脉冲磁控溅射氮化铬薄膜及其性能研究

采用新型脉冲磁控溅射技术制备了一系列氯化铬膜，对所制备的不同厚度薄膜进行了AFM和SEM形貌等分析．测定了薄膜的膜基结合强度和硬度，并对薄膜的摩擦学性能进行了研究。结果表明：通过使用铬过渡层可以提高膜基结合强度，镀层厚度对镀层摩擦学性能有影响，膜厚为1200nm的氯化铬膜试样显示出来高硬度、低摩擦系数和良好的抗磨性。     

A comparative study of CrNx coatings Synthesized by dc and pulsed dc magnetron sputtering

Chromium nitride (CrN_x) coatings were prepared by reactively sputtering chromium metal target with various nitrogen flow rate percentages (f_N2) using a closed field unbalanced magnetron sputtering system operated in dc and middle frequency pulsed condition (100 kHz and 50% duty cycle). In this study, plasma examination proved that a large amount of ions with a wide range of ion energies (up to 65 eV and mainly from 10-30 eV region) was identified in the pulsed plasma compared to the low ion flux and energy (0-10 eV) in a dc discharged plasma. The results showed that the phase structure of CrN_x coatings was changed from nitrogen doped Cr(N) to pure β-Cr₂N, and to a mixture of β-Cr₂N and c-CrN and then to pure c-CrN phases with an increase in the f_N2 in both dc and pulsed conditions. However, the pulsed CrN_x coatings exhibit lower N concentrations than dc CrN_x coatings prepared under the same f_N2, which leads to the existing of β-Cr₂N phase within a wide range of f_N2 (30-50%). In comparison with the typical large columnar structure in the dc sputtered coatings, the pulsed CrN_x coatings exhibit dramatic microstructure improvements which benefited from the improved plasma density and ion bombardment from the pulsed plasma, where the super dense and nearly equi-axial structures were observed in a wide range of f_N2. The microstructure improvements contributed to the enhancements in the hardness and wear resistance of pulsed CrN_x coatings. In the pulsed CrN_x coatings, the hardness values were above 30 GPa when the f_N2 is in the range of 30-40%, which is related to the formation of the β-Cr₂N phase. With the formation of a mixture of β-Cr₂N and c-CrN phases in the coatings deposited with 40-50% f_N2, a low COF of 0.36 and wear rate of 1.66 × 10^− 6 mm³ N^− 1 m^− 1 can be achieved.     

Cathodic arc plasma deposited TiAlSiN thin films using an Al-15 at.% Si cathode

Thin films of TiAlSiN were deposited on SKD 11 tool steel substrates using two cathodes, of Ti and Al-15 at.% Si, in a cathodic arc plasma deposition system. The influence of AlSi cathode arc current and substrate bias voltage on the mechanical and structural properties of the films was investigated. The TiAlSiN films had a multilayered structure in which nanocrystalline cubic TiN layers alternated with nanocrystalline hexagonal AlSiN layers. The hardness of the films decreased with the increase of the AlSi cathode arc current. The hardness of the films also decreased as the bias voltage was raised from − 50 V to − 200 V. The maximum hardness of 43 GPa was observed at the films deposited at the pressure 0.4 Pa, Ti cathode arc current 55 A, Al cathode arc current 35 A, temperature 250 °C and bias voltage of − 50 V.     

离子束增强反应磁控溅射低温快速沉积AlN膜

本文采用氮离子束增强反应磁控溅射,在低温下沉积了 AlN 薄膜.用 X 射线衍射和 X 射线光电子谱对薄膜的晶体结构和电子结构进行了分析,结果表明,随着离子源中氮离子束流的增加,薄膜组成由面心立方的 Al 转变为密排立方的 AlN.氮离子在薄膜制备中的引入,有效地降低了沉积温度,提高沉积速率,并实现了薄膜 N/Al 化学计量比的控制.对 AlN 薄膜的紫外-可见光透射谱和红外吸收谱也进行了测定.     

Micro-hardness, microstructures and thermal stability of (Ti,Cr,Al,Si)N films deposited by cathodic arc method

(Ti,Cr,Al,Si)N films were deposited by cathodic arc method using TiCrAlSi alloy cathodes. It was found that the microstructures of (Ti,Cr,Al,Si)N were closely related to (Al+Si) content. The crystal structure of (Ti,Cr,Al,Si)N was NaCl-type structure up to the (Al+Si) content of 0.60, where it changed to a hexagonal structure. The maximum hardness of 33 GPa was obtained at the lowest (Al+Si) content of 0.56, still in the cubic structure. The micro-hardness decreased down to 28 GPa as the crystal structure changed from NaCl-type to wurtzite-type.To investigate the thermal stabilities of (Ti,Cr,Al,Si)N, the films were annealed in a vacuum furnace. In Ti_0.20Cr_0.20Al_0.55Si_0.05N with cubic structure, the phase segregation occurred by annealing at over 900 °C, while Ti_0.22Cr_0.22Al_0.44Si_0.12N remained in cubic phase up to 1000 °C. The micro-hardness of Ti_0.20Cr_0.20Al_0.55Si_0.05N increased and that of Ti_0.22Cr_0.22Al_0.44Si_0.12N decreased at 1000 °C. Ti_0.20Cr_0.11Al_0.58Si_0.11N with a cubic and hexagonal mixture phase held its (c,h)-mixture phase up to 1000 °C, while there was an indication of an increase both in micro-hardness and in cubic ratio after annealing.In this paper, the micro-hardness and microstructure of (Ti,Cr,Al,Si)N are discussed as a function of annealing temperature and investigated by X-ray diffraction and electron microscopy.     

柱弧离子镀和非平衡磁控溅射镀制备Ti-N-C黑色硬质膜

采用柱弧离子镀和中频孪生靶非平衡磁控溅射镀膜技术制备了Ti-N-C多层复合黑色硬质膜.采用轮廊仪扫描电子显微镜(SEM)、分光光度计、显微硬度计等手段研究了所得膜层的各项性能.结果表明,两种工艺都可以获得颜色较深的黑色硬质膜,柱弧离子镀制备黑色硬质膜的效率高、力学性能更好;中频孪生靶非平衡磁控溅射制备的黑色硬质膜表面光滑、颜色更深.     

Nanostructure transition in Cr-C-N coatings deposited by pulsed closed field unbalanced magnetron sputtering

Cr-C-N coatings with different compositions, i.e. (C + N)/Cr atomic ratios (x) of 0.81-2.77, were deposited using pulsed closed field unbalanced magnetron sputtering by varying the chromium and graphite target powers, the pulse configuration and the ratio of the nitrogen flow rate to the total gas flow rate. Three kinds of nanostructures were identified in the Cr-C-N coatings dependent on the x values: a nano-columnar structure of hexagonal closed-packed (hcp) Cr₂(C,N) and face-centered cubic (fcc) Cr(C,N) at x = 0.81 and 1.03 respectively, a nanocomposite structure consisting of nanocrystalline Cr(C,N) embedded in an amorphous C(N) matrix at x = 1.26 and 1.78, and a Cr-containing amorphous C(N) structure at x = 2.77. A maximum hardness of 31.0 GPa and a high H/E ratio of 1.0 have been achieved in the nc-Cr(C,N)/a-C(N) nanocomposite structure at x = 1.26, whereas the coating with a Cr-containing amorphous C(N) structure had a minimum hardness of 10.9 GPa and a low H/E ratio of 0.08 at x = 2.77. The incorporation of carbon into the Cr-N coatings led to a phase transition from hcp-Cr₂(C,N) to fcc-Cr(C,N) by the dissolution into the nanocrystallites, and promoted the amorphization of Cr-C-N coatings with the precipitation of amorphous C(N). It was found that a high x value over 1.0 in the Cr-C-N coatings is the composition threshold to the nanostructure transition.     

Modulated pulse power sputtered chromium coatings

Cr coatings were deposited using continuous dc magnetron sputtering (dcMS) and modulated pulse power sputtering (MPP) techniques in a closed field unbalanced magnetron sputtering system at equivalent average target powers. It was found that MPP sputtering exhibited higher deposition rates than in dcMS when the average target power density was above 14 W cm^− 2 for the Cr coating depositions. Plasma diagnostics confirmed a significant increase in the numbers of both target material (Cr) and gas (Ar) ions in the MPP plasma as compared to the dc plasma. The substrate peak current densities measured in the MPP depositions (104-324 mA cm^− 2) have been increased by over a factor of 50 to those in the dcMS conditions (2-5.5 mA cm^− 2). The enhanced ion flux bombardment from the highly ionized MPP plasma led to the formation of denser microstructure and finer grain size in the MPP Cr coatings than in the dcMS Cr coatings. In addition, MPP sputtered Cr coatings exhibited improved hardness and adhesion.     

Influence of annealing temperature on the structural, mechanical and wetting property of TiO2 films deposited by RF magnetron sputtering

TiO₂ films have been deposited on silicon substrates by radio frequency magnetron sputtering of a pure Ti target in Ar/O₂ plasma. The TiO₂ films deposited at room temperature were annealed for 1 h at different temperatures ranging from 400 °C to 800 °C. The structural, morphological, mechanical properties and the wetting behavior of the as deposited and annealed films were obtained using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, nanoindentation and water contact angle (CA) measurements. The as deposited films were amorphous, and the Raman results showed that anatase phase crystallization was initiated at annealing temperature close to 400 °C. The film annealed at 400 °C showed higher hardness than the film annealed at 600 °C. In addition, the wettability of film surface was enhanced with an increase in annealing temperature from 400 °C to 800 °C, as revealed by a decrease in water CA from 87° to 50°. Moreover, the water CA of the films obtained before and after UV light irradiation revealed that the annealed films remained more hydrophilic than the as deposited film after irradiation.     

Characterization and properties of CrN films deposited by ion-source-enhanced middle frequency magnetron sputtering

CrN films with deposition rates of 130-180 nm/min were deposited on Si (111) and carbamide alloy substrates by an ion-source-enhanced middle frequency magnetron sputtering system. Increasing of ion source voltages promoted the growth of CrN films with preferred orientation of (200). The deposited CrN films are composed of nanocrystalline particles with sizes of ∼20 nm embedded in polycrystalline matrix. The hardness of the CrN films increases from 1300 Kg/mm² without ion source bombardment to 2400 Kg/mm² with ion source voltages of 1000 V. Origins for the increasing of hardness can be attributed to dislocation strengthening and densification effects.     

Structure, hardness and thermal stability of TiAlN and nanolayered TiAlN/CrN multilayer films

TiAlN films were deposited on silicon (1 1 1) substrates from a TiAl target using a reactive DC magnetron sputtering process in Ar+N₂ plasma. Films were prepared at various nitrogen flow rates and TiAl target compositions. Similarly, CrN films were prepared from the reactive sputtering of Cr target. Subsequently, nanolayered TiAlN/CrN multilayer films were deposited at various modulation wavelengths (Λ). X-ray diffraction (XRD), energy dispersive X-ray analysis, nanoindentation and atomic force microscopy were used to characterize the films. The XRD confirmed the formation of superlattice structure at low modulation wavelengths. The maximum hardness of TiAlN/CrN multilayers was 3900 kg/mm², whereas TiAlN and CrN films exhibited maximum hardnesses of 3850 and 1000 kg/mm², respectively. Thermal stability of TiAlN and TiAlN/CrN multilayer films was studied by heating the films in air in the temperature range (T_A) of 500-900 °C for 30 min. The XRD spectra revealed that TiAlN/CrN multilayers were stable up to 800 °C and got oxidized substantially at 900 °C. On the other hand, the TiAlN films were stable up to 700 °C and got completely oxidized at 800 °C. Nanoindentation measurements performed on the films after heat treatment showed that TiAlN retained a hardness of 2200 kg/mm² at T_A=700 °C and TiAlN/CrN multilayers retained hardness as high as 2600 kg/mm² upon annealing at 800° C.     

CrN/AlN superlattice coatings synthesized by pulsed closed field unbalanced magnetron sputtering with different CrN layer thicknesses

CrN/AlN superlattice coatings with different CrN layer thicknesses were prepared using a pulsed closed field unbalanced magnetron sputtering system. A decrease in the bilayer period from 12.4 to 3.0 nm and simultaneously an increase in the Al/(Cr + Al) ratio from 19.1 to 68.7 at.% were obtained in the CrN/AlN coatings when the Cr target power was decreased from 1200 to 200 W. The bilayer period and the structure of the coatings were characterized by means of low angle and high angle X-ray diffraction and transmission electron microscopy. The mechanical and tribological properties of the coatings were studied using the nanoindentation and ball-on-disc wear tests. It was found that CrN/AlN superlattice coatings synthesized in the current study exhibited a single phase face-centered cubic structure with well defined interfaces between CrN and AlN nanolayers. Decreases in the residual stress and the lattice parameter were identified with a decrease in the CrN layer thickness. The hardness of the coatings increased with a decrease in the bilayer period and the CrN layer thickness, and reached the highest value of 42 GPa at a bilayer period of 4.1 nm (CrN layer thickness of 1.5 nm, AlN layer thickness of 2.5 nm) and an Al/(Cr + Al) ratio of 59.3 at.% in the coatings. A low coefficient of friction of 0.35 and correspondingly low wear rate of 7 × 10^− 7 mm³N^− 1m^− 1 were also identified in this optimized CrN/AlN coating when sliding against a WC-6%Co ball.     

射频功率对氧化铬薄膜的力学性能和耐磨损性能的影响

利用射频反应磁控溅射法在45钢基体上制备了氧化铬薄膜.采用XRD测试了薄膜的晶体结构,用Tribo-Indentor纳米力学测试系统得到了薄膜的硬度及微观形貌,在UMT显微力学测试仪上测试了薄膜的耐磨损性能,在此基础上讨论了铬靶溅射功率对薄膜的力学性能和耐磨损性能的影响.结果表明:在射频功率较低的情况下薄膜为Cr2O3结构.随着射频功率的提高,薄膜表面的大颗粒物质增多,硬度下降.射频功率增大时,磨损体积增加,薄膜的耐磨损性能下降.     

Influence of the ion-atom flux ratio on the mechanical properties of chromium nitride thin films

In this paper we report the mechanical properties of chromium nitride (CrN) thin films deposited at different levels of ion bombardment and their relationship with the microstructural parameters, such as grain size, preferred orientation and residual stress. The samples were deposited by unbalanced magnetron sputtering changing the substrate-target distance and the substrate bias, keeping other deposition condition fixed. The mechanical properties were obtained by nanoindentation performed on 1.8 μm thick samples. Under the different deposition conditions all of the CrN films were approximately stoichiometric, but clear variations in the microstructure were seen. The hardness was nearly constant at 24-27 GPa even when the grain size, residual stress and crystalline orientation changed. However, the elastic modulus showed a steady increase from 300 to 350 GPa, proportional to the variations in grain size and the residual stress level.     

磁控溅射TiAlVN薄膜中V含量对其结构和抗腐蚀性能的影响

向TiAlN薄膜中添加V可改善薄膜性能.采用磁控溅射技术沉积了不同V含量的TiAlVN薄膜,通过能谱仪、台阶仪、X射线衍射仪(XRD)和原子力显微镜(AFM)分析薄膜的成分、厚度、相结构和表面形貌,用动电位极化的方法研究薄膜的抗腐蚀性能.结果表明:TiAlVN薄膜属于面心立方(fcc)和六方密排(hcp)二重结构,晶格...     

Hysteresis and process stability in reactive high power impulse magnetron sputtering of metal oxides

In the further development of reactive sputter deposition, strategies which allow for stabilization of the transition zone between the metallic and compound modes, elimination of the process hysteresis, and increase of the deposition rate, are of particular interest. In this study, the hysteresis behavior and the characteristics of the transition zone during reactive high power impulse magnetron sputtering (HiPIMS) of Al and Ce targets in an Ar-O₂ atmosphere as a function of the pulsing frequency and the pumping speed are investigated. Comparison with reactive direct current magnetron sputtering (DCMS) reveals that HiPIMS allows for elimination/suppression of the hysteresis and a smoother transition from the metallic to the compound sputtering mode. For the experimental conditions employed in the present study, optimum behavior with respect to the hysteresis width is obtained at frequency values between 2 and 4 kHz, while HiPIMS processes with values below or above this range resemble the DCMS behavior. Al-O films are deposited using both HiPIMS and DCMS. Analysis of the film properties shows that elimination/suppression of the hysteresis in HiPIMS facilitates the growth of stoichiometric and transparent Al₂O₃ at relatively high deposition rates over a wider range of experimental conditions as compared to DCMS.     

等离子体源辅助磁控溅射法低温(200℃)制备多晶硅薄膜

利用电感耦合等离子体辅助中频直流脉冲磁控溅射技术在200℃成功制备出多晶硅薄膜.详细介绍了等离子体源辅助磁控溅射技术制备多晶硅的工艺过程,并对辅助等离子体源放电功率对硅薄膜结晶度的影响进行了研究.利用拉曼散射、X射线衍射、傅里叶红外光谱对所制备的硅薄膜进行了表征.     

Influence of thickness on the crystallography and surface topography of TiN nano-films deposited by reactive DC and pulsed magnetron sputtering

TiN films of 50 nm and 500 nm thickness were deposited on M2 tool steel substrates by reactive closed field unbalanced magnetron sputtering operating in direct current (DC) and pulsed magnetron sputtering (PMS) modes. Parameters of the crystallographic structure and surface roughness and their evolution during the films growth were analyzed via X-ray diffraction and atomic force microscopy. The obtained results show that all the analyzed films have polycrystalline and mono-phase (TiN) structures. In the 50 nm films, the in plane crystallographic texture that formed was 100% {111}. During film growth a weakening of the preferred crystallographic orientation and a decrease of the concentration of lattice imperfections occurred. Both processes are more pronounced in the film deposited by PMS compared to that deposited by DC sputtering. Film growth is accompanied by increasing of surface smoothness. Pulsing the target power led to a decrease of the mean surface roughness of both the 50 nm and 500 nm films.     

The fabrication and application of ZnO:Al thin films in low-frequency inductively coupled plasma fabricated silicon solar cell

A home-made radio frequency magnetron sputtering is used to systematically study the structural, electrical, and optical properties of aluminum doped zinc oxide (ZnO:Al) thin films. The intensity of the (002) peak exhibits a remarkable enhancement with increasing film thickness. Upon optimization, we achieved low resistivity of 4.2 × 10^− 4 Ω cm and high transmittance of ~ 88% for ZnO:Al films. Based on the present experimental data, the carrier transport mechanism is discussed. It is found that the grain boundary scattering needs to be considered because the mean free path of free carrier is comparable to the grain size. The 80 nm-ZnO:Al thin films are then deposited onto low-frequency inductively coupled plasma fabricated silicon solar cells to assess the effect of ZnO:Al thin films on the performance of the solar cells. Optimized ZnO:Al thin films are identified as transparent and conductive oxide thin film layers.     

Structural and mechanical properties of multi-element (AlCrMoTaTiZr)Nx coatings by reactive magnetron sputtering

(AlCrMoTaTiZr)N_x high-entropy films were deposited on silicon wafer and cemented carbide substrates from a single alloy target by reactive RF magnetron sputtering under a mixed atmosphere of Ar and N₂. The effect of nitrogen flow ratio R_N on chemical composition, morphology, microstructure, and mechanical properties of the (AlCrMoTaTiZr)N_x films was investigated. Nitrogen-free alloy film had an amorphous structure, while nitride films with at least 37 at.% N exhibited a simple NaCl-type FCC (face-centered cubic) structure. Mixed structures occurred in films with lower nitrogen contents. Films with the FCC structure were thermally stable without phase decomposition at 1000 °C after 10 h. The (AlCrMoTaTiZr)N film deposited at R_N = 40% exhibited the highest hardness of 40.2 GPa which attains the superhard grade. The main strengthening mechanisms for this film were grain-size and solid-solution strengthening. A residual compressive stress of 1.04 GPa was small to account for the observed hardness. The nitride film was wear resistant, with a wear rate of 2.8 × 10^− 6 mm³/N m against a loaded 100Cr6 steel ball in the sliding wear test. These high-entropy films have potential in hard coating applications.