The adhesion of copper films deposited onto aluminum nitride

Good adhesion between copper film and AlN substrate is obtained when the surface of AlN is laser-irradiated prior to copper film deposition and post deposition annealing is conducted. Surface chemistry of AlN substrates before and after laser irradiation and the interfacial reactions of copper film/AlN couples were studied with Auger Electron Spectroscopy (AES) to understand the adhesion mechanisms. The surface of as-received AlN substrates was covered with a thin sheath of Al₂O₃. Laser irradiation removed the surface Al₂O₃ layers, smoothened the surface, and decomposed AlN leaving metallic aluminum on the surface. The interfacial reactions in the copper film/AlN couple are affected by the amounts of oxygen and metallic aluminum available at the interface. The adhesion mechanism is the formation of a Cu-O-Al compound at the interface of copper film/AlN couple. Since copper does not react with AlN, laser induced decomposition of AlN seems to be the driving force for the formation of the compound. This revised version was published online in September 2006 with corrections to the Cover Date.     

Preparation and properties of SiO2 matrix composites doped with AlN particles

SiO₂ matrix composites doped with AlN particles were prepared by hot-pressing process. Mechanical properties of SiO₂ matrix composites can be greatly improved by doping with AlN particles. Flexural strength and fracture toughness of 30 vol%AlN-SiO₂ composite sintered at 1400°C reached 200 MPa and 2.96 MPa·m^1/2. XRD analysis indicated that, up to 1400°C, no chemical reaction occurred between SiO₂ matrix and AlN particles suggesting an excellent chemical compatibility of SiO₂ matrix with AlN particles. The influences of hot-pressing temperature and the content of AlN particles on dielectric properties of SiO₂-AlN composites were studied. The temperature and frequency dependency of dielectric properties of SiO₂-AlN composites were also studied. Residual flexural strength of SiO₂-AlN composites decreased with increasing temperature difference. The critical temperature difference was estimated about 600°C.     

Microstructure and properties of spark plasma sintered AlN ceramics

Spark plasma sintering (SPS) is a newly developed technique that enables poorly sinterable aluminum nitride (AlN) powder to be fully densified. It is addressed that pure AlN sintered by SPS has relatively low thermal conductivity. In this work, SPS of AlN ceramic was carried out with Y₂O₃, Sm₂O₃ and Li₂O as sintering aids. Effects of additives on AlN densification, microstructure and properties were investigated. Addition of sintering aids accelerated the densification, lowered AlN sintering temperature and was advantageous to improve properties of AlN ceramic. Thermal conductivity and strength were found to be greatly improved with the present of Sm₂O₃ as sintering additive, with a thermal conductivity value about 131 Wm⁻¹K⁻¹ and bending strength about 330 MPa for the 2 wt% Sm₂O₃-doped AlN sample SPS at 1,780 °C for 5 min. XRD measurement revealed that additives had no obvious effect on the AlN lattice parameters. Observation by SEM showed that AlN ceramics prepared by SPS method manifested quite homogeneous microstructure. However, AlN grain sizes and shapes, location of secondary phases varied with the additives. The thermal conductivity of AlN ceramics was mainly affected by the additives through their effects on the growth of AlN grain and the location of liquid phases.     

Hot-pressed AlN-Cu metal matrix composites and their thermal properties

AlN-Cu metal matrix composites containing AlN volume fractions between 0.1 and 0.5 were fabricated firstly by liquid phase sintering of AlN using Y₂O₃ as a sintering aid and then by hot pressing the powder mixtures of sintered AlN and Cu at 1050°C with a pressure of 40 MPa under flowing nitrogen. With Y₂O₃ additions of 1.5 to 10 wt%, the densification of AlN could be achieved by liquid phase sintering at 1900°C for 3 h and subsequently slow cooling. The sintered AlN showed a maximum thermal conductivity of 166 W/m/K at a Y₂O₃ level of 6 wt%. Dense AlN-Cu composites with AlN contents up to 40 vol% were achieved by hot pressing. The thermal conductivity and the coefficient of the thermal expansion (CTE) of the composites decreased with increasing AlN volume fractions, giving typical values of 235 W/m/K and 12.6 × 10^–6/K at an AlN content of 40 vol%.     

Erosion mechanisms of aluminium nitride ceramics at different impact angles

In this paper, erosion wear behaviour of aluminium nitride (AlN) ceramics is studied. The influence of particle hardness and shape on erosion of the AlN surface is examined. The effect of varying the impingement angle on the weight loss and the roughness parameters of AlN ceramics testing sample is also determined. Therefore, erosive wear behaviour of AlN ceramics was investigated using SiC and SiO₂ particles as erodents, at following impact angles: 30°, 45°, 60°, 75° and 90°. Scanning electron microscopy (SEM) was used to analyze the eroded surfaces in order to determine erosion mechanisms. The roughness parameters (R_a, R_z and R_max), before and after erosion with SiO₂ and SiC particles at 30° and 90° angles of impingement, respectively, were determined using a profilometer. It was found that the impact angle is influencing the erosion wear of the AlN ceramics and maximum erosion takes place at impact angle of 90°. The results indicate that hard, angular SiC particles cause more damage than softer, more rounded SiO₂ particles.     

Preparation of AlN-Cu composite powders by electroless plating of controlled oxidized nitride particles to prevent degradation by hydrolysis

The present work describes the preparation of AlN-Cu composite powders by electroless plating. Initially, the hydrolysis reaction of the ceramic particles in the electroless solution was studied as a reference element for the design of a protective surface barrier that enabled the coating process, with no ceramic phase degradation. The metal source of the electrolytic bath was copper sulfate, with formaldehyde as the reducing agent, under alkaline conditions of pH 12. The microstructural characterization indicated the formation and growth of aluminum hydroxides from AlN particles, inhibiting the coating of Cu by increasing the OH⁻ ions in the solution. As the exposure time increased, the ellipsoidal bayerite grew from AlN and transformed into prismatic particles of the thermodynamically more stable gibbsite phase. To prevent the degradation of AlN, a controlled oxidation stage was implemented to form a protective barrier of non-reactive alumina on the surface through thermal treatment in oxidizing atmospheres. An atmosphere of dry air was found to be more appropriate than pure oxygen for the formation of a continuous and dense layer of crack-free alumina on nitride surfaces, and a temperature of 1000 °C for 1 h enabled the formation of 3.9 by weight of α-Al₂O₃, capable of reducing the hydrolysis reaction of AlN. The process of autocatalytic deposition on the passivated particles, applied in three consecutive steps of metallization, led to AlN-Cu composite powders with 29 wt% Cu. Finally, the coated powders were treated in a hydrogen-reducing atmosphere at 400 °C to remove traces of the Al(OH)₃ phase encountered, as well as to improve the adhesion of the nanostructured deposit of the cauliflower-like structure to the AlN surfaces, obtaining AlN-Cu composite powders suitable for the preparation of metal/ceramic composites.     

Titanium diboride particle-reinforced aluminium with high wear resistance

A TiB₂ particle (61 vol%, 4 m mean size) reinforced aluminium fabricated by liquid-aluminium infiltration was subjected to unlubricated rolling wear and was found from the weight loss to be 1.5 times more wear resistant than 17-4 ph stainless steel, twice as wear resistant as 1020 steel, 7.5 times more wear resistant than 2024 aluminium, and 12.8 times more wear resistant than the aluminium matrix. This wear resistance is attributed to the lack of particle pull-out and the ability of the TiB₂ particles to protect the softer underlying matrix from abrasion. This composite was approximately three times more wear resistant than AlN particle (50 vol%)-reinforced aluminium. The greater wear resistance of Al/TiB₂ compared to Al/AlN is due to the slow wear of the TiB₂ particles and the AlN particle pull-out. A slight decline in tensile strength and no effect on the modulus was observed in Al/TiB₂ after heating at 300 or 600°C for 240 h. This high-temperature stability is attributed to the lack of reactivity between TiB₂ and the aluminium matrix.     

The effect of carbon coating of AIN powder on sintering behavior and thermal conductivity

High thermal conductive AlN ceramics doped with Y₂O₃ were produced by sintering the powders obtained after applying a carbon coating to the surface of AlN powder grains. During sintering at 1800°C for 1 hour, the carbon reacts with the surface of the AlN grains by carbothermal-reduction of Al₂O₃, and also with the Al₂Y₄O₉ intermediate phase to form AlN, Y₂O₃ and CO. By adding 0.56 mass% of carbon, almost all the Al₂Y₄O₉ is reacted and the thermal conductivity increases from 184 W/(m · K) to 224 W/(m · K). Further carbon addition decreases the thermal conductivity and also the final sintered density.     

Superior high-temperature resistance of aluminium nitride particle-reinforced aluminium compared to silicon carbide or alumina particle-reinforced aluminium

Aluminium-matrix composites containing AlN, SiC or Al₂O₃ particles were fabricated by vacuum infiltration of liquid aluminium into a porous particulate preform under an argon pressure of up to 41 MPa. Al/AlN had similar tensile strengths and higher ductility compared to Al/SiC of similar reinforcement volume fractions at room temperature, but exhibited higher tensile strength arid higher ductility at 300–400 °C and at room temperature after heating at 600 °C for 10–20 days. The ductility of Al/AIN increased with increasing temperature from 22–400 °C, while that of Al/SiC did not change with temperature. At 400 °C, Al/AlN exhibited mainly ductile fracture, whereas Al/SiC exhibited brittle fracture due to particle decohesion. Moreover, Al/AlN exhibited greater resistance to compressive deformation at 525 °C than Al/SiC. The superior high-temperature resistance of Al/AlN is attributed to the lack of a reaction between aluminium and AlN, in contrast to the reaction between aluminium and SiC in Al/SiC. By using Al-20Si-5Mg rather than aluminium as the matrix, the reaction between aluminium and SiC was arrested, resulting in no change in the tensile properties after heating at 500 °C for 20 days. However, the use of Al-20Si-5Mg instead of aluminium as the matrix caused the strength and ductility to decrease by 30% and 70%, respectively, due to the brittleness of Al-20Si-5Mg. Therefore, the use of AIN instead of SiC as the reinforcement is a better way to avoid the filler-matrix reaction. Al/Al₂O₃ had lower room-temperature tensile strength and ductility compared to both Al/AlN and Al/SiC of similar reinforcement volume fractions, both before and after heating at 600 °C for 10–20 days. Al/Al₂O₃ exhibited brittle fracture even at room temperature, due to incomplete infiltration resulting from Al₂O₃ particle clustering.     

Reactive metallic layers produced on AlN, Si3N4 and SiC ceramics

The paper presents the results of studies on the joining of non-oxide ceramics with copper with the use of intermediary metallic layers. AlN ceramics was covered with Mo, Mn, FeSi, Ti intermediary layers, Si₃N₄ ceramics – with Cu, Mn, Ti layers, and SiC ceramics – with Cr, TiCu layers. Although the individual metallic layers were synthesized under different conditions, all the structures contained barrier layers formed during the synthesis process. With the AlN and Si₃N₄ ceramics, the barrier layer was composed of TiN, which was well wetted by the metallic and oxide phases. With the SiC ceramics, the role of the barrier layer was played by the Ti₃SiC₂ phase. The thickness of the barrier layers of both types (TiN, Ti₃SiC) was about 1 m. They were well wetted by the metallic solders, coherent with the ceramic surface, and, within the brazed multi-layer joints, they constituted a continuous microstructure.     

The preparation and properties of Y2O3/AlN anti-reflection films on chemical vapor deposition diamond

Yttrium oxide (Y₂O₃) films have successfully been applied as anti-reflection (AR) and anti-oxidation films for diamond. For significant adhesion improvement between Y₂O₃ coating and diamond, aluminum nitride (AlN) as an interlayer is introduced. Y₂O₃ and AlN films were prepared by RF magnetron sputtering of Y₂O₃ ceramic target in Ar atmosphere and pure Al metal target in Ar + N₂ atmosphere, respectively. The Y₂O₃ and AlN films were studied by X-ray diffraction, X-ray photoelectron spectroscopy, Atomic force microscopy and Spectroscopic ellipsometry. Adherent Y₂O₃/AlN films on high optical quality chemical vapor deposition diamond with optimum thicknesses for infrared transmission enhancement in 8-10 μm were obtained by a Fourier transform infrared spectrometer. More than 28% increase in maximum transmission was observed for Y₂O₃/AlN//Diamond//AlN/Y₂O₃. Comparing between the designed and experimental AR effects for Y₂O₃/AlN film in 8-10 μm wavebands, experimental average AR effects are smaller for the absorption and scattering loss. AR effects for the Y₂O₃/AlN films on CVD diamond are proved to be excellent.     

Adhesion Properties of Milled CuO-CeO2/γ-Al2O3 on Metallic Substrate for Automotive Catalytic Converter

Adhesion properties of CuO-CeO₂/γ-Al₂O₃ layers on FeCrAl metallic substrate was investigated, where the hybrid preparation method between suspension and sol-gel is further combined with the mechanical milling process of the slurry. Poor coating adhesion was observed when the slurry is vigorously stirred, where the milled powders are agglomerated, and the stirring process hardly reduces the particle size. The combined method was found to significantly improve the adhesion property between the milled CuO-CeO₂ catalytic layer and the γ-Al₂O₃ washcoat, compared with the vigorous stirring of the slurry. The so-called “over-milling” phenomenon was also exhibited, where the elongated large particles are observed after sintering of the longer-milled powders, leading to the lowered adhesion quality.     

Thermally conducting aluminum nitride polymer-matrix composites

Thermally conducting, but electrically insulating, polymer-matrix composites that exhibit low values of the dielectric constant and the coefficient of thermal expansion (CTE) are needed for electronic packaging. For developing such composites, this work used aluminum nitride whiskers (and/or particles) and/or silicon carbide whiskers as fillers(s) and polyvinylidene fluoride (PVDF) or epoxy as matrix. The highest thermal conductivity of 11.5 W/(m K) was attained by using PVDF, AlN whiskers and AlN particles (7 μm), such that the total filler volume fraction was 60% and the AlN whisker–particle ratio was 1:25.7. When AlN particles were used as the sole filler, the thermal conductivity was highest for the largest AlN particle size (115 μm), but the porosity increased with increasing AlN particle size. The thermal conductivity of AlN particle epoxy-matrix composite was increased by up to 97% by silane surface treatment of the particles prior to composite fabrication. The increase in thermal conductivity is due to decrease in the filler–matrix thermal contact resistance through the improvement of the interface between matrix and particles. At 60 vol.% silane-treated AlN particles only, the thermal conductivity of epoxy-matrix composite reached 11.0 W/(m K). The dielectric constant was quite high (up to 10 at 2 MHz) for the PVDF composites. The change of the filler from AlN to SiC greatly increased the dielectric constant. Combined use of whiskers and particles in an appropriate ratio gave composites with higher thermal conductivity and low CTE than the use of whiskers alone or particles alone. However, AlN addition caused the tensile strength, modulus and ductility to decrease from the values of the neat polymer, and caused degradation after water immersion.     

Structure and strength of AlN/V bonding interfaces

AlN ceramics are bonded using vanadium metal foils at high temperatures in vacuum. Different bonding temperatures were used in the range 1373–1773 K with bonding times of 0.3–21.6 ks. The AlN/V interfaces of the bonded joints were investigated using SEM, electron probe microanalysis and X-ray diffraction. A bonding temperature of 1573 K was found to be suitable to activate both parts to initiate a phase reaction at the interface, because a thin V(Al) solid solution layer formed adjacent to the ceramic at 1573 K just after 0.9 ks, and a small flake-shaped V₂N reaction product formed inside the vanadium central layer. The formation of V(Al) and V₂N controls the interfacial joining of the AlN/V system at 1573 K up to 5.4 ks bonding time. The pure vanadium layer quickly changed to vanadium-containing V₂N. The diffusion path could be predicted for the AlN/V joints up to 0.9 ks at 1573 K following the sequence AlN/V(Al)/V₂N/V, while after 0.9 ks, the interface structure changed to AlN/V(Al)/V₂N + V by the growth Of V₂N into the vanadium. The AlN/V joints shovyed no ternary compounds at the interface. A maximum bond strength could be obtained for a joint bonded at 1573 K after 5.4 ks having a structure of AlN/V(Al)/V₂N + V. At 7.2 ks, nitrogen, resulting from AlN decomposition, escaped and the remaining aluminium reacted with V(Al) to form V₅Al₈ intermetallic, which is attributable to the decrease in bond strength.     

Synthesis of spherical Al2O3 and AlN powder from C@Al2O3 composite powder

A novel approach has been taken to produce (1) spherical Al₂O₃ particles by decarbonisation and (2) spherical AlN particles by nitridation and subsequent decarbonisation of C@Al₂O₃ composite particles. C@Al₂O₃ composite particles have been prepared by heterogeneous nucleation and crystallisation of Al(NO₃)₃ on surfactant encapsulated carbon nano particles followed by evaporative decomposition of the nitrate. Overpressure (0.4 MPa) of nitrogen and a temperature range (1723–1873 K) have been used for nitridation. Whiskers as well as spherical particles of AlN have been observed in the final product. The final product has been characterised by X-Ray Diffraction, Scanning Electron Microscope and Carbon–Hydrogen–Nitrogen content analysis by Elemental Analyser and the mechanism of the nitridation reaction has been analysed. The average size of the spherical AlN particles consisting of crystallites in nano-dimensions (30–50 nm) could be varied from 100 nm to 8 μm by changing the composition of the sol.     

Microstructural characteristics and evolution of Ti2AlN/TiAl composites with a network reinforcement architecture during reaction hot pressing process

The microstructural evolution of TiAl matrix composites with a novel network distribution of Ti₂AlN particle reinforcement was studied. The composites were synthesized by reaction hot pressing method using pure Al and nitrided Ti powders as initial materials. Pure Ti powders nitrided at 600 °C for a certain time in an atmosphere of flowing nitrogen turned into new compound Ti(N) powders, which have a shell of titanium nitrides (such as TiN, Ti₂N and TiN_0.3) and a core of Ti–N solid solution. Within the composites synthesized, Ti₂AlN particles, produced by in situ reaction, exhibit a network distribution. The special shell/core structure of the compound Ti(N) powders contributes to this architecture. Nitriding time of the Ti powders greatly affects the microstructure of the composites. Increasing the nitriding time is beneficial to the distribution of Ti₂AlN particles in a continuous network form. However, too long nitriding time can result in the aggregation of Ti₂AlN particles and thus destroy the uniformity of the network structure. The in-situ synthesized Ti₂AlN/TiAl composites with uniform network structure have a superior mechanical property, and their compressive strengths at 800 °C and 1000 °C are 1112 MPa and 687 MPa, respectively.     

Hardness,wear resistance and bonding strength of nano structured functionally graded Ni-Al2O3 composite coatings fabricated by ball milling method

Using initial powder mixtures with different Ni:Al₂O₃ weight ratios ranging from 1:1 to 16:1, nano structured Ni-Al₂O₃ composite coatings were deposited onto an aluminum plate by means of a planetary ball mill. It was shown that initial charges with Ni:Al₂O₃ weight ratios of 4:1 and greater, yielded well-compact coatings. Coating deposited from the powder charge with Ni:Al₂O₃ weight ratio of 4:1, contained 20?vol% of alumina particles in the Ni matrix and submitted the highest hardness value (657?±?28?Hv) and wear resistance. Nevertheless, composite coating containing smallest amount of alumina particles showed the highest cohesive strength of 9.8?±?0.3?MPa. In the next step, nano structured functionally graded composite coatings were produced by the deposition of two separate layers containing different amounts of alumina particles. Although the graded coating showed superior hardness and wear resistance compared with the non-graded coatings, it suffers from low cohesive strength attributed to the presence of alumina particles at the interface region between the two layers. To overcome the poor adhesion between two layers, a thin intermediate plain Ni one was deposited between two layers leading to 80% and 30% improvement in the adhesion strength and wear resistance, respectively.     

Mechanical strength of ultra-fine Al-AlN composites produced by a combined method of plasma-alloy reaction,spray deposition and hot pressing

Ultra-fine Al-AlN composites with high packing density were produced by the simple sequential process consisting of nitrogen plasma-alloy reaction, spray deposition and hot-pressing. The AlN content,V _f, was controlled in the range below about 40 vol % by changing the nitrogen partial pressure in the plasma-alloy reaction. The density of the Al-AlN composite withV _f=36% after hot-pressing for 7.2 ks at 673 K was 2.96 Mg m^–3 which is nearly the same as the theoretical density. The constituent phases were f c c aluminium and hexagonal AlN and their lattice parameters are nearly the same as those of pure aluminium and AlN phases. The grain size and interparticle spacing of the AlN particles were as small as about 90 and 50 nm, respectively. The Vickers hardness number, Young's modulus and compressive strength of the dense Al-AlN composite were 193, 112 GPa and 628 MPa, and the high hardness above 100 was maintained in the temperature range below 673 K. It was therefore concluded that the sequential process is a useful technique to produce ultra-fine metal-ceramic composites with high mechanical strengths.     

Mechanism of in situ formation of AlN in Al melt using nitrogen gas

In situ processing of AlN particle reinforced aluminum composites was investigated using a gas bubbling method with nitrogen gas as the gaseous precursor and pure aluminum as the starting matrix in the temperature range of 1173–1573 K. The products were characterized using XRD, SEM, and EDS techniques. Experimental results showed that it is feasible to synthesize AlN particle reinforced Al composites in situ using purified nitrogen gas. Significant AlN was synthesized by bubbling deoxidized N₂ through Al melt. The AlN particles synthesized in situ were small in size (<10 m) and were enriched in the top part of the product formed in the crucible. Directly bubbling commercial purity nitrogen gas did not lead to formation of significant AlN due to the deleterious effect of the trace oxygen impurities in the bubbling gas. The deleterious effect of trace oxygen impurities on the mechanism of formation of AlN in the Al-N system was critically analyzed from both thermodynamic and kinetic points of view. Chemisorption of O₂ molecules at the gas bubble-Al melt interface is more favorable and much faster than that of N₂, thereby inhibiting chemisorption of N₂ molecules. Significant AlN can be formed only at the content of oxygen below a critical value in the N₂ bubbling gas.     

Low temperature co-fired AlN multilayer substrates

A process for low temperature co-fired AlN multilayer substrates is introduced. Some key factors about this technology are delineated and discussed. A two-step burnout process may solve the contradiction between tungsten oxidation and carbon removal. Sintering with additives appears to improve densification at low temperature. DyN was found as a second phase in AlN ceramics, which suggests that Dy₂O₃ efficiently removes oxygen from the AlN lattice. The microstructure of AlN ceramics is ideal for achieving high thermal conductivity. Analysis of the AlN-W interface showed there were no second phases, but there was probably an intricate interlocking structure between the grains of tungsten and AlN. Co-firing at 1650°C for 4 h produced an AlN multilayer substrate with a thermal conductivity of up to 130 W m⁻¹ K⁻¹. This revised version was published online in July 2006 with corrections to the Cover Date.