和拉曼光谱(Raman)对其进行表征分析.结果表明,在五种配比下,纳米Si晶粒的平均尺寸均随着偏离羽辉轴向夹角的增大而减小;各个角度处,纳米Si晶粒的平均尺寸均随着混合环境气体平均原子质量的增加而呈现先减小后增大的趋势.从传输动力学角度,对结果进行了定性分析.     

纳米晶粒多晶Si薄膜的低压化学气相沉积

利用低压化学气相沉积(LPCVD)方法,以充Ar的SiH4作为反应气体源,在覆盖有热生长SiO2层的p-(100)Si衬底上制备了具有均匀分布的纳米晶粒多晶Si膜(nc-poly-Si).采用扫描电子显微镜(SEM)、原子力显微镜(AFM)和拉曼谱等检测手段,测量和分析了沉积膜层的表面形貌、晶粒尺寸与密度分布等结构特征.结果表明,nc-poly-v膜中Si晶粒的尺寸大小和密度分布强烈依赖于衬底温度、SiH4浓度与反应气压等工艺参数.典型实验条件下生长的Si纳米晶粒形状为半球状,晶粒尺寸约为40nm,密度分布约为4.0×1010cm-2和膜层厚度约为200nm.膜层的沉积机理分析指出,衬底表面上Si原子基团的吸附、迁移、成核与融合等热力学过程支配着nc-poly-Si膜的生长.     

不同衬底表面上大晶粒多晶Si薄膜的制备

利用高频感应加热化学气相沉积(HFCVD)工艺,以H2稀释的SiH4作为反应气体源,分别在n-(111)Si衬底上常规热生长的SiO2层、织构的SiO2层和纳米晶粒多晶Si薄膜表面上,制备了具有均匀分布的大晶粒多晶Si膜.采用扫描电子显微镜(SEM)和X射线衍射(XRD)等检测手段,测量和分析了沉积膜层的表面形貌、晶粒尺寸、密度分布与择优取向等结构特征.结果表明,多晶Si膜中Si晶粒的尺寸大小和密度分布不仅与衬底温度、SiH4浓度与反应气压等工艺参数有关,而且强烈依赖于衬底的表面状态.本实验获得的最好的薄膜中,Si晶粒平均尺寸约为2.3 μm,密度分布约为3.8×107/cm2.对薄膜的沉积机理分析表明,衬底表面上Si原子基团的吸附、迁移、成核与融合等热力学过程支配着大晶粒多晶Si膜的生长.     

LICVD法纳米硅制备过程中的成核及生长

自行设计制备了激光诱导化学气相沉积法(LICVD)纳米制粉装置,利用该装置制备的纳米硅粉其粒度波动在30～60nm之间.通过对不同反应气体流量条件下的激光能量阈值研究表明,随反应气体流量的增加,所需激光能量阈值大致成线性增加.利用透射电镜和高分辨电镜对其形貌进行了表征,并对其成核与生长进行了分析,在成核长大初期,晶核周围的Si原子浓度较高,纳米硅晶应以层状长大方式为主.当纳米晶中有螺型位错等晶体缺陷形成时,会为Si原子的"落座"提供生长所需的台阶源,晶粒将以螺旋状生长方式长大.在长大过程中,纳米晶会发生跳跃式长大现象.以跳跃方式长大的晶粒通常在两晶粒的结合面处伴有晶体缺陷发生或亚晶界产生.较低的反应气体流速条件下,纳米硅的择优生长方向为<112>晶向;而在较高的反应气体流速条件下其择优生长方向变为<111>晶向.     

氧气流量对MgxZn1-xO薄膜择优取向的影响

利用脉冲激光沉积技术,选用靶材为Mg0.5Zn0.5O陶瓷靶材,在非晶石英衬底上研究氧气流量对MgxZn1-xO合金薄膜生长取向的影响.结果表明:在低压、低氧气流量条件下薄膜的成核生长主要受控于晶面的表面能,薄膜为(200)晶向;在沉积压强8.0Pa时,随着氧气流量的增加,反应粒子的能量降低,不同取向晶粒的生长速率发生变化,导致MgZnO薄膜的生长取向由(200)择优取向转变为(111)择优取向.当氧气流量过大(70 sccm)时,由于氧气分子迁移能的提高,MgZnO薄膜呈现多个不同生长取向.     

脉冲激光沉积碳薄膜生长中氢气的作用

采用石墨靶,通过脉冲激光沉积技术在温度为20℃的玻璃和硅衬底上沉积出厚度为100nm的碳薄膜,所用的激光源是ArF激光(λ＝193nm, 24ns). 通过调节氢气流量使反应室的压力在1.33×10-5～133Pa之间变化. 拉曼光谱测量显示有一1550cm-1为中心的宽峰, 这与用其他方法制备的典型类金刚石碳(DLC)膜相类似, 随着增大氢气压力,膜的吸收系数减小, 而光带隙增大. 在氢气压力为133Pa下沉积的薄膜具有大于2.5eV的光带隙, 比无氢气气氛下沉积的薄膜的光带隙大1倍. 结果表明, 氢气对蚀刻sp2键是有效的. 在PLD法中, 从靶中喷射的等离子体物质和氢分子预先被离解成原子氢, 与CVD法的情况相同,这些原子氢必定起到蚀刻sp2键的作用.     

溶剂热法制备Al掺杂ZnO薄膜的机理研究

采用溶剂热法在玻璃衬底上制备Al掺杂的ZnO薄膜,研究了溶剂热过程中升温、恒温和降温三个阶段分别对薄膜物相和形貌的影响,探讨了薄膜的生长机理.结果表明,升温阶段只是形核过程,基片仅在升温阶段与前驱液接触不能形成薄膜;基片在升温-恒温阶段与前驱液接触可制备(002)择优取向的薄膜;恒温阶段既有成核过程又有晶体生长过程,基片仅在恒温阶段与前驱液接触可以制备薄膜;降温阶段薄膜继续生长.     

加氮对直流电弧等离子体喷射金刚石膜生长、形貌和质量的影响

利用直流等离子体喷射化学气相沉积法制备掺氮的金刚石厚膜.本文研究了在甲烷/氩气/氢气中加入氮气对金刚石膜生长、形貌和质量的影响.反应气体的比例由质量流量计控制,在固定氢气(5000sccm)、氩气(3000sccm)、甲烷(100sccm)流量的情况下改变氮气的流量,即反应气体中氮原子和碳原子的变化比例(N/ C比)范围是从0.06到0.68.同时金刚石膜在固定的腔体压力(4kPa)和衬底温度(800℃)下生长.金刚石膜用扫描电镜(SEM)、拉曼谱和X射线衍射表征.结果表明,氮气在反应气体中的大量加入对直流等离子体喷射制备金刚石膜的形貌、生长速率、晶体取向、成核密度等有非常显著的影响.     

Effect of AlN doping on the growth morphology of SiC

AlN doped SiC films were deposited on on‐axis Si‐face 4H‐SiC (0001) substrates by the physical vapor transport (PVT) method. Thick film in the range of 20 μm range was grown and morphology was characterized. Films were grown by physical vapor deposition (PVD) in a vertical geometry in the nitrogen atmosphere. We observed that nucleation occurred in the form of discs and growth occurred in hexagonal geometry. The X‐ray studies showed (001) orientation and full width of half maxima (FWHM) was less than 0.1° indicating good crystallinity. We also observed that film deposited on the carbon crucible had long needles with anisotropic growth very similar to that of pure AlN. Some of the needles grew up to sizes of 200 μm in length and 40 to 50 μm in width. It is clear that annealing of SiC‐AlN powder or high temperature physical vapor deposition produces similar crystal structure for producing AlN‐SiC solid solution. SEM studies indicated that facetted hexagons grew on the top of each other and coarsened and merged to form cm size grains on the substrate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of temperature and carrier gas flow amount on the formation of GaN nanorods by the HVPE method

We fabricated one-dimensional GaN nanorods on AlN/Si (1 1 1) substrates at various temperatures, and carrier gas flow amount, using the hydride vapor phase epitaxy (HVPE) method. An AlN buffer layer of 50 nm thickness was deposited by RF sputtering for 25 min. Stalagmite-like GaN nanorods formed at a growth temperature of 650 °C. The diameters and lengths of GaN nanorods increase with growth time, whereas the density of nanorods decreases. And we performed the experiments by changing the carrier gas flow amount at a growth temperature of 650 °C and HCl:NH₃ flow ratio of 1:40. GaN nanorods, with an average diameter of 50 nm, were obtained at a carrier gas flow amount of 1340 sccm. The shape, structures, and optical characteristics of the nanorods were investigated by field-emission scanning electron microscopy, X-ray diffraction, and photoluminescence.     

TEM investigations of GaN layers grown on silicon and sintered GaN nano‐ceramic substrates

GaN nano‐ceramics were analyzed using transmission electron microscopy (TEM), showing that these ceramics are characterized by highly disoriented grains of the linear size of 100–150 nm. These GaN ceramics were used as substrates for GaN epitaxy in standard MOVPE conditions. For the comparison, MOVPE GaN layers on silicon substrates were grown using similar conditions. It is shown that MOVPE growth of GaN layers is highly anisotropic for both cases. However, the disorientation of the highly mismatched GaN layer on silicon is different from that characterizing GaN layer deposited on the ceramic substrate. In the latter case the disorientation is much higher, and three dimensional in nature, causing creation of polycrystalline structure having large number of the dislocations. In the case of the GaN layer grown on the silicon substrate the principal disorientation is due to rotation around c‐axis, causing creation of mosaic structure of edge dislocations. Additionally, it is shown that the typical grain size in AlN nucleation layer on Si is smaller, of order of 20 nm. These two factors contribute to pronounced differences in later stage of the growth of GaN layer on the ceramic. Due to high growth anisotropy an appropriately thick GaN layer can, eventually, develop flat surfaces suitable for construction of optoelectronic and electronic structures. As shown by the TEM data, this can be achieved only at the cost of creation of the relatively large density of dislocations and stacking faults. The latter defects were not observed for the GaN growth on Si substrates. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of deposition pressure on microstructure and properties of hydrogenated carbon nitride films prepared by DC-RF-PECVD

Hydrogenated carbon nitride (a-CN:H films) were deposited on n-type (1 0 0) silicon substrates making use of dual direct current radio frequency plasma enhanced chemical vapor deposition (DC-RF-PECVD), at working pressure of 2–20 Pa, using a mixed gas of CH₄ and N₂ as the source gas. The growth rate, composition, bonding structure of the deposited films were characterized by means of XPS and FTIR, and the mechanical properties of the deposited films were investigated by nano-indentation test. It was found that the parameters for the DC-RF-PECVD process had significant effects on the growth rate, structure and properties of the deposited films. The growth rate of the deposited films increased at first with increasing deposition pressure, then saturated with further increase of the deposition pressure. The N/C ratio inside the deposited films increased with increasing working pressure except that it was as much as 0.50 at a working pressure of 5.0 Pa. The nano-hardness of the films decreased with increasing deposition pressure. CN radicals were remarkably formed in the deposited films at higher pressures, and their contents are related to the nitrogen concentrations in the deposited films.