直流、射频磁控溅射制备钌薄膜的微观结构及电学性能分析

为了探索直流和射频磁控溅射制备钌薄膜的微观结构及性能差异,进而指导薄膜制备工艺优化。采用直流和射频磁控溅射法在SiO2/Si(100)衬底上沉积不同时间和温度的钌薄膜;通过高分辨场发射扫描电镜、X射线衍射仪、原子力显微镜、四探针等方法研究不同溅射电源下制备的钌薄膜的微观结构和电学性能。结果表明,在相同溅射条件下,DC-Ru薄膜的结晶性优于RF-Ru薄膜;其厚度大于RF-Ru薄膜,满足tDC≈2tRF;其沉积速率高于RF-Ru薄膜,满足vDC≈2vRF。然而,其电阻率却高于RF-Ru薄膜,这主要得益于RF-Ru薄膜的致密度较高,从而降低了电子对缺陷的散射效应。     

Structural investigations of YSZ coatings prepared by DC magnetron sputtering

(ZrO₂)_1−x(Y₂O₃)_x thin films were sputter-deposited from metallic targets in various reactive argon-oxygen gas mixtures. Structural investigations have been realised by X-ray Diffraction (XRD), Raman spectroscopy and Transmission Electron Microscopy (TEM). The coatings microstructure have been characterised by TEM and their morphology by Scanning Electron Microscopy (SEM) on brittle-fracture cross sections. Chemical compositions have been achieved by Electron Probe Micro-Analysis (EPMA) and by Energy Dispersive Spectroscopy (EDS). Finally, attention was paid to the film optical properties, as assessed via Optical Transmission Interferometry (OTI) as well as spectrophotometry.In a first part, we have studied the influence of the argon pressure on the chemical, structural and morphological properties of the coatings. In a second part, we have observed the effect of the yttria content on the structure of the films.     

Fabrication and its characteristics of hard coating Ti-Al-N system prepared by DC magnetron sputtering

Pseudobinary Ti1-xAlxN films were synthesized on Si (100) wafer by DC magnetron sputtering method using Ti1-dAlx alloy targets with different Al contents. The composition of the Ti1-AlxN films was determined by electron probe microanalysis (EPMA). Structural characteristic was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution TEM (HRTEM). First principles virtual crystal calculations for the Ti1-xAlxN disordered alloys were used for the XRD simulations. The crystalline structure of the Ti0. 61Al0. 39N film was found to be a metastable single phase with NaCl (B1) structure. Its lattice constant, determined by XRD, was less than that of pure TiN. With the increase of Al content, the lattice constant of B1 phase was continually decreased, while würtzite (B4) structure was observed in the Ti0. 40Al0. 60N film. When x reached 0. 75, the B1 phase disappeared, and only 34 phase was remained. The critical Al content for the phase transition from NaCl to würtzite structure in this paper was about 0. 60, which could be explained by both the thermodynamic model and the electron theory. As-deposited Ti1-xAlxN films exhibited excellent mechanical properties. Hardness measurements of Ti1-xAlxN films showed a high value of 45GPa for x=0. 39 and was decreased to value of 27 Gpa with increasing Al at x=0. 60.     

调制脉冲磁控溅射峰值靶功率密度对纯Ti镀层沉积行为的影响

调制脉冲磁控溅射可通过改变强/弱离化阶段的脉冲强度和占空比等电场参量,大幅调控镀料粒子的离化率、沉积能量和数量,可实现对沉积镀层形核与生长过程的精确把控。本文在非平衡闭合磁场条件下,采用调制脉冲磁控溅射技术,通过对其强离化脉冲阶段的脉冲宽度和靶功率进行调控获得持续增大的峰值靶功率密度,并在此条件下制备多组纯Ti镀层,对其微观形貌和力学性能进行了检测分析。研究结果表明,当强离化脉冲阶段的峰值靶功率密度由0.15 kW×cm-2持续增大至0.86 kW×cm-2时,所制备的纯Ti镀层具有11nm的平均晶粒尺寸、较其他峰值靶功率密度条件下制备镀层更为致密的组织结构、平整的表面质量（表面粗糙度Ra为11nm）和良好的力学性能。     

直流溅射沉积CrAlN和CrN薄膜微观结构与摩擦性能分析研究

采用直流反应溅射在304不锈钢表面沉积CrAlN和CrN薄膜。利用X射线衍射仪（XRD）,扫描电子显微镜（SEM）,X射线光电子能谱仪（XPS）,原子力显微镜（AFM）等表征Al元素的加入对CrN薄膜成分与组织结构的影响。采用摩擦磨损试验机和3 mm的Si3N4作为对偶球测试其在不同环境下的摩擦性能,并利用Nanomap 500LS三维轮廓仪表征磨痕轮廓。研究结果表明,CrN薄膜主要物相是CrN和Cr2N相,CrAlN薄膜主要物相是CrAlN和Cr2N相。CrN薄膜的（200）晶面的CrN相呈择优取向,而CrAlN薄膜的（200）晶面的CrAlN相也呈择优取向。在CrAlN沉积的过程中,部分的Cr原子被Al原子替代形成有利于细化晶粒和提高薄膜的综合性能。因此,在所有的实验环境中,CrAlN薄膜都比CrN薄膜具有更好的抗磨损性能和低的磨损率。     

Structurally laminated CrN films deposited by multi pulse modulated pulsed power magnetron sputtering

The paper presents the results on the deposition of nanoscale structurally laminated CrN films using a novel multi pulse modulated pulsed power (MPP) magnetron sputtering technique. With the multi pulse MPP approach, thin films with a structural modulation in the nanometer range are obtained by alternately switching two (or even more) high power MPP pulses on the same target, which have different pulse lengths, frequencies and powers. Each pulse was turned on for a pulse repeat duration during which this given pulse shape was repeated. In this study, CrN films have been deposited in a closed field unbalanced magnetron sputtering system using the multi pulse MPP technique by varying the pulse repeat duration of two different pulses. The CrN films were also deposited by dc magnetron sputtering (dcMS) and single pulse MPP techniques for comparison. The microstructure and properties of the films were characterized using glancing incident X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nanoindentation, and ball-on-disk wear tests. The structure and properties of the multi pulse MPP CrN films depended on the pulse repeat duration. The highest hardness of 30.5 GPa and an H/E ratio of 0.9 have been achieved in the multi pulse MPP CrN films. The wear rate of the single pulse MPP and multi pulse MPP CrN films decreased by a factor of 5.8–17 as compared to the dcMS CrN films.     

退火温度对直流磁控溅射制备Ru薄膜微观结构及膜基结合力的影响

采用磁控溅射法在Mo衬底上制备了Ru薄膜,利用真空退火炉、EDS、XRD,台阶仪及纳米划痕仪等设备研究了不同退火温度对Ru薄膜化学成分、相结构、残余应力及膜基结合力的影响。结果表明,不同退火温度处理下的Ru薄膜呈六方Ru结构,具有（002）择优取向,当退火温度为600 ℃时,薄膜出现氧化相。退火处理能够改善薄膜结晶程度。随退火温度的升高,薄膜残余应力逐渐降低,膜基结合力先升高后降低,当退火温度为300 ℃时,膜基结合力最高,约为17.6 N。     

Silver-palladium alloy deposited by DC magnetron sputtering method as lubricant for high temperature application

The silver-palladium(Ag-Pd) alloy coating as a solid lubricant was investigated for its application to the high temperature stud bolts used in nuclear power plants. A hex bolt sample was prepared in the following steps: 1) bolt surface treatment using alumina grit blasting for cleaning and increasing the surface area; 2) nickel(Ni) film coating as a glue layer on the surface of the bolt; and 3) Ag-Pd alloy coating on the Ni film. The films were deposited by using a direct current(DC) magnetron sputtering system. The thickness and composition of the Ag-Pd alloy film have effect on the friction coefficient, which was determined using axial force measurement. A 500 nm-thick Ag-Pd (80:20, molar ratio) alloy film has the lowest friction coefficient of 0.109. A cyclic test was conducted to evaluate the durability of bolts coated with either the Ag-Pd (80:20) alloy film or N-5000 oil. In a cycle, the bolts were inserted into a block using a torque wrench, which was followed by heating and disassembling. After only one cycle, it was not possible to remove the bolts coated with the N-5000 oil from the block. However, the bolts coated with the Ag-Pd (80:20) alloy could be easily removed up until 15 cycles.     

磁控溅射法制备的羟基磷灰石—氧化锆涂层的力学性能(英文)

采用磁控溅射法在Ti6Al4V钛合金基体上制备羟基磷灰石(HA)-氧化锆(ZrO2)复合涂层,通过SEM、EDS、XRD和划痕法对50HA-50ZrO2和75HA-25ZrO2(质量分数,%)涂层进行表征,分析HA含量对涂层残余应力的影响。实验结果表明,HA-ZrO2复合涂层的物相为HA、ZrO2和Y2O3,在复合过程中HA部分发生分解,产生TCP和CaO等杂质相;涂层表面呈多孔状,有利于类骨组织的生长,50HA-50ZrO2和75HA-25ZrO2深层的表面粗糙度分别为1.61μm和2.92μm;涂层结合界面为机械结合方式,划痕法测量的50HA-50ZrO2和75HA-25ZrO2深层界面结合强度分别为30N和17.5N,随着HA含量的增加,涂层结合强度呈现下降的趋势;50HA-50ZrO2和75HA-25ZrO2涂层的残余应力分别为(-399.1±3)MPa和(-343.2±20.3)MPa,适当增加HA可以减小涂层的残余应力。     

溅射功率和气压对直流磁控溅射制备钨薄膜的影响

钨薄膜具有高熔点、高导电性、优异的耐化学腐蚀性和强抗辐照性等特性,广泛的应用于微电子、核能工程等领域。由于薄膜的结构和性能对沉积参数具有很强的依赖性,因此控制沉积过程的工艺参数对获得优异性能的钨薄膜至关重要。采用DC磁控溅射技术在硅衬底上制备钨薄膜,探究了溅射功率和气压对钨薄膜沉积速率、电阻率和相结构的影响。采用原子力显微镜、XRD、轮廓仪、四探针电阻测量表征了薄膜的微观结构和电学性能。结果表明,薄膜的沉积速率受溅射功率和气压共同影响,随功率的增加呈线性增加,随溅射气压的增加先达到峰值,然后下降。薄膜的电阻率和表面粗糙度的大小依赖于溅射气压,且随溅射气压的增加而增加,薄膜电阻率的增加可能是由于表面粗糙度的增加导致的。在恒定的溅射功率下,β-W的形成主要取决于溅射气压,几乎所有β-W相都在高溅射气压下形成,然而,当溅射功率足够大,在较高的气压下也会观察到部分α-W相的形成。钨薄膜中特定相结构(α-W/β-W)的形成,不仅取决于沉积气压,还与溅射功率相关,归根可能与入射到基片的原子能量相关。     

316L不锈钢直流磁控溅射制备铝膜的工艺研究

采用直流磁控溅射在316L不锈钢上制备了高质量的Al膜,并利用扫描电镜、X射线衍射仪分别对镀层的形貌和结构及应力进行了分析。结果表明,温度、溅射功率之间的合理配置才能制备致密性高、表面缺陷少的Al膜,较优工艺参数温度为170℃、溅射功率1400 W;温度比溅射功率更容易改善结晶度,当溅射功率高、基体温度低,薄膜趋向非晶态;制备的薄膜应力小,最大约为0.176 GPa,微结构对应力影响大。     

Microstructure control of CrNx films during high power impulse magnetron sputtering

The microstructure and composition of CrN_x (0 ≤ x≤ 1) films grown by reactive high power pulsed magnetron sputtering (HIPIMS or HPPMS) have been studied as a function of the process parameters: N₂-to-Ar discharge gas ratio, (f_N2/Ar), negative substrate bias (V_s), pulsing frequency, and energy per pulse. The film stoichiometry is found to be determined by the composition of the material flux incident upon the substrate during the active phase of the discharge with no nitrogen uptake between the high power pulses. Scanning electron microscopy investigations reveal that for 0 < f_N2/Ar < 0.15 and 150 V bias, a columnar film growth is suppressed in favor of nano-sized grain structure. The phenomenon is ascribed to the high flux of doubly charged Cr ions and appears to be a unique feature of HIPIMS. The microstructure of column-less films for 100 V ≤ V_s ≤ 150 V is dominated by the CrN and hexagonal β-Cr₂N phases and shows a high sensitivity to V_s. As the amplitude of V_s decreases to 40 V and self-biased condition, the film morphology evolves to a dense columnar structure. This is accompanied by an increase in the average surface roughness from 0.25 nm to 2.4 nm. CrN_x samples grown at f_N2/Ar ≥ 0.3 are columnar and show high compressive stress levels ranging from −7.1 GPa at f_N2/Ar = 0.3 to −9.6 GPa at f_N2/Ar = 1. The power-normalized deposition rate decreases with increasing pulse energy, independent of f_N2/Ar. This effect is found to be closely related to the increased ion content in the plasma as determined by optical emission spectroscopy. The HIPIMS deposition rate normalized to DC rate decreases linearly with increasing relative ion content in the plasma, independent of f_N2/Ar and pulsing frequency, in agreement with the so-called target-pathways model. Increasing frequency leads to a finer grain structure and a partial suppression of the columnar growth, which is attributed to the corresponding increase of the time-averaged mean energy of film-forming ions arriving at the substrate.     

Nd-Fe-B薄膜的磁控溅射法制备与组织结构

对直流磁控溅射法制备Nd-Fe-B薄膜工艺进行了研究.在不同的溅射功率、溅射气压、溅射时间等条件下制备薄膜,并对薄膜进行了AFM、XRD分析.结果表明,Nd-Fe-B薄膜的沉积速率、表面形貌及相结构与溅射功率、溅射气压、溅射时间密切相关.薄膜的沉积速率随磁控溅射功率的增加而增加,薄膜表面晶粒尺寸和表面粗糙度随溅射功率增加而增大.沉积速率随溅射气压的升高先增大后减小.低功率溅射时,薄膜中出现α-Fe、Nd2Fe14B相相对较少,随溅射功率增加,α-Fe相消失,Nd2Fe14B相增多.综合考虑各种因素,最佳溅射功率为100～130 W.     

磁控溅射制备SiC薄膜及其高温抗氧化性

用射频磁控溅射法在单晶Si(100)基片上制备了SiC薄膜.将制备的薄膜分别在800、900和1000℃空气气氛中退火120 min.用X射线衍射仪和傅里叶变换红外光谱仪测试了薄膜的结构,用X射线光电子能谱仪测试了薄膜元素的组成和状态,用场发射扫描电子显微镜测试了薄膜表面的形貌.结果表明:经800℃空气退火后,薄膜表面生成了一层SiO2保护层,阻止了内部SiC薄膜的继续氧化,因此SiC薄膜在800℃具有较好的高温抗氧化性;随着退火温度的升高,SiC薄膜被进一步氧化,经1000℃空气退火后,薄膜已大部分转变为SiO2.     

Investigation of Niobium oxynitride thin films deposited by reactive magnetron sputtering

Niobium oxynitride films were deposited using reactive magnetron sputtering of a niobium target in an Ar/O₂/N₂ atmosphere with fixed nitrogen flux in direct current (DC) and pulsed modes. For the DC sputtering mode the deposition rate was found to be twice as high as for the pulsed mode at lower oxygen to nitrogen ratios (O/N). Morphology investigation by scanning electron microscopy and atomic force microscopy showed that the coatings are getting very smooth with increasing oxygen content (average roughness R_a < 0.4 nm at oxygen contents > 40 at.%). X-ray diffraction measurements revealed that the niobium oxynitride films are X-ray amorphous for oxygen contents > 40 at.%. The electrical conductivity of the coatings was studied by the 4 point-probe method and was found to decrease with increasing oxygen content. Optical properties of Nb-O-N films were analysed by spectroscopic ellipsometry and transmission spectroscopy. The refractive index of transparent and semi-transparent films was found to be in the range of 2.3 and 2.6 (at 633 nm). The experimental results will be discussed with respect to the O/N ratios (range 1.2 < O/N < ∞) or the oxygen content (range 33.7 at.% < O < 67.3 at.%) in the films as measured by Rutherford backscattering spectroscopy and particle induced X-ray emission.     

磁控溅射法制备Cu_2ZnSnS_4薄膜及其性能表征

利用磁控溅射法将Cu/Sn/Zn S前驱体沉积在钙钠玻璃基片上,再通过硫化该前驱体制备Cu2ZnSnS4薄膜。利用X射线衍射仪、拉曼光谱仪、扫描电子显微镜、能谱仪、霍尔效应测量系统和紫外可见分光光度计研究了Cu2ZnSnS4薄膜的微观结构、表面形貌、化学成分、电学和光学性能。结果表明,CZTS薄膜的微观结构依赖于硫化温度和时间。在480℃硫化3 h的薄膜为沿(112)晶面择优取向生长的纯相CZTS薄膜,该薄膜的禁带宽度是1.51 e V,其电阻率和载流子浓度分别为0.39Ω·cm和4.07×1017cm-3。     

Growth characteristics of MoS2 coatings prepared by unbalanced bipolar DC magnetron sputtering

MoS2 coatings were prepared by unbalanced bipolar DC magnetron sputtering under different argon pressures and for different deposition times, and the structure and morphology of MoS2 coatings were determined and observed respectively by X-ray diffractometry and scanning electron microscopy. The results show that at lower argon pressures of 0.15 Pa and 0.40 Pa, MoS2 coatings are formed with the （002） basal plane parallel to the surface, whereas the coating deposited at the argon pressure above 0.60 Pa has the （002） basal plane perpendicular to the surface. Two stages can be classified for the formation of MoS2 coating. At the initial stage of coating formation, the （002） basal plane with S-Mo-S layer structure grows on the substrate whatever the argon pressure is. And then the coating under 0.40 Pa argon pressure still grows with （002） laminate structure, but the coatings under 0.88 Pa and 1.60 Pa argon pressures turn to grow with the mixed basal and edge orientations. The morphology and structure of MoS2 coatings are highly related to their growth rate and the energy of sputtered particles.     

Control of reactive high power impulse magnetron sputtering processes

High power impulse magnetron sputtering (HIPIMS) is a technologically important physical vapour deposition (PVD) process that is able to provide a highly ionised flux of sputtered species. It is thought to be particularly important for applications where there is a need to coat 3D features (e.g. vias and trenches in semiconductor applications). HIPIMS may have other added benefits, as compared to DC or medium frequency AC/pulse-DC magnetron sputtering, related to better coating structure-property relationship control through self-species (sputtered metal) plasma/ion assistance.Many of the technologically important thin films (e.g. transparent conductive oxides, permeation barrier coatings, etc.) are sputtered from metal targets in a reactive gas atmosphere, usually Ar + O₂ or N₂, to ensure industrially relevant coating deposition rates. Enhanced structure-property relationship control of these thin film materials is highly desirable; hence, it also is desirable to use HIPIMS in a reactive deposition mode. Preliminary trials of reactive HIPIMS however have indicated that the control of this process using conventional means, such as conventional plasma emission monitoring (PEM) is difficult. Thus, the application of reactive HIPIMS is rather limited and the potential benefits are not realised, especially in the areas where precise process control and long term stability in a reactive environment are required.In this paper reactive HIPIMS process (Ti in Ar/O₂ atmosphere) is investigated and various control options are evaluated. The application of a recently developed PEM based reactive HIPIMS control method is reported. Performance of the developed technique is compared to that of the conventional PEM, Penning-PEM and λ-sensor based methods. It is shown that conventional PEM is impractical to control reactive HIPIMS, while the constant reactive gas flow method does not lead to a stable deposition process. The new PEM based process control technology was shown to provide precise control and stable operation of reactive HIPIMS discharges anywhere within the hysteresis loop. It was also found to be superior when compared to oxygen partial pressure control based techniques.     

Microstructure and mechanical property evaluation of pulsed DC magnetron sputtered Cr–B and Cr–B–N films

CrB₂ and four Cr–B–N films with high Cr/B ratio and various nitrogen contents were deposited by a co-sputtering process using a bipolar asymmetric pulsed DC reactive magnetron sputtering system. The structures and BN bonding nature of the thin films were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR), respectively. The surface and cross sectional morphologies of the thin films were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface roughness of the thin films was explored by atomic force microscopy (AFM). Nanoindentation, microscratch and ball-on-disk wear techniques were used to evaluate the hardness, and tribological properties of the thin films, respectively.The microstructure of the Cr–B–N thin films changed from a coarse columnar structure to a glassy and featureless morphology as the nitrogen content increased from 15.2 at.% to 54.5 at.%, whereas the corresponding structure developed from an amorphous state to a nanocomposite structure consisting of CrN nanograins and amorphous BN phases. It was found that high hardness, good tribological and brittle properties were obtained for the CrB₂ coating. The hardness and elastic modulus of the Cr–B–N thin films decreased with increasing nitrogen content until the nanocomposite structure of nanocrystalline CrN grains and an amorphous BN matrix was formed. However, the hardening effect induced by the nanocomposite structure was limited due to the fact that the small CrN nanograins were surrounded by a thick intergranular soft amorphous BN layer. On the other hand, the fracture toughness and resistance against elastic strain to failure of the Cr–B–N coatings were effectively enhanced by the addition of nitrogen.