Alteration of internal stresses in SiO2/Cu/TiN thin films by X-ray and synchrotron radiation due to heat treatment

A break of wiring by stress-migration becomes a problem with an integrated circuit such as LSI. The present study investigates residual stress in SiO₂/Cu/TiN film deposited on glass substrates. A TiN layer, as an undercoat, was first deposited on the substrate by arc ion plating and then Cu and SiO₂ layers were deposited by plasma coating. The crystal structure and the residual stress in the deposited multi-layer film were investigated using in-lab. X-ray equipment and a synchrotron radiation device that emits ultra-high-intensity X-rays. It was found that the SiO₂ film was amorphous and both the Cu and TiN films had a strong {1 1 1} orientation. The Cu and TiN layers in the multi thick (Cu and TiN:1.0 μm)-layer film and multi thin (0.1 μm)-layer film exhibited tensile residual stresses. Both tensile residual stresses in the multi thin-layer film are larger than the multi thick-layer film. After annealing at 400 °C, these tensile residual stresses in both the films increased with increasing the annealing temperature. Surface swelling formations, such as bubbles were observed in the multi thick-layer film. However, in the case of the multi thin-layer films, there was no change in the surface morphology following heat-treatment.     

Effect of thermal annealing on the mechanical properties of low-emissivity physical vapor deposited multilayer-coatings for architectural applications

Low-emissivity (low-E) coatings comprising a stack of multiple physical vapor deposited metallic and dielectric layers play an important role in energy management of modern buildings. The production process of such architectural glazings often requires that the coatings withstand a short-term thermal load of up to 700 °C. Here, we report on thermally-induced variations in the mechanical properties of representative large-area magnetron-sputtered low-E stacks on glass, developed specifically for high temperature stability. Coatings are investigated before and after heat treatment by bulge testing, curvature analyses using Stoney's equation, and nanoindentation. For as-deposited coatings, an in-plane residual compressive stress about 48 MPa and Young's modulus of 120 GPa are found, depending on the type of substrate. Short-term exposure to up to 700 °C converts this situation to in-plane residual tensile stress of > 400 MPa, while Young's modulus decreases to about 105 GPa. These changes in the residual stress state are explained on the basis of structural, topological and dimensional changes in the coating stack. They identified as one of the primary factors governing temperature-resistance of low-E coatings.     

Microstructure and mechanical properties of nanostructure multilayer CrN/Cr coatings on titanium alloy

Five different nanostructured, multilayer coatings (CrN/Cr)x8 with different thickness ratio of Cr and CrN layers were deposited by PAPVD (Plasma Assisted Physical Vapour Deposition) vacuum arc method on Ti6Al4V titanium alloy. The microstructure, chemical and phase composition of the CrN and Cr sub-layers were characterized by SEM with EDX and Cs-corrected dedicated STEM on cross-sections prepared by focus ion beam. Besides, hardness and Young's modulus of the (Cr/CrN)x8 coatings has been measured. The adhesion has been tested by scratch test method. The obtained (CrN/Cr) multilayer coatings, 5-6 μm in thickness, have homogeneous and nanocrystalline structure, free of pores and cracks. The microstructures of Cr and CrN layers consist of columnar grains below 100 nm in diameter. The hardness and Young's modulus of these coatings depend linearly on thickness ratio of Cr and CrN layers. The decrease of the thickness ratio Cr/CrN 0.81 to 0.15 results in the increase of hardness from 1275 HV to 1710 HV and Young's modulus from 260 GPa to 271 GPa.     

Raman spectroscopy characterization of diamond films on steel substrates with titanium carbide arc-plated interlayer

Diamond chemical vapour deposition (CVD) on steel represents a difficult task. The major problem is represented by large diffusion of carbon into steel at CVD temperatures. This leads to very low diamond nucleation and degradation of steel microstructure and properties. Recent work [R. Polini, F. Pighetti Mantini, M. Braic, M. Amar, W. Ahmed, H. Taylor, Thin Solid Films 494 (2006) 116] demonstrated that well-adherent diamond films can be grown on high-speed steels by using a TiC interlayer deposited by the PVD-arc technique. The resulting multilayer (TiC/diamond) coating had a rough surface morphology due to the presence of droplets formed at the substrate surface during the reactive evaporation of TiC. In this work, we first present an extensive Raman investigation of 2 μm, 4 μm and 6 μm thick diamond films deposited by hot filament CVD on TiC interlayers obtained by the PVD-arc technique. The stress state of the diamond was dependent on both the films thickness and the spatial position of the coating on the substrate. In fact, on the top of TiC droplets, the stress state of the diamond was much lower than that of diamond in flatter substrate areas. These results showed that diamond films deposited on rough TiC interlayers exhibited a wide distribution of stress values and that very large compressive stress exists in the diamond film grown on flat regions of steel substrates with a TiC interlayer. Diamond films could accommodate stresses as large as 10 GPa without delamination.     

Mechanical and microstructural characteristics of detonation gun sprayed NiCrAlY + 0.4 wt% CeO2 coatings on superalloys

The microstructure and mechanical properties of detonation gun sprayed NiCrAlY + CeO₂ alloy coatings deposited on superalloys were investigated. The morphologies of the coatings were characterized by using the techniques such as optical microscopy, X-ray diffraction and field emission scanning electron microscopy/energy-dispersive analysis. The coating depicts the formation of dendritic structure and the microstructural refinement in the coating was due to ceria. Average porosity on three substrates was less than 0.58% and surface roughness of the coatings was in the range of 6.17–6.94 μm. Average bond strength and microhardness of the coatings were found to be 58 MPa and 697–920 H_V, respectively.     

Experimental study on buckle evolution of thin inorganic layers on a polymer substrate

In this paper the behavior of a 250 nm and a 350 nm thick Indium tin oxide (ITO) layers deposited on a 200 μm thick high temperature aromatic polyester substrate (Arylite™) and spin coated with a 3 μm silica-acrylate hybrid coating (Hard Coat) is discussed. In-situ optical microscopy of the layered structures under uniaxial compressive strain was used to determine the buckle delamination rate at different applied strains. The effect of applied uniaxial compressive strain and layer thickness on the evolution of buckle width and height was investigated. The biaxial-residual stress, uniaxial compressive stress, poor adhesion at the interface and Poisson’s ratio are believed to be responsible for the formation of telephone-cord buckling.     

Strong amorphization of high-entropy AlBCrSiTi nitride film

Amorphous coatings, particular nitride systems, are of interest for numerous practical applications. Nevertheless, at present only a few amorphous nitride coating systems have been considered, the most notably being the (TM, Si)N system (transition metal (TM) = Ti, Zr, W, Mo). The present study provides an alternative approach for producing amorphous nitride films with high thermal stability up to 700 °C for 2 h. Films are deposited from an equimolar AlBCrSiTi target in various argon/nitrogen atmospheres at different substrate temperatures. It is found that above the nitrogen flow ratio (i.e. R_N = N₂/N₂ + Ar) of 28.6% a near equal ratio between target elements and nitrogen is approached, thus indicating the coatings have the chemical formula of (AlBCrSiTi)N. The glancing-angle X-ray diffractometer and transmission electron microscope investigations indicate that the coatings, regardless of nitrogen concentration or deposition temperature (up to 500 °C), are amorphous. Thermal treatment shows that the amorphous structure of this (AlBCrSiTi)N coating is maintained up to 700 °C when annealing for 2 h in vacuum. At annealing temperatures of 800 °C and above, the amorphous films transform into a simple NaCl-type face-centered cubic solid solution. Even after annealing at 1000 °C for 2 h, the grain size is only 2 nm. High entropy effect, large lattice distortion effect, and sluggish diffusion effect are proposed to account for the formation of amorphous nitrides.     

马氏体气阀钢多元共渗层的组织及性能

用固体粉末法,在4Cr10Si2Mo马氏体气阀钢表面制备了Al—Cr二元渗层及Al—Cr—Ce三元渗层,研究了渗层的显微组织和成分分布,测定了渗层由表及里的显微硬度。Al—Cr渗层厚度约为3501μm,硬度为580Hv;Al-Cr—Ce渗层厚度约为420μm,硬度为500Hv。     

Study on behavior of NiAl coating with different Ni/Al ratios

β-NiAl coatings with different Ni/Al ratios were deposited on K403 superalloy substrates via magnetron sputtering. The phase transformation and diffusion phenomenon of the NiAl/Ni-based superalloy system after vacuum annealing at 900 and 1000 °C were analyzed using X-Ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and energy dispersive X-ray spectrometry (EDS). The effect of coating concentrations on the outward diffusion behavior of substrate elements was discussed. The high Cr concentrations in the Al-rich NiAl coatings were caused by the intense interdiffusion between Al and Cr. The Ti, W and Mo partitioned to γ′-Ni₃Al in the coatings. Several possible reasons for the formation of γ′-Ni₃Al at the surface of Ni-rich NiAl coating were identified, including: diffusion behavior of W and Mo in β-NiAl, destabilizing effect of substrate elements on β-NiAl, and diffusion rates of Ni and Al in β-NiAl. The volume change in β ⇛ γ′ transformation process shows Ni uphill diffused to the γ′-Ni₃Al islands at the surface of Ni-rich NiAl coatings. The IDZ (interdiffusion zone) thickness and precipitates in IDZ were related to the Al initial concentrations in the coatings.     

Nature in corrosion-erosion surface for [TiN/TiAlN]n nanometric multilayers growth on AISI 1045 steel

The aim of this work is to characterize the electrochemical behavior of [TiN/TiAlN]n multilayer coatings under corrosion-erosion condition. The multilayers with bilayer numbers (n) of 2, 6, 12, and 24 and/or bilayer period (Λ) of 1500 nm, 500 nm, 250 nm, 150 nm and 125 nm were deposited by magnetron sputtering technique on Si (100) and AISI 1045 steel substrates. Both, the TiN and the TiAlN structures for multilayer coatings were evaluated via X-ray diffraction analysis. Mechanical and tribological properties were evaluated via nanoindentation measurements and scratch test respectively. Silica particles were used as abrasive material on corrosion-erosion test in 0.5 M of H₂SO₄ solution at impact angles of 30° and 90° over surface. The electrochemical characterization was carried out using polarization resistance technique (Tafel), in order to observe changes in corrosion rate as a function of the bilayer number (n) or the bilayer period (Λ) and the impact angle. Corrosion rate values of 9115 μm y for uncoated steel substrate and 2615 μm y for substrate coated with n = 24 (Λ = 125 nm) under an impact angle of 30° were found. On the other hand, for an impact angle of 90° the corrosion rate exhibited 16401 μm y for uncoated steel substrate and 5331 μm y for substrate coated with n = 24 (Λ = 125 nm). This behavior was correlated with the curves of mass loss for both coated samples and the surface damage was analyzed via scanning electron microscopy images for the two different impact angles. These results indicate that TiN/TiAlN multilayer coatings deposited on AISI 1045 steel represent a practical solution for applications in corrosive-erosive environments.     

Wear resistant coatings: Silica sol-gel reinforced with carbon nanotubes

Pin-on-disc wear experiments have been carried out on sol-gel silica coatings reinforced with 0.1 wt.% carbon nanotubes (CNTs) deposited on WE54 magnesium alloy substrates by the dip-coating technique. Sol-gel solutions were fabricated using two different procedures: mechanical mixing (MM) and ultrasonic probe mixing. Dry sliding wear tests have been carried out at load of 1 N, speed of 0.1 m/s and sliding distance of 60 m. Friction coefficients were obtained from the tests and the specific wear rates (k) were calculated. The fabrication procedure of the coating influences its morphology and wear resistance. Friction coefficient was found to vary slightly with the addition of the CNTs. The wear volume of the magnesium substrate coated decreased by 40% and 80%, in terms of k, by using unreinforced and CNT-reinforced MM coatings, respectively. In MM layers reinforced with CNT uniform dispersion of the nanotubes was reached and toughening of the ceramic coating by pull-out and crack bridging mechanisms was observed.     

Interaction of highly dissociated low pressure hydrogen plasma with W-C thin film deposits

Thin film deposits of carbon and tungsten on stainless steel substrate were prepared by RF sputtering of a tungsten target in acetylene atmosphere. At the target bias of − 1700 V and the target current of 30 mA cm^− 2, a rather uniform film containing 50 at.% of C and 50 at.% of W was deposited. The thickness of the deposited film was about 1 μm. Samples were exposed to highly dissociated hydrogen plasma created by a microwave discharge at the power of 1000 W. Some samples were heated additionally by concentrated solar radiation. After plasma treatment, the samples were characterized by X-Ray Diffraction and Auger Electron Spectroscopy. The results showed that aggressive hydrogen plasma allows for the removal of carbon from the deposits at moderated temperatures. Prolonged treatment showed formation of highly crystalline pure tungsten, and finally the tungsten film interacted with the substrate forming a thin film rich of Fe₇W₆ compound. The range of temperature and/or treatment time for the removal of carbon from the W-C film was found very narrow.     

Suppression of de-wetting of copper coatings on carbon substrates by metal (Cr, Mo, Ti) doped boron interlayers

Boron coatings doped with Cr, Ti or Mo were deposited on plane substrates of vitreous carbon (“Sigradur G”) by magnetron sputtering from a composite target. The amount of included metal was determined by Auger electron spectroscopy and found to be in the range of 1-4 at%. The metal content relative to boron was chosen to be in the range of 3 at% for all interlayers. Onto these interlayers a Cu film of 300 nm thickness was deposited by magnetron sputtering. After that the Cu coated samples were subjected to heat treatment of 800 °C for 30 min.The heat treated samples were investigated by scanning electron microscopy and time of flight secondary ion mass spectroscopy (TOF-SIMS). Different intensities of de-wetting of the Cu coatings could be observed. It was possible to quantify the de-wetting process by determining the area density of holes formed within the Cu coating after thermal treatment. Interlayers which lead to the lowest hole density will be considered as candidate materials for optimizing the thermal properties of the Cu/C interface in subsequent experiments.     

Intermetallische Oxidationsschutzschichten für Titanlegierungen

Intermetallic Oxidation-Resistant Coatings for Titanium Alloys Intermetallic Ti-Al coatings were deposited onto near-a titanium alloy TIMETAL 1100 using magnetron sputtering. Two coating systems were investigated: gradient layers with increasing A1 con- tent towards the surface of the coatings and a multilayer system consisting of three single layers ofTi₃Al, TiAl and TiAl₃. The over- all coating thickness was 4 μm and 16 μm for both systems. Isother- mal oxidation tests at 750 °C revealed good oxidation resistance and effective oxygen prevention from the substrate by the coatings. Room temperature tensile tests after long-term exposure to air 600°C proved the beneficial influence of the coatings on the ductility of the base material. The coatings are highly ductile under creep conditions thus keeping oxygen away from the substrate alloy even at high straining. In some cases creep lifetime was consider- ably prolonged. No detrimental influence of the Ti-A1 coatings on the fatigue properties of TIMETAL I100 was found for the 4pm multilayer coatings, whereas fatigue limit under repeated strain was slightly decreased for the 16μm coatings.     

Electrochemical corrosion behavior of carbon-based thin films in chloride ions containing electrolytes

Commercially available carbon-based thin films consisting of single layers of amorphous diamond-like carbon or multilayers of crystalline TiAlN or CrN with diamond-like carbon top coatings were evaluated in relation to their electrochemical corrosion behavior in chloride ions containing electrolytes. The hardened working steel (an alloy of 0.9% C, 4.1% Cr, 4.9% Mo, 1.8% V, 6.4% W) was used as a substrate material.The potentiodynamic corrosion behavior of coated samples was tested in 3.5 wt.% NaCl solution and Hank's balanced body solution, HBBS (0.89 wt.% NaCl, further chlorides, sulfates, carbonates and phosphates). The multi-layers TiAlN + a-C:H:W and CrN + a-C:H:W exhibited only a minor improvement in corrosion resistance. Single layers of amorphous diamond-like carbon coating without hydrogen (a-C) spall off during the corrosion tests in chloride containing media. A minor improvement of the corrosion resistance is possible. The a-C:H and the a-C:H:Si, which contain hydrogen, showed the best corrosion resistance with a 100 times lower corrosion current density.     

Microstructure and tribological property of nanocrystalline Co–W alloy coating produced by dual-pulse electrodeposition

The nanocrystalline Co–W alloy coatings were produced by dual-pulse electrodeposition from aqueous bath with cobalt sulfate and sodium tungstate (Na₂WO₄). Influence of the current density and Na₂WO₄ concentration in bath on the microstructure, morphology and hardness of the Co–W alloy coatings were investigated using an X-ray diffraction, a scanning electronic microscope and a Vickers hardness tester, respectively. In addition, the friction and wear properties of the Co–W alloy coating electrodeposited under different condition were evaluated with a ball-on-disk UMT-3MT tribometer. The correlation between the electrodeposition condition, the microstructure and alloy composition, and the hardness and tribological properties of the deposited Co–W alloy coatings were discussed in detail. The results showed that the microhardness of the deposited Co–W alloy coating was significantly affected by its average grain size, W content and crystal orientation. Smaller grain size, higher W content and strong hcp (1 0 0) orientation favor the improvement of the hardness for Co–W alloy coatings. The deposited Co–W alloy coating could obtain the maximum microhardness over 1000 kgf mm⁻² by careful control of the electrodeposition conditions. The tribological properties of the electrodeposited Co–W alloy coating were greatly affected by its grain size, microhardness, surface morphologies and composition, and could be significantly improved by optimizing the electrodeposition condition.     

真空等离子喷涂碳化硼涂层制备与抗激光辐照性能研究

采用真空等离子喷涂技术,在不锈钢基体上制备碳化硼(B₄C)涂层,并对涂层的组成、结构、沉积效率、结合强度以及抗激光辐照性能进行了表征.结果显示,真空等离子喷涂B₄C涂层中没有出现明显的B₂O₃相,表明真空等离子喷涂可有效避免B₄C氧化现象.采用较细的粉末制备的B₄C涂层较为致密.较高的喷涂功率和较大的氢气流量,有助于改善粉末的熔化程度,从而提高涂层的沉积效率和结合强度.在适宜的工艺参数下,涂层的沉积效率与结合强度可分别达72%与49MPa.激光辐照试验表明,在不锈钢表面沉积B₄C涂层,可以明显改善其抗激光辐照性能.     

钼基体上真空等离子体喷涂钨涂层的研究

采用真空等离子体喷涂(VPS)技术制备出厚度超过0.8 mm的金属钨涂层,并对涂层进行了高温热处理.结果显示:金属钨涂层主要呈层状结构,其密度可达到理论密度的98%以上;工艺参数对喷涂涂层性能有较大影响,特别是对涂层密度、结合强度有影响;高温热处理引起界面结构变化,形成钨钼混合层,且再结晶形成细小的晶粒;和CVD方法以及常压等离子体喷涂方法制备的钨涂层相比,低压等离子体喷涂具有明显的优势.     

Synthesis and characterization of W reinforced carbon coatings produced by Combined Magnetron Sputtering and Ion Implantation technique

W-containing carbon coatings were deposited on plain carbon steel and titanium substrates by Combined Magnetron Sputtering and Ion Implantation (CMSII) technique. A target made of fine grain graphite with cylindrical tungsten pins mounted in the area of maximum sputtering rate was used. High voltage pulses (− 30 kV, 20 μs, and 25 Hz) were superposed over the DC bias. By adjusting the processing parameters nanocomposite nc-WC_1 − x/a-C coatings with a W content from 20 to 45 at.%, with a hardness of 12-22 GPa and a friction coefficient in the range of 0.12-0.22 were produced. These coatings have a thickness of 10-13 μm, good wear resistance and a good thermal stability up to 673 K.     

Microstructure and corrosion characteristics of CrN/NiP sputtering thin films

The CrN top layer and NiP interlayer were sequentially deposited to form a CrN/NiP composite coating through sputtering technique. The CrN/NiP coating systems deposited at 350 °C, 450 °C, and 550 °C, showed amorphous/nanocrystalline, nanocrystallize with precipitations, and fully crystallized microstructure respectively for the NiP interlayers. With the introduction of NiP interlayer, the coating assemblies exhibited superior corrosion characteristics than single CrN coatings. The amorphous NiP interlayer deposited at 350 °C revealed a lower corrosion current as compared to those with crystallized NiP layers owing to their structural defects in the alloy layer. With the combination of CrN and NiP layers the corrosion attach was retarded and a better corrosion resistance was found for the CrN/NiP composite coating.