反应溅射VN/SiO2纳米多层膜的微结构与力学性能

采用V和SiO₂靶通过反应溅射方法制备了一系列具有不同SiO₂和VN调制层厚的VN/SiO₂纳米多层膜. 利用X射线衍射、X射线能量色散谱、高分辨电子显微镜和微力学探针表征了多层膜的微结构和力学性能. 结果表明：在Ar，N₂混和气体中，射频反应溅射的SiO₂薄膜不会渗氮. 单层膜时以非晶态存在的SiO₂，当其厚度小于1nm时，在多层膜中因VN晶体层的模板效应被强制晶化，并与VN层形成共格外延生长. 相应地，多层膜的硬度得到明显提高，最高硬度达34GPa. 随SiO₂层厚度的进一步增加，SiO₂层逐渐转变为非晶态，破坏了与VN层的共格外延生长结构，多层膜硬度也随之降低. VN调制层的改变对多层膜的生长结构和力学性能也有影响，但并不明显. 关键词： 2纳米多层膜')" href="#">VN/SiO₂纳米多层膜 共格外延生长 非晶晶化 超硬效应     

Crystallization of amorphous SiC and superhardness effect in TiN/SiC nanomultilayers

TiN/SiC nanomultilayers with various constituent layer thicknesses were prepared by magnetron sputtering using TiN and SiC ceramic targets. X-ray diffractometer, scanning electron microscope, energy dispersive spectrometer, high-resolution transmission electron microscope, atomic force microscope and nanoindenter were employed to study the growth, microstructure and mechanical properties of these films. Experimental results revealed that amorphous SiC, which is more favorable under normal sputtering conditions, was forced to crystallize and grew epitaxially with TiN layers at thicknesses of less than 0.8 nm. The resultant films were found to form strong columnar structures, accompanied with a remarkable hardness increment. Maximal nanoindentation hardness as high as 60.6 GPa was achieved when SiC thickness was ∼0.6 nm. A further increase of SiC thickness caused the formation of amorphous SiC, which blocked the epitaxial growth of the multilayers, resulting in the decline of film's hardness. Additionally, investigations on multilayers different in TiN layer thicknesses showed that they are insensitive in both microstructure and hardness to the fluctuation of TiN layer thickness. The formation of epitaxially grown structure between crystalline SiC and TiN layers was found to be responsible for the obtained superhardness in multilayers.     

反应磁控溅射ZrN/AlON纳米多层膜的晶体生长和超硬效应

采用Zr靶和Al₂O₃靶通过在Ar，N₂混合气氛中进行反应磁控溅射的方法制备了不同AlON调制层厚和不同ZrN调制层厚的两个系列的ZrN/AlON纳米多层膜.利用X射线能量色散谱仪、X射线衍射仪、高分辨透射电子显微镜和微力学探针研究了多层膜的成分、微结构和力学性能.结果表明，在Ar，N₂混合气氛中对Al₂O₃进行溅射的过程中，N原子会部分取代Al₂O₃中的氧原子，形成AlON化合物.在ZrN/AlON纳米多层膜中，由于受到ZrN晶体调制层的模板作用，溅射条件下以非晶态存在的AlON层在其厚度小于0.9nm时被强制晶化并与ZrN层形成共格外延生长；相应地，多层膜的硬度明显提高，最高硬度达到33.0GPa.进一步增加多层膜中AlON调制层的厚度，AlON层形成非晶结构，破坏了多层膜的共格外延生长，导致其硬度逐步降低. 关键词： ZrN/AlON纳米多层膜 外延生长 非晶晶化 力学性能     

Crystallization of amorphous Si3N4 and superhardness effect in HfC/Si3N4 nanomultilayers

HfC/Si₃N₄ nanomultilayers with various thicknesses of Si₃N₄ layer have been prepared by reactive magnetron sputtering. Microstructure and mechanical properties of the multilayers have been investigated. The results show that amorphous Si₃N₄ is forced to crystallize and grow coherently with HfC when the Si₃N₄ layer thickness is less than 0.95 nm, correspondingly the multilayers exhibit strong columnar structure and achieve a significantly enhanced hardness with the maximum of 38.2 GPa. Further increasing Si₃N₄ layer thickness leads to the formation of amorphous Si₃N₄, which blocks the coherent growth of multilayer, and thus the hardness of multilayer decreases quickly.     

TiN/TiB2异结构纳米多层膜的共格生长与力学性能

采用多靶磁控溅射法制备了一系列具有不同TiB₂调制层厚度的TiN/TiB_{2纳米多层膜.利用x射线衍射仪、高分辨电子显微镜和微力学探针研究了TiB2层厚变化对多层膜生长结构和力学性能的影响.结果表明，在fcc-TiN层(111)生长面的模板 作用下，原为非晶态的TiB2层在厚度小于2.9nm时形成hcp晶体态，并与fcc-TiN 形成共格外延生长；其界面共格关系为{111}TiN//{0001}TiB2，〈110〉TiN//〈1120〉TiB2.由于共格界面存在晶格失配 度，多层膜中形成拉、压交变的应力场，导致多层膜产生硬度和弹性模量升高的超硬效应， 最高硬度和弹性模量分别达到46.9GPa和465GPa.继续增加TiB2层的厚度，TiB2形成非晶态并破坏了与TiN层的共格外延生长，多层膜形成非晶TiN层和非晶TiB< sub>2层交替的调制结构，其硬度和弹性模量相应降低. 关键词： 2}纳米多层膜')" href="#">TiN/TiB₂纳米多层膜 共格生长 晶体化 力学性能     

Structure and mechanical properties of titanium nitride/carbon nitride multilayers

The structure and mechanical properties of the multilayers consisting of 5-73 nm thick titanium nitride (TiN) and 4.6 nm thick carbon nitride (CN) have been investigated. It has been found that the CN layers are amorphous and the TiN layers thinner than 17 nm are amorphous. The TiN layers become crystallized as the thickness is increased to 30 nm or thicker. The hardness from the composite response of the multilayered films and their substrates determined using continuous stiff measurement is smaller than the film-only hardness (without substrate effects) calculated using Bhattacharya-Nix empirical equation. The hardness increases with raising the thickness of TiN layers. With the crystallization of the TiN layer, the multilayers become even harder than that calculated based on the rule of mixtures. However, no enhancement in hardness has been observed when the TiN layers are amorphous.     

TiN/Al2O3纳米多层膜的共格外延生长及超硬效应

采用多靶磁控溅射法制备了一系列具有不同Al₂O₃调制层厚度的TiN/Al₂O₃纳米多层膜. 利用X射线能量色散谱、X射线衍射、扫描电子显微镜、高分辨透射电子显微镜和微力学探针表征了多层膜的成分、微结构和力学性能. 研究结果表明，在TiN/Al₂O₃纳米多层膜中，单层膜时以非晶态存在的Al₂O₃层在厚度小于1.5 nm时因TiN晶体层的模板效应而晶化，并与TiN层形成共格外延生长，相应地，多层膜产生硬度明显升高的超硬效应，最高硬度可达37.9 GPa. 进一步增加多层膜中Al₂O₃调制层的层厚度，Al₂O₃层逐渐形成非晶结构并破坏了多层膜的共格外延生长，使得多层膜的硬度逐步降低. 关键词： 2O₃纳米多层膜')" href="#">TiN/Al₂O₃纳米多层膜 外延生长 非晶晶化 超硬效应     

Characterization of hydrogenated amorphous carbon thin films by end-Hall ion beam deposition

Pure hydrogenated amorphous carbon (α-C:H) and nitrogen doped hydrogenated amorphous carbon (α-C:H:N) thin films were prepared using end-Hall (EH) ion beam deposition with a beam energy ranging from 24 eV to 48 eV. The composition, microstructure and mechanical properties of the films were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning probe microscopy (SPM), and nano-scratch tests. The films are uniform and smooth with root mean square roughness values of 0.5-0.8 nm for α-C:H and 0.35 nm for α-C:H:N films. When the ion energy was increased from 24 eV to 48 eV, the fraction of sp³ bonding in the α-C:H films increased from 36% to 55%, the hardness increased from 8 GPa to 12.5 GPa, and the Young's modulus increased from 100 GPa to 130 GPa. In the α-C:H:N films, N/C atomic ratio, the hardness and Young's modulus of the α-C:H:N films are, 0.087, 15 and 145 GPa, respectively. The results indicate that both higher ion energy and a small amount of N doping improve the mechanical properties of the films. The results have demonstrated that smooth and uniform α-C:H and α-C:H:N films with large area and reasonably high hardness and Young's modulus can be synthesized by EH ion source.     

TiCN/TiNbCN multilayer coatings with enhanced mechanical properties

Enhancement of mechanical properties by using a TiCN/TiNbCN multilayered system with different bilayer periods (Λ) and bilayer numbers (n) via magnetron sputtering technique was studied in this work. The coatings were characterized in terms of structural, chemical, morphological and mechanical properties by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nanoindentation. Results of the X-ray analysis showed reflections associated to FCC (1 1 1) crystal structure for TiCN/TiNbCN films. AFM analysis revealed a reduction of grain size and roughness when the bilayer number is increased and the bilayer period is decreased. Finally, enhancement of mechanical properties was determined via nanoindentation measurements. The best behavior was obtained when the bilayer period (Λ) was 15 nm (n = 200), yielding the highest hardness (42 GPa) and elastic modulus (408 GPa). The values for the hardness and elastic modulus are 1.6 and 1.3 times greater than the coating with n = 1, respectively. The enhancement effects in multilayer coatings could be attributed to different mechanisms for layer formation with nanometric thickness due to the Hall-Petch effect; because this effect, originally used to explain the increase in hardness with decreasing grain size in bulk polycrystalline metals, has also been used to explain hardness enhancements in multilayers taking into account the thickness reduction at individual single layers that make the multilayered system. The Hall-Petch model based on dislocation motion within layers and across layer interfaces, has been successfully applied to multilayers to explain this hardness enhancement.     

TiN/SiC纳米多层膜的生长结构与力学性能

研究了TiN/SiC纳米多层膜中立方SiC（B1cubic SiC）的形成及其对TiN/SiC多层膜力学性能的影响.结果表明：在TiN/SiC多层膜中，非晶态的SiC层在厚度小于0.6nm时形成立方结构并与TiN形成共格外延生长的超晶格柱状晶，使多层膜产生硬度和弹性模量显著升高的超硬效应，最高硬度超过60GPa.SiC随着层厚的增加转变为非晶相，从而阻止了多层膜的共格外延生长，使薄膜呈现TiN纳米晶和SiC非晶组成的层状结构特征，同时多层膜的硬度和弹性模量下降.TiN/SiC纳米多层膜产生的超硬效应与立方 关键词： 立方碳化硅 TiN/SiC纳米多层膜 外延生长 超硬效应     

Nanolayered multilayer coatings of CrN/CrAlN prepared by reactive DC magnetron sputtering

Single-phase CrN and CrAlN coatings were deposited on silicon and mild steel substrates using a reactive DC magnetron sputtering system. The structural characterization of the coatings was done using X-ray diffraction (XRD). The XRD data showed that both the CrN and CrAlN coatings exhibited B1 NaCl structure with a prominent reflection along (2 0 0) plane. The bonding structure of the coatings was characterized by X-ray photoelectron spectroscopy and the surface morphology of the coatings was studied using atomic force microscopy. Subsequently, nanolayered CrN/CrAlN multilayer coatings with a total thickness of approximately 1 μm were deposited on silicon substrates at different modulation wavelengths (Λ). The XRD data showed that all the multilayer coatings were textured along {2 0 0}. The CrN/CrAlN multilayer coatings exhibited a maximum nanoindentation hardness of 3125 kg/mm² at a modulation wavelength of 72 Å, whereas single layer CrN and CrAlN deposited under similar conditions exhibited hardness values of 2375 and 2800 kg/mm², respectively. Structural changes as a result of heating of the multilayer coatings in air (400-800 °C) were characterized using XRD and micro-Raman spectroscopy. The XRD data showed that the multilayer coatings were stable up to a temperature of 650 °C and peaks pertaining to Cr₂O₃ started appearing at 700 °C. These results were confirmed by micro-Raman spectroscopy. Nanoindentation measurements performed on the heat-treated coatings revealed that the multilayer coatings retained hardness as high as 2250 kg/mm² after annealing up to a temperature of 600 °C.     

Intrinsic mechanical properties of ultra-thin amorphous carbon layers

In this work, we extracted the film's hardness (H_F) of ultra-thin diamond-like carbon layers by simultaneously taking into account the tip blunting and the substrate effect. As compared to previous approaches, which did not consider tip blunting, this resulted in marked differences (30-100%) for the H_F value of the thinner carbon coatings. We find that the nature of the substrate influences this intrinsic film parameter and hence the growth mechanisms. Moreover, the H_F values generally increase with film thickness. The 10 nm and 50 nm thick hydrogenated amorphous carbon (a-C:H) films deposited onto Si have H_F values of, respectively, ∼26 GPa and ∼31 GPa whereas the 10 nm and 50 nm thick tetrahedral amorphous carbon (t-aC) films deposited onto Si have H_F values of, respectively, ∼29 GPa and ∼38 GPa. Both the a-C:H and t-aC materials also show higher density and refractive index values for the thicker coatings, as measured, respectively by X-ray reflectometry and optical profilometry analysis. However, the Raman analysis of the a-C:H samples show bonding characteristics which are independent of the film thickness. This indicates that in these ultra-thin hydrogenated carbon films, the arrangement of sp² clusters does not relate directly to the hardness of the film.     

Structure evolution and mechanical properties enhancement of Al/AlN multilayer

A set of Al/AlN multilayers with various modulation periods were prepared using DC magnetron sputtering method. Low angle X-ray diffraction (LAXRD) was used to analyze the layered structure of multilayers. The phase structure of the films was investigated with grazing angle X-ray diffraction (GAXRD). LAXRD results indicate that well-defined multilayer modulation structures are formed for the relatively larger modulation periods. However, the loss of mutilayered structure is detected in the multilayer with low modulation period. A very wide amorphous peak is observed in multilayer with modulation period of 4 nm. The multilayers show obvious crystallization at larger modulation periods, however, the diffraction peaks are much wider than the Al single layer because of the interruption of the continuous columnar grain growth by alternating deposition processes. Nanoindentation experiments were performed to study the mechanical properties as a function of multilayer modulation period. It is found that the hardness of the multilayers is greater than the hardness calculated from rule of mixtures. With the modulation periods adjusted, the multilayers are even harder than its hard component (AlN). A maximum hardness of 24.9 GPa, about 1.9 times larger than its hard component (AlN) and 3.7 times larger than the hardness calculated from the rule of mixtures, is found at the multilayer with modulation period of 16 nm. The wear test results show that the multilayers possess lower and stable friction coefficient, and superior wear properties.     

Effect of gas flow ratio on the microstructure and mechanical properties of boron phosphide films prepared by reactive magnetron sputtering

Boron phosphide films were grown on silicon substrate by radio frequency reactive magnetron sputtering using boron target and hydrogen phosphine at different gas flow ratios (PH₃/Ar) at lower temperature. The chemical composition, microstructure and mechanical properties were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectrum, FTIR spectrum, surface profilometer and nano-indenter. The results indicate that the atomic ratio (P/B) rises from 1.06 up to 1.52 with the gas flow ratio increasing from 3/50 to 15/50. Simultaneously, the hardness and Young's modulus decrease from 25.4 GPa to 22.5 GPa, and 250.4 GPa to 238.4 GPa, respectively. Microstructure transforms from microcrystalline state to amorphous state along with the gas flow ratio increasing. Furthermore higher gas flow ratio leads to lower stress. The BP film prepared at the gas flow ratio of 3/50 can be contributed with the best properties.     

Enhanced hardness in B-doped ZnO thin films on fused quartz substrates by pulsed-laser deposition

B-doped ZnO thin films have been fabricated on fused quartz substrates using boron-ZnO mosaic target by pulsed-laser deposition technique, and the mechanical properties have been studied by nanoindentation continuous stiffness measurement technique and transmission electron microscope (TEM). Nanoindentation measurement revealed that the hardness of B-doped ZnO films, 9.32 ± 0.90 to 12.10 ± 1.00 GPa, is much greater than that of undoped ZnO films and very close to that of traditional semiconductor Si. The mean transmittance (%) is larger than 81% in the visible range (380-780 nm) for all the films, and the Hall effect measurement showed that the carrier density is around 2 × 10²⁰ cm⁻³ and the resistivity lower than 3 × 10⁻³ Ω cm. TEM characteristics show undoped thin films have more amorphous area between grains while the B-doped ZnO films have thin grain boundaries. We suggest that the grain boundaries act as the strain compensation sites and the decrease in thickness of grain boundaries enhances the hardness of the B-doped ZnO films.     

Enhancement of surface mechanical properties by using TiN[BCN/BN]n/c-BN multilayer system

The aim of this work is to improve the mechanical properties of AISI 4140 steel substrates by using a TiN[BCN/BN]_n/c-BN multilayer system as a protective coating. TiN[BCN/BN]_n/c-BN multilayered coatings via reactive r.f. magnetron sputtering technique were grown, systematically varying the length period (Λ) and the number of bilayers (n) because one bilayer (n = 1) represents two different layers (t_BCN + t_BN), thus the total thickness of the coating and all other growth parameters were maintained constant. The coatings were characterized by Fourier transform infrared spectroscopy showing bands associated with h-BN bonds and c-BN stretching vibrations centered at 1400 cm⁻¹ and 1100 cm⁻¹, respectively. Coating composition and multilayer modulation were studied via secondary ion mass spectroscopy. Atomic force microscopy analysis revealed a reduction in grain size and roughness when the bilayer number (n) increased and the bilayer period decreased. Finally, enhancement of mechanical properties was determined via nanoindentation measurements. The best behavior was obtained when the bilayer period (Λ) was 80 nm (n = 25), yielding the relative highest hardness (∼30 GPa) and elastic modulus (230 GPa). The values for the hardness and elastic modulus are 1.5 and 1.7 times greater than the coating with n = 1, respectively. The enhancement effects in multilayered coatings could be attributed to different mechanisms for layer formation with nanometric thickness due to the Hall-Petch effect; because this effect, originally used to explain increased hardness with decreasing grain size in bulk polycrystalline metals, has also been used to explain hardness enhancements in multilayered coatings taking into account the thickness reduction at individual single layers that make up the multilayered system. The Hall-Petch model based on dislocation motion within layered and across layer interfaces has been successfully applied to multilayered coatings to explain this hardness enhancement.     

Laser shock wave consolidation of nanodiamond powders on aluminum 319

A novel coating approach, based on laser shock wave generation, was employed to induce compressive pressures up to 5 GPa and compact nanodiamond (ND) powders (4-8 nm) on aluminum 319 substrate. Raman scattering indicated that the coating consisted of amorphous carbon and nanocrystalline graphite with peaks at 1360 cm⁻¹ and 1600 cm⁻¹ respectively. Scanning electron microscopy revealed a wavy, non-uniform coating with an average thickness of 40 μm and absence of thermal effect on the surrounding material. The phase transition from nanodiamond to other phases of carbon is responsible for the increased coating thickness. Vicker's microhardness test showed hardness in excess of 1000 kg_f/mm² (10 GPa) while nanoindentation test indicated much lower hardness in the range of 20 MPa to 2 GPa. Optical surface profilometry traces displayed slightly uneven surfaces compared to the bare aluminum with an average surface roughness (R_a) in the range of 1.5-4 μm depending on the shock wave pressure and type of confining medium. Ball-on-disc tribometer tests showed that the coefficient of friction and wear rate were substantially lower than the smoother, bare aluminum sample. Laser shock wave process has thus aided in the generation of a strong, wear resistant, durable carbon composite coating on aluminum 319 substrate.     

Effect of interfacial diffusion on microstructure and properties of FePt/B4C multifunctional multilayer composite films

FePt/B₄C multilayer composite films were prepared by magnetron sputtering and subsequent annealing in vacuum. By changing Fe layer thickness of [Fe/Pt]₆/B₄C films, optimal magnetic property (8.8 kOe and remanence squareness is about 1.0) is got in [Fe(5.25 nm)/Pt(3.75 nm)]₆/B₄C sample whose composition is Fe rich and near stoichiometric ratio. The characterizations of microstructure demonstrate that the diffusion of B and C atoms into FePt layer depends strongly on B₄C interlayer thickness. When B₄C interlayer thickness of [Fe(2.625 nm)/Pt(3.75 nm)/Fe(2.625 nm)/B₄C]₆ films is bigger than 3 nm, stable value of grain size (6-6.5 nm), coercivity (6-7 kOe) and hardness (16-20 GPa) is observed. Finally, the multifunctional single FePt/B₄C composite film may find its way to substitute traditional three-layer structure commonly used in present data storage technology.     

Structure and mechanical properties of Al/AlN multilayer with different AlN layer thickness

Nanometer scale Al/AlN multilayers have been prepared by dc magnetron sputtering technique with a columnar target. A set of Al/AlN multilayers with the Al layer thickness of 2.9 nm and the AlN layer thickness variation from 1.13 to 6.81 nm were determined. Low angle X-ray diffraction (LAXRD) was used to analyze the layered structure of multilayers. The phase structure of the coatings was investigated with grazing angle XRD (GAXRD). Mechanical properties of these multilayers were thoroughly studied using a nanoindentation and ball-on-disk micro-tribometer. It was found that the multilayer hardness and reduced modulus showed no strong dependence on the AlN layer thickness. Al2.9 nm/AlN1.13 nm multilayer had more excellent tribological properties than single layers and other proportion multilayers with a lowest friction coefficient of 0.15. And the tribological properties of all the multilayers are superior to the AlN single layer.