射频磁控溅射制备(AlCrTiZrNb)N高熵合金薄膜的微观组织和力学性能

研究了氮含量对(Al Cr Ti Zr Nb)N高熵合金薄膜微观结构和力学性能的影响,利用射频磁控溅射工艺在不同N2和Ar流量比下制备了(Al Cr Ti Zr Nb)N高熵合金薄膜。结果表明,随着氮气流量的升高,(Al Cr Ti Zr Nb)N薄膜的沉积速率逐渐下降,Al Cr Ti Zr Nb合金薄膜的结构由非晶态转变为由Me-N(金属氮化物)构成的面心立方固溶体结构,(Al Cr Ti Zr Nb)N薄膜的择优生长取向为(200)晶面。同时随着N2流量的增加,(Al Cr Ti Zr Nb)N高熵合金薄膜的硬度首先快速升高,随后略微降低。当N2∶Ar=1∶1时,(Al Cr Ti Zr Nb)N薄膜硬度最大值28.324 GPa,此时(Al Cr Ti Zr Nb)N薄膜呈现单一的面心立方固溶体结构,饱和Me-N相的形成与各元素的固溶强化作用是其硬度的增长的主要原因。     

反应溅射(Al,Ti)(O,N)涂层的微结构与力学性能

采用Al-Ti镶嵌复合靶在Ar、N2和O2混合气体中反应溅射制备了一系列(Al,Ti)(O,N)涂层.并采用EDS、XRD、TEM和微力学探针研究了薄膜的化学成分、微结构和力学性能.结果表明,随氧分压的提高,涂层中氧含量逐步增加,氮含量相应减少,(Al Ti):(O N)的化学计量比仍约为1:1,涂层保持与(Al,Ti)N涂层相同的NaCl结构.低氧含量时薄膜在(111)方向上择优生长,随着氧含量的提高,涂层生长的择优取向发生改变,高氧含量薄膜样品呈现强烈(200)织构的柱状晶.与此同时,(Al,Ti)(O,N)涂层的硬度和弹性模量也仍保持在与(Al,Ti)N涂层相当的35GPa和370～420GPa的高值.由于涂层中形成了相当含量的氧化物,这类涂层的抗氧化能力有望得到提高.     

射频磁控溅射(Ti,Al)N薄膜性能的研究

采用射频磁控溅射，用Al靶和Ti靶同时溅射沉积（Ti，Al）N薄膜。研究表明：不同Al靶功率沉积的薄膜中始终存在面心立方结构（B1型），当Al靶功率大于250W薄膜中面心立方结构（B1型）和六方结构（B4型）共存。随Al成分的增加，B1型结构晶格常数减小，薄膜择优取向由B1型（111）向B4型（002）转变。薄膜表面随Al靶功率增加分别呈岛状、纤维状和柱状增长。（Ti，Al）N薄膜的硬度随Al靶功率的增加呈上升趋势。等离子体发射光谱分析显示，在相同工艺条件下Al靶比Ti靶先进入非金属态溅射模式，导致在相同功率下Al溅射速率低于Ti溅射速率。     

铜铟铝硒薄膜离子束溅射制备与表征

采用离子束溅射方法,在玻璃衬底上沉积Cu,In,Al和Se,在同一真空环境下进行退火处理,制备得到铜铟铝硒(CIAS)太阳电池吸收层薄膜。利用扫描电镜、X射线衍射仪、能谱仪、四探针系统、分光光度计分别对薄膜的表面形貌、物相结构、晶粒尺寸、元素含量、电阻率和禁带宽度等特性进行分析。结果表明:通过控制铜铟、Cu、Al、Se各靶材的镀膜时间,实现在Cu In Se2薄膜上掺杂Al元素,制备的CIAS薄膜呈现黄铜矿结构。薄膜(112)衍射峰峰位,表面电阻率和禁带宽度随着铝含量的增加而增加,调节Al元素的含量可以使薄膜表面均匀。当Al的原子分数比X(Al)=14.47%时,(112)衍射峰最强,半高宽最小,结晶最好。当X(Al)=11.8%,N(Al)/(N(In)+N(Al))=0.37,禁带宽度为2.12 e V,薄膜表面形貌最均匀。     

Al含量对真空电弧沉积ZrAlN薄膜性能的影响

利用等离子体辅助电弧沉积技术在高速钢片和单晶硅片P(100)上沉积ZrAlN多元薄膜,利用扫描电镜、能谱分析、X射线衍射对薄膜进行了结构和形貌表征,利用显微硬度计、摩擦磨损试验仪对薄膜的性能进行了检测,并研究了铝含量对薄膜组织结构、形貌、显微硬度及耐磨性能等的影响.结果表明:ZrAlN多元薄膜有(111)面的择优取向,随Al含量的增加,(111)衍射峰的位置向小角度偏移,当Al原子分数大于3%时,薄膜中出现AlN相;随着Al含量的增加,薄膜的硬度和耐磨损性能先增加后降低,在Al原子分数为3%时,获最高硬度1570 HV0.5N和最小磨痕宽度93μm,这是薄膜中Al含量不同引起晶体结构变化造成的.     

非平衡磁控溅射制备氮化硅薄膜及其性能研究

采用非平衡磁控溅射技术,通过改变氮气和氩气分压比P(N2)/P(Ar),在钛合金(Ti6Al4V)表面制备出不同结构及性能的氮化硅薄膜.结果显示,制备的氮化硅薄膜为非晶态结构,随着氮气分压的增加,Si-N键的含量增加,其对应的红外吸收峰逐渐变宽,并向高波数偏移.氮化硅薄膜的显微硬度、耐磨性随着P(N2)/P(Ar)的增加而先增加,当P(N2)/P(Ar)为0.25时,随着P(N2)/P(Ar)的增加,薄膜硬度及耐磨性稍有降低.氮化硅薄膜具有较好的膜/基结合力,当增大氮气和氩气分压比,薄膜的脆性随之增加.     

电弧离子镀Cr1-xAlxN硬质薄膜的成分、结构与性能

采用电弧离子镀的分离靶弧流调控技术在硬质合金基体上制备了4组不同Al含量的Cr_1-xAl_xN硬质薄膜, 采用SEM、XPS、GIXRD、Nanoindenter及划痕仪分别表征了薄膜的形貌、成分、相结构和力学性能。结果表明: 4组薄膜厚度分别为1.28、1.42、1.64和1.79 μm; 成分x随着Al靶的弧流相对增大而增大, 分别为x=0.41、0.53、0.64和0.73; 相结构与成分密切相关, 当x=0.41时, 薄膜呈单一的c-(Cr,Al)N相, 而当x≥0.53时, 则由c-(Cr,Al)N相和hcp-AlN相混相构成; 随着Al含量增加, 晶粒尺寸先减小后增大, 在x=0.64时达到最小值8.9 nm; 相应地硬度则先增大后减小, 在x=0.64时达到峰值35.3 GPa; 4组Cr_1-xAl_xN薄膜的膜基结合良好, 结合力均在60 N以上。综合测试结果发现, 当x=0.53时, Cr_1-xAl_xN薄膜的韧性最佳, 弹性恢复系数最高为57.4%, 同时兼具较高的硬度34.7 GPa, 此时薄膜具有最佳的综合性能。     

CrAlYN纳米多层薄膜的微观结构和抗高温氧化性能研究

采用非平衡磁控溅射离子镀技术在M2工具钢和单晶Si表面沉积不同Y含量的Cr Al YN纳米多层薄膜,并在静态空气中进行1000℃的高温氧化实验。透射电子显微镜、扫描电镜、X射线衍射、能量色散谱、纳米压痕和划痕实验等研究结果表明:Cr Al YN纳米多层薄膜呈现fcc晶体结构,调制周期为Cr N/YN+Al N/Cr N/Al N。Cr Al YN纳米多层薄膜的抗高温氧化性能随着Y含量提高呈现先提高后下降的趋势,Y含量为1.13%(原子比)时,薄膜表现出最优的力学性能,当Y含量增加到2.67%时,薄膜的力学性能明显下降。     

TC4合金表面磁控溅射W-Al-N复合膜的摩擦磨损和高温抗氧化性能

目前,在WN中加入Al制备多元复合膜的研究国内外报道较少。通过射频磁控溅射法,以不同Al靶功率在Si(100)和TC4合金上制备了不同Al含量的W-Al-N复合膜。采用扫描电镜、能谱仪、X射线衍射仪、纳米压痕仪(CSM)、摩擦磨损试验机、高温氧化试验研究了W-Al-N复合膜的微结构、力学性能、摩擦磨损性能及高温抗氧化性能。结果表明:随着Al含量的增加,W-Al-N复合膜的择优取向发生变化,(111)和(220)衍射峰逐渐消失,复合膜主要呈(200)择优取向生长;复合膜的硬度先增加后减小,当Al含量为32.40%(原子分数,下同)时硬度达到最大值37 GPa,此时表征复合膜抵抗塑性变形能力的变量H~3/E~(*2)也达到最大值0.308;室温下,随Al含量的增加,W-Al-N复合膜的摩擦系数与单层WN薄膜的相比变化不大,磨损率先降低后增大,在硬度最大处得到磨损率最低值9×10~(-9)mm~2/N;W_(0.676)Al_(0.324)N复合膜的摩擦系数在200℃时降低,随后随温度的升高先增大后减小;Al的加入提高了复合膜的高温抗氧化性能,起始氧化温度由WN单层膜的400℃提高到复合膜的800℃。     

非平衡磁控溅射氮化钛薄膜及其性能研究

采用非平衡磁控溅射技术,在钛合金(Ti6Al4V)表面沉积氮化钛薄膜。通过改变氮气和氩气分压比(PN/PAr)和基体偏压,制备出不同结构、性能的氮化钛薄膜。采用X射线衍射技术、原子力显微镜、PS-168型电化学测量系统、CSEM球盘摩擦磨损实验机、HXD-1000 knoop显微硬度仪等研究了薄膜的结构、表面形貌、耐腐蚀性能与机械性能。结果表明,采用非平衡磁控溅射技术制备出了致密的氮化钛薄膜。当PN/PAr较小时,氮化钛薄膜中存在Ti2N时,Ti2N相可以有效提高薄膜的硬度和耐磨损性能;当PN/PAr增加到0.1时,薄膜硬度达到最大,耐磨损性能最优;随着PN/PAr的继续增大,氮化钛薄膜中主要存在TiN相,氮化钛薄膜的复合硬度和耐磨损性能降低。在钛合金(Ti6Al4V)表面沉积氮化钛薄膜可以显著提高其在Hanks类体液中的耐腐蚀性能。     

Mechanical properties and phase structure of (TiAlZr)N films deposited by multi arc ion plating

A series of Ti-Al-Zr alloy targets with the atomic ratio of (Al + Zr)/(Ti + Al + Zr) from 0.29 to 0.40 were used directly to prepare (Ti,Al,Zr)N multi component hard reactive films on high speed steel substrates by multi arc ion plating (MAIP) technology. The surface morphology, the cross-fracture microstructure, the surface compositions and the phase structure of the (Ti,Al,Zr)N films were investigated by scanning electronic microscope (SEM) and X-ray diffraction (XRD). The dense columnar microstructure was obtained in all of the (Ti,Al,Zr)N films, though micro-droplets evidently existed on the surface of the films. The XRD analysis revealed f.c.c. structure only existing in all of the (Ti,Al,Zr)N films. The lattice parameter was changed with varying the Al and Zr contents in alloy targets.The micro-hardness of film surface and the adhesive property of film/substrate were measured. All the (Ti,Al,Zr)N films displayed excellent mechanical properties. The adhesive strength, in terms of critical load, was larger than 100N and the hardness was bigger than 3000Kg(f)/mm². The (Ti,Al,Zr)N film displayed the highest micro-hardness as the atomic ratio of (Al + Zr)/(Ti + Al + Zr) in Ti-Al-Zr alloy target reached 0.40. The present results suggest the expectant substitution of (Ti,Al,Zr)N films for TiN, (Ti,Al)N and (Ti,Zr)N hard films in industrial application and the technical advantage of Ti-Al-Zr alloy targets in preparing (Ti,Al,Zr)N hard films by multi arc ion plating.     

(Ti,Al,Zr)N多元氮梯度硬质反应膜的组织结构和性能

采用多弧离子镀技术和Ti-Al合金靶及Zr单质靶的组合,在高速钢基体上制备了(Ti,Al,Zr)N多元N梯度硬质反应膜.分别用扫描电镜、X射线衍射仪观察测定(Ti,Al,Zr)N梯度膜膜层的表面、断面形貌、成分以及相结构,研究了(Ti,Al,Zr)N多元氮梯度硬质反应膜的组织结构和性能.结果表明,与TiN、(Ti,Al...     

室温磁控溅射制备(Ti,Zr)N薄膜及其性能研究

采用直流反应磁控溅射工艺,在载波片和Al基材上制备出金黄色的(Ti,Zr)N薄膜.(Ti,Zr)N薄膜具有比TiN薄膜更高的硬度和更强的耐腐蚀性能.用XRD衍射方法和扫描隧道显微镜对薄膜的晶体结构、微观表面形貌和电子结构进行了测试分析.XRD结果表明,(Ti,Zr)N薄膜为多晶态,存在TiN和ZrN两种分离相;从表面形貌可知,薄膜表面平整,晶粒排列致密且无连接松散的大颗粒;STS谱表明,Zr掺杂后,禁带宽度仍为1.64eV,但在禁带内增加了新能级,新能级的宽度分别为0.33eV和0.42eV,这也正是掺杂Zr后,薄膜仍呈现金黄色的主要原因.     

Deposition process,microstructure and mechanical behaviours of RF magnetron sputtered (Ti,Al)N thin films

Abstract

Thin films of (Ti,Al)N with different Al contents were co-deposited using one Ti and one Al targets by radio frequency (RF) pulsed magnetron sputtering. Their composition, microstructure, nanohardness, surface morphology and deposition process were investigated by energy dispersive spectrometer system, X-ray diffraction, nanoindentation, atomic force microscopy and optical emission spectrum. A face cubic centred (fcc) TiN (B1) structure was found in the thin films when Al target power was low. When Al target power was increased, an additional hexagonal AlN (B4) structure appeared. With increasing Al content, the resulting films gradually changed from B1 structure to that of B4, accompanying with decrease of the lattice constant of B1 structure. Simultaneously, the preferred orientation of B4 structural thin films gradually transformed from (111) to (200). The mode of thin films transformed from island to fibre, subsequently to column with increasing Al target power. Optical emission spectrum analysis indicated that Al target surface reached non-metal sputtering mode earlier than that of Ti target under the same deposition parameters, which resulted in a lower sputtering rate of Al target than Ti target and loss of Al content in (Ti,Al)N thin films.     

Effects of bias voltage on the microstructure and mechanical properties of (Ti,Al,Cr)N hard films with N-gradient distributions

(Ti,Al,Cr)N hard reactive films were deposited on high speed steel substrates by multi-arc ion plating (MAIP) technology using pure Cr and Ti-50Al(at.%) alloy targets. The partial pressure of N₂ was raised step by step in each deposition process. The surface morphology, the cross-sectional morphology of fracture sample, the surface compositions and the phase structure of the (Ti,Al,Cr)N films were investigated by scanning electronic microscope (SEM) and X-ray diffraction (XRD). The dense columnar microstructure was obtained in all of the (Ti,Al,Cr)N films, though micro-droplets evidently existed on the surface of the films. The micro-hardness of the film surface, the adhesive strength of the film/substrate and the thermal shock resistance were investigated. The results revealed the effects of bias voltage on the composition, phase structure, and mechanical properties. The improved balanced properties of a micro-hardness of about 50 GPa, an adhesive strength larger than 200 N and a thermal shock resistance of 7-8 cycles were reached at a bias voltage of 150 V. The present super-hard (Ti,Al,Cr)N films with N-gradient distribution may be an actual substitution of TiN, (Ti,Al)N, (Ti,Cr)N and single-layer (Ti,Al,Cr)N hard films.     

多弧离子镀(Ti,Al,Zr,Cr)N多组元氮化物膜的研究

采用多弧离子镀技术,使用Ti Al Zr合金靶和Cr靶,在W18Cr4V高速钢基体上沉积(Ti,Al,Zr,Cr)N多组元氮化物膜.利用扫描电镜(SEM)、电子能谱仪(EDS)和X射线衍射(XRD)对薄膜的成分、结构和微观组织进行测量和表征;利用划痕仪、显微硬度计测评薄膜的力学性能.结果表明,获得的多组元氮化物膜仍具有B1 NaCl型的TiN面心立方结构;薄膜的成分除-50V偏压外,其它偏压下的变化均不明显;增大偏压可减少薄膜表面的液滴污染,提高薄膜的显微硬度及膜/基结合力,最高值可分别达到HV3300和190N.     

AZ31镁合金表面磁控溅射Zr(Al,Ti)-SiN_x复合薄膜及其耐蚀性能

镁合金表面沉积薄膜可以提高其耐蚀性,但现有的几种沉积方法得到的膜疏松、与基体结合力差,影响了其耐腐蚀性能.为此,采用磁控溅射法在AZ31镁合金表面制备了Al,Zr,Ti膜及其与SiN_x的复合薄膜.用扫描电镜、X射线衍射、XPS研究了金属膜及其与SiNi_x复合薄膜的晶体结构、表面形貌和化学成分.结果表明:所制备的SiN_x薄膜为非晶态的富N膜;Zr膜的耐腐蚀性最好,Al膜的保护性最差;Zr-SiN_x复合薄膜比AZ31镁合金的腐蚀电流密度降低了3个数量级,Ti-SiN_x复合薄膜在阳极极化区出现了钝化.SiN_x复合薄膜的耐腐蚀性优于AZ31镁合金和单一金属膜.     

Electrical characterization of wurtzite (Al,B)N thin films

Wurtzite aluminum nitride (w-AlN) thin films are of great interest for electro-acoustic applications and their material properties have in recent years been extensively studied. One way to tailor material properties is to vary the composition by adding other elements. Boron is an element that can take the place of aluminum in the crystal lattice of w-AlN. In the present study, polycrystalline w-(Al,B)N thin films were grown on p-Si(100) and Al/p-Si(100) substrates by pulsed DC reactive magnetron sputtering from a single Al/B target. MIS and MIM structures were fabricated to investigate the electrical properties of w-(Al,B)N thin films. Important dielectric thin film properties for microelectronics applications are the breakdown field, the permittivity (κ) and leakage current through the film. The (Al,B)N thin film is found to have a dielectric strength of ～3 × 10⁶ V cm^?1 and a κ close to 12. The measured leakage current through the film is assumed to be mainly due to Frenkel–Poole emission with a trap energy at 0.71 eV below the conduction band edge.     

Electrical characterization of wurtzite (Al,B)N thin films

Wurtzite aluminum nitride (w-AlN) thin films are of great interest for electro-acoustic applications and their material properties have in recent years been extensively studied. One way to tailor material properties is to vary the composition by adding other elements. Boron is an element that can take the place of aluminum in the crystal lattice of w-AlN. In the present study, polycrystalline w-(Al,B)N thin films were grown on p-Si(100) and Al/p-Si(100) substrates by pulsed DC reactive magnetron sputtering from a single Al/B target. MIS and MIM structures were fabricated to investigate the electrical properties of w-(Al,B)N thin films. Important dielectric thin film properties for microelectronics applications are the breakdown field, the permittivity (κ) and leakage current through the film. The (Al,B)N thin film is found to have a dielectric strength of ∼3 × 10⁶ V cm⁻¹ and a κ close to 12. The measured leakage current through the film is assumed to be mainly due to Frenkel–Poole emission with a trap energy at 0.71 eV below the conduction band edge.     

退火处理Fe(Co)Al(Zr)O系薄膜磁性能的研究

采用射频磁控溅射装置在氩气氛下制备了Fe(Co)Al(Zr)O系薄膜.用X射线衍射仪、透射电镜及其选区衍射来分析薄膜的微结构.用振动样品磁强计、磁导计等测量了矫顽力Hc、饱和磁化强度Ms及磁导率等磁性参数.通过退火处理研究了Fe(Co)Al(Zr)O系薄膜的磁性能.Fe(Co)Al(Zr)O系薄膜磁各向异性是由形状各向异性引起的.