Oxidation behavior of AlN substrate at low temperature

The oxidation onset and the kinetics of polycrystalline AlN substrates were studied by measuring the weight percent of oxygen in the surface layer and the surface roughness with energy dispersive X-ray spectroscopy (EDX) and atomic force microscopy (AFM), respectively. The oxidation started in the temperature range 800–900 °C and the entire surface of the AlN substrate was covered with an Al₂O₃ oxide layer below 1100 °C. The oxidation kinetics followed a linear rate law below 1000 °C and a parabolic rate law above 1100 °C. Above 1100 °C, the surface roughness increased abruptly by the irregular shape of overgrown oxide, which might enhance the adhesion of metal to the AlN surface in a metallization process. With an increase of the oxidation temperature above 1200 °C, the oxide layer split during cooling due to the thermal expansion mismatch between the AlN matrix and the Al₂O₃ oxide layer.     

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.     

Si对SiC－Al系统浸润行为的影响

用液滴技术（Ｔｈｅ　Ｓｅｓｓｉｌｅ　Ｄｒｏｐ　Ｔｅｃｈｎｉｑｕｅ）、ＳＥＭ、ＥＤＳ等研究了Ｓｉ对ＳｉＣ－Ａｌ系统浸润行为的影响，结果表明，在较低温度下，Ｓｉ在熔融Ａｌ合金中的含量不明显影响Ａｌ对ＳｉＣ的浸润行为，然而，在高温下ＳｉＣ和Ａｌ的接触角θ值随时间而减小的速率随Ｓｉ含量的增加而增大；ＳｉＣ－Ａｌ系统从非浸润到浸润的转变温度随Ｓｉ含量的增加而降低；Ｓｉ的添加引起Ａｌ合金在ＳｉＣ表面扩展和向ＳｉＣ基体渗透，而且扩展和渗透的程度随Ｓｉ含量增加而增大。说明在Ａｌ合金中添加Ｓｉ可促进对ＳｉＣ的浸润。本研究还证实了基体参加反应可增强金属Ａｌ对ＳｉＣ陶瓷的浸润能力。     

Flux-assisted spreading of an Al–7 wt%Si alloy on TiC

The effect of a K–Al–F-based flux was investigated on the wettability of TiC by an Al–7 wt%Si alloy in the interval of temperatures between 660 and 900 °C in Ar and in atmospheric air. Null spreading was observed without flux whereas perfect wetting was enabled by the flux in both atmospheres. The liquid flux, which provides a locally protective atmosphere by spreading on the surfaces of the substrate and eventually on the Al alloy, dissolves the aluminium oxide covering the molten alloy enabling thus direct contact between the liquid alloy and the TiC substrate. The low tensions for the solid/flux and liquid metal/flux interfaces facilitate spontaneous spreading and instantaneous wetting. Meanwhile, the flux is displaced to the lateral periphery of the substrate and to the surface of the liquid. Under the resolution of the scanning electron microscope, microstructural examination of the interfaces did not reveal reaction products. Rapid infiltration of the alloy into TiC/flux compacts, at low temperatures, correlated well with the flux-assisted spreading kinetics observed.     

Wetting and evaporation behaviors of molten Mg–Al alloy drops on partially oxidized α-SiC substrates

The wetting and evaporation behaviors of Mg–Al alloys over a full composition range on partially oxidized polycrystalline α-SiC substrates were studied in a flowing Ar atmosphere using an improved sessile drop method. The time dependence of the changes in contact angle and drop geometry was monitored and representative wetting stages were identified. The initial contact angles at 1173 K were 100° for pure Al and 76° for pure Mg, with the maximum value of 106° for the 7.6 mol.% Mg–Al alloy. The interfacial reaction and the evaporation of Mg led to the decrease in the apparent contact angle in the spreading stage and their respective contribution was evaluated. After the pinning of the triple line, the decrease in the contact angle resulted from the diminishing drop volume as a consequence of the Mg evaporation. The effects of Mg concentration on the wetting and evaporation behaviors were discussed. A mechanism for the time-dependent diminishing drop volume was proposed in light of the competition between the Mg evaporation and its diffusion from the drop bulk to the surface. Finally, the interfacial reaction was analyzed based on thermodynamic considerations.     

Characteristics of aerosol-synthesized AlN particles

Particulate characteristics were investigated for AlN synthesized by a thermochemical reaction of aluminium aerosol with ammonia gas. The product powders had a decreasing specific surface area between 15.7 and 36.7 m²g^–1, with increasing reaction temperature from 1100–1500 °C, and the powders with large surface area were strongly hygroscopic. Although the powders were severely aggregated and had a small amount of unreacted aluminium, light milling and post heat treatment made them ultrafine and completely converted. When sintered with 0.5% yttrium at 1900 °C, full densification and high thermal conductivity of about 130 Wm^–1 K^–1 were obtained.     

Vertically aligned one-dimensional AlN nanostructures on conductive substrates: Synthesis and field emission

Herein we report the synthesis of vertically aligned AlN nanostructures on conductive substrates through the chemical reaction between AlCl₃ and NH₃ in the temperature range of 650-850 °C. The morphologies of the AlN nanostructures could be controllably modulated from cone-like to rod-like geometries by increasing the reaction temperature. The formation mechanism of the AlN nanostructures on the nitrified Ti substrates has been discussed based on the analysis of the intermediate products. The field emission (FE) property of AlN nanocones grown on the nitrified Ti substrate is better than that for AlN nanocones on Si substrate. The improvement of FE property can be attributed to the lower resistance between AlN nanocones and the nitrified Ti substrate because the conductive titanium nitride film can directly contact with AlN emitters while a high-resistive silica layer would easily form between Si substrate and AlN nanocones. These results indicate that the deposition of nanoscale filed emitters on conductive substrates is an effective way to improve the FE behavior, and may find potential applications in FE devices.     

The effect of silicon on the wettability and interfacial reaction in AlN/Cu alloy systems

Wetting behavior of AlN by Cu alloys has been studied in vacuum through sessile drop technique. The contact angle was determined by high temperature photography and shape analysis software. Pure copper does not wet AlN. The contact angle of the AlN/Cu system at 1200 °C is 138°. Adding 20 at% Si leads to the decrease of the contact angle from 138° to 96°, and a reaction layer forms in the interfacial area. The addition of Si can also improve the wettability of AlN/Cu10Ti (the atomic ratio of Cu:Ti is 90:10) system. The contact angle of the system decreases to the values less than 20° at 1200 °C by adding 20 at% or 27 at% Si. During the wetting experiment, Ti diffuses to and reacts with AlN, leading to the formation of TiN. Addition of Si can retard the reaction between Ti and AlN by forming a Si-rich layer, mainly composed of Ti-Si compound, between the reaction layer, mainly composed of TiN, and the CuSiTi alloy. The Si-rich layer also contributes to the improvement of the wettability of the system. In the meantime, the addition of Si contributes to the decrease of the stress in the interfacial area and to the bonding at the interfaces.     

Thermal stability of N-polar n-type Ohmic contact for GaN-based light emitting diode on Si substrate

Thermal stability of N-polar n-type Ohmic contact for GaN light emitting diode (LED) on Si substrate was investigated. Al/Ti/Au were deposited as the contacts on the N-polar n-type GaN with and without AlN buffer layer on the surface, respectively, and both contacts exhibited Ohmic behaviors. The samples with AlN showed excellent Ohmic contact thermal stability when annealed below 700 °C, while the samples without AlN experienced serious degradation on electrical properties after being annealed in the temperature range of 250-600 °C. After the process of aging at 30 mA (155 A/cm²) and room temperature for 1000 h, operating voltage increase less than 0.05 V for LEDs with AlN but more than 0.45 V for LEDs without AlN. Therefore, we conclude that the existence of AlN buffer layer is a key of forming high stable Ohmic contact for GaN-based vertical structure LED on Si substrate.     

Influence of incidence angle and distance on the structure of aluminium nitride films prepared by reactive magnetron sputtering

Aluminum nitride (AlN) films were reactively deposited on (100) oriented silicon substrates by reactive radio frequency (RF) magnetron sputtering for different incidence angles and distances between substrate and target.X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to consider the influence of process parameters such as reactive gas flow rate, grazing incidence angle (α), and distance (d) between substrate and target surface on the property of AlN films. XRD results showed that AlN film prepared at a constant distance (d) of 3 cm and an incidence angle of 45° revealed a mixture of AlN (002), (100), and (101) planes, while the film prepared at α = 0° revealed a strong AlN (002) orientation which has a perpendicular growth direction to the substrate surface. AFM results showed that AlN film prepared at α = 0° exhibited more flat surface morphology than that of film prepared at α = 45°.     

Synthesis of boride and nitride ceramics in molten aluminium by reactive infiltration

The infiltration of solid powder mixtures with molten aluminium has been investigated as a potential route for the synthesis of ceramic/metal composites. Either titanium or tantalum powder was mixed with boron nitride flakes for the reaction powder mixture. The infiltration occurred spontaneously at 1473K for both [Ti+BN] and [Ta+BN] powder mixtures. Owing to reactions between the starting materials, both boride and nitride ceramics were produced in molten aluminium. TiB2 and AlN were produced from the [Ti+BN] powder mixture, and TaB2 and AlN were produced from the [Ta+BN] powder mixture. When the [Ti+BN] powder mixture was used, a reaction producing Al3Ti took place immediately after the infiltration of the molten aluminium, and a subsequent reaction producing TiB2 and AlN proceeded gradually. The time required to convert BN flakes to TiB2 and AlN particles at 1473K was in the range of 1800–3600 s. On the other hand, when the [Ta+BN] powder mixture was used, there was an initial incubation period to allow the tantalum and molten aluminium to react with each other. The reaction between tantalum, BN and aluminium took place after this incubation period. This revised version was published online in November 2006 with corrections to the Cover Date.     

The wetting of carbon by aluminium and aluminium alloys

The contact angle made by molten aluminium with vitreous carbon was measured by the sessile drop method in vacuum at temperatures up to 1100° C. The effect on wetting behaviour of the oxide layer on the molten metal was highlighted by using two samples of aluminium in different states of oxidation. The investigation involved the variation of certain parameters affecting the stability of the oxide film, e.g. the temperature, additions of Ti, Si, Cr, Be, Ca and Li to aluminium and the time held at a certain temperature. The state of the molten aluminium surface under various experimental conditions was determined indirectly by surface tension measurements.     

Effect of substrate on the nucleation and growth of aluminum films deposited from methylpyrrolidine alane

Methylpyrrolidine alane complex was used to deposit aluminum films on various types of substrates in a low pressure chemical vapor deposition reactor. The films grow easily on metallic and transition metal oxide surfaces, but not on any other tested semiconductor and dielectric substrates below 200 °C, showing strong substrate dependency. The free energies of precursor adsorption, surface dissociation reaction and product desorption, as well as the film wettability to substrate are among the key factors which affect the energy barrier for nucleation or deposition selectivity. In general, a metal substrate can enhance nucleation because it catalyzes the surface reactions and bonds strongly with aluminum. The oxidation-reduction reaction may occur between the precursor and substrate on a metal oxide surface. The reduced metal sites can be the seed nuclei and are possibly responsible for Al growth on the surfaces of transition metal oxides.     

Wetting of aluminium oxide by molten aluminium and other metals

The sessile drop technique has been used to measure the contact angle of molten aluminium, aluminium-nickel and aluminium-copper alloys, copper and gold, with sapphire, ruby and recrystallised alumina. Measurements were madein vacuo, and as a function of time and temperature over the range 800 to 1500° C. Cinematography and time-lapse photography were used. At temperatures below 950° C, sessile drops of aluminium reached equilibrium only after a period of time which increased with decrease in temperature and could be in excess of one hour. A rapid increase in contact area occurred around 900° C. Above 1150° C drops of aluminium and of the aluminium alloys were observed to spread and contract repeatedly. Contractions were observed with both polycrystalline and single-crystal alumina, although they were much more pronounced with the latter, and were associated with the formation of a series of reaction rings on the plaque. Ruby and sapphire behaved similarly. The shape of the rings depended on the crystallographic orientation of the plaque: the reaction profile tended to terminate in certain low index directions. Neither contractions nor reaction was observed with copper or gold. The observations are discussed in terms of the combined effects of evaporation, chemical reactivity and interfacial tensions in the system.     

Wettability of aluminium nitride by tin–aluminium melts

The wettability of aluminium nitride by Sn–Al melts was studied by the sessile drop method in a vaccum of 2 × 10^–3 Pa at 1100 °C over the whole concentration region. The minimum interval on the contact-angle concentration dependence curve was observed at intermediate composition. For comparison, experiments were also performed on porous AlN. Wetting of porous nitride is worse than the dense nitride. The results have been analysed on the basis of the relation between wettability and the chemical interface reactivity in solid–liquid metal systems.     

Determination of interfacial properties between AlN and aluminum beneath salt at high temperature

Aluminum nitride is of interest as a material for electrolysis cells in the aluminum industry due to its chemical stability when in contact with molten aluminum and/or cryolite-based salt melts. It has also been considered in combination with electrically conductive materials (i.e. AlN/Al-composite) as a material for drained cathode systems in Hall-Heroult processes. Knowledge of the interfacial properties of AlN in contact with molten aluminum and/or cryolite-based melts is therefore important. This paper reports observations of the wettability of AlN by aluminum under salt cover at high temperature using an X-ray technique. Results obtained in this work combined with previously published data are used for the assessment of the work of adhesion of molten aluminum on AlN under vacuum as well as under a cryolitic salt. Scanning electron microscopy examination of metallographic sections was used to confirm the nature of the interfaces. The measured contact angle between AlN and molten aluminum beneath a salt cover at 850 °C is 136° demonstrating the non-wettability of AlN by liquid aluminum under these conditions. The work of adhesion of molten aluminum on AlN is higher under vacuum than under salt. Previously published data allowed the determination of the interfacial properties between liquid aluminum and AlN under a salt cover. The interfacial energy between molten aluminum and salt is 773 mN/m at 850 °C. The work of adhesion of aluminum on AlN is 217 and 1322 mN/m under salt and under vacuum, respectively.     

Application of reaction synthesis principles to thermal spray coatings

Reaction synthesis principles have been extended to plasma spraying to obtain coatings consisting of mixed oxide phases and iron aluminides. Elemental powders of iron and aluminium were fed through a d.c. plasma torch to deposit intermetallic coatings on carbon steel substrates. Carbon steel substrates were also pre-heated with a plasma flame to create an iron oxide surface on the substrate such that an exothermic thermite reaction takes place when molten splats of aluminium impinge the pre-heated substrate at sub- or supersonic velocities. A thermite reaction between iron oxide and aluminium allowed the formation of alumina, FeAl2O4, iron, and iron aluminide phases. The presence of FeAl2O4 and Al2O3 increased the surface hardnesses of the coating, and the hardnesses of the coatings are significantly higher than the hardnesses of steel substrate, and aluminium particles. X-ray analysis of the coatings, microstructural observations, and microhardness measurements suggest that plasma spraying conditions can be tailored to obtain coatings with high hardness values with in situ synthesized reinforcements (spinel and alumina) or iron aluminide phases. Aluminium-rich phases were observed in the as-deposited coatings when a mixture of aluminium and iron or aluminium and nickel were fed through the plasma gun in ratios equivalent to Fe3Al, FeAl, Ni3Al, and NiAl. In some cases, annealing allowed the formation of iron-rich or nickel-rich aluminide phases. High solidification rates of molten splats allowed very limited diffusional reactions between the splats of aluminium and iron, or aluminium and nickel because the available diffusional time for exothermic interfacial reactions is limited to a fraction of a second at best. Oxidation of part of the aluminium led to the formation of alumina in the as-deposited coatings, and therefore, a vacuum plasma spraying technique is desirable to obtain intermetallic phases. The results suggest that reactive spraying will allow deposition of coatings by utilizing the heats of reaction between the constituents, and reactive spraying will broaden the engineering applications of reaction synthesis techniques.     

Nitridation reactions of molten Al-(Mg,Si) alloys

The isothermal nitridation of magnesium- and silicon-doped aluminium melt at 1273 K was investigated. With increasing Mg/Si ratio and decreasing oxygen content in the nitriding atmosphere, four major reaction mechanisms may be separated: (i) a passivating surface nitridation, (ii) a volume nitridation with precipitation of isolated AlN in the aluminium matrix, (iii) a volume nitridation resulting in a three-dimensionally interconnected AlN/Al composite microstructure, and (iv) a break-away nitridation with complete conversion of aluminium to AlN. The behavioural transition of the nitridation mechanism is reflected by the growth direction and the crystal morphology of AlN which change from inward (mechanisms i, ii) to outward (mechanisms iii, iv) growth of the reaction product with [0 0 0 1] as the dominating growth direction. Attempts are made to define the critical magnesium and silicon contents for the regime of controlled AlN/Al composite growth (mechanism iii) at 1273 K, in order to develop novel AlN/Al composite materials.     

Self-limiting low-temperature growth of crystalline AlN thin films by plasma-enhanced atomic layer deposition

We report on the self-limiting growth and characterization of aluminum nitride (AlN) thin films. AlN films were deposited by plasma-enhanced atomic layer deposition on various substrates using trimethylaluminum (TMA) and ammonia (NH₃). At 185 °C, deposition rate saturated for TMA and NH₃ doses starting from 0.05 and 40 s, respectively. Saturative surface reactions between TMA and NH₃ resulted in a constant growth rate of ~ 0.86 Å/cycle from 100 to 200 °C. Within this temperature range, film thickness increased linearly with the number of deposition cycles. At higher temperatures (≥ 225 °C) deposition rate increased with temperature. Chemical composition and bonding states of the films deposited at 185 °C were investigated by X-ray photoelectron spectroscopy. High resolution Al 2p and N 1s spectra confirmed the presence of AlN with peaks located at 73.02 and 396.07 eV, respectively. Films deposited at 185 °C were polycrystalline with a hexagonal wurtzite structure regardless of the substrate selection as determined by grazing incidence X-ray diffraction. High-resolution transmission electron microscopy images of the AlN thin films deposited on Si (100) and glass substrates revealed a microstructure consisting of nanometer sized crystallites. Films exhibited an optical band edge at ~ 5.8 eV and an optical transmittance of > 95% in the visible region of the spectrum.     

The influence of surface roughness and pre-oxidation state on the wettability of aluminium nitride by commercial brazes

The effects of roughness (Ra = 0.17–0.20 m) and of pre-oxidation of the AlN ceramic surface on its wettability and contact interaction with commercial brazing alloys CB4 and CB5 of Ag-Cu-Ti composition have been studied. Wettability has been determined by the sessile drop method at three holding temperatures (810, 900 and 950°C). Particularities of the interface interaction have been identified by microprobe analysis for pre-oxidized samples. Experimental data are compared with data for samples polished to Ra = 0.02–0.03 m not subjected to pre-oxidation. The results show that, for the systems under study, surface roughness does not influence the contact angle value significantly. Pre-oxidation of the AlN in air at 1250°C, however, tends to reduce wettability as a result of the replacement of braze-aluminium nitride interaction by braze-surface aluminium oxide interaction.