Fabrication of Al2O3/AlN composite ceramics with enhanced performance via a heterogeneous precipitation coating process

To improve the thermal and mechanical properties of Al₂O₃/AlN composite ceramics, a novel heterogeneous precipitation coating (HPC) approach was introduced into the fabrication of Al₂O₃/AlN ceramics. For this approach, Al₂O₃ and AlN powders were coated with a layer of amorphous Y₂O₃, with the coated Al₂O₃ and AlN powders found to favor the formation of an interconnected YAG second phase along the grain boundaries. The interconnected YAG phase was designed to act as a diffusion barrier layer to minimize the detrimental interdiffusion between Al₂O₃ and AlN particles. Compared with samples prepared by a conventional ball-milling method, the HPC Al₂O₃/AlN composites exhibited less AlON formation, a higher relative density, a smaller grain size and a more homogeneous microstructure. The thermal conductivity, bending strength, fracture toughness and Weibull modulus of the HPC Al₂O₃/AlN composite ceramics were found to reach 34.21 ± 0.34 W m⁻¹ K⁻¹, 475.61 ± 21.56 MPa, 5.53 ± 0.29 MPa m^1/2 and 25.61, respectively, which are much higher than those for the Al₂O₃ and Al₂O₃/AlN samples prepared by the conventional ball-milling method. These results suggest that HPC is a more effective technique for preparing Al₂O₃/AlN composites with enhanced thermal and mechanical properties, and is probably applicable to other composite material systems as well.     

Effects of YH2 addition on pressureless sintered AlN ceramics

A new type of non-oxide sintering additive of YH₂ was introduced for the fabrication of AlN ceramics with high thermal conductivity and flexural strength. The effects of YH₂ addition (0–5 wt%) on the phase composition, densification, microstructure, thermal conductivity and flexural strength of pressureless sintered AlN ceramics were investigated and compared with those Y₂O₃-added samples (1–5 wt%). The addition of 1 wt% YH₂ led to an in-situ reduction reaction with oxygen impurities, the formation of Y₂O₃ and finally the formation of yttrium aluminate, which in turn improved densification and microstructure. A high flexural strength (408.69 ± 28.23 MPa) was achieved. The addition of 3 wt% YH₂ increased the average grain size and purified the lattice. All these effects are believed to help achieve a high thermal conductivity of 184.82 ± 1.75 W·m^?1·K^?1. Although the thermal conductivity was close to the value of 3 wt% Y₂O₃-added sample, its strength was much increased to 381.53 ± 43.41 MPa. Meanwhile, it demonstrated a good combination of the thermal conductivity and flexural strength than the values reported in some literature. However, further increasing the YH₂ addition to 5 wt% resulted in a high N/O ratio that inhibited the densification behavior of AlN ceramics. The current study showed that AlN ceramics with excellent thermal and mechanical properties could be obtained by the introduction of a suitable YH₂ additive.     

Secondary phases,microstructures and properties of AlN ceramics sintered by adding nitrate sintering additives

AlN ceramics were sintered at a temperature range from 1650 to 1800°C through adding the Ca and Y nitrate sintering additives. Secondary phases, microstructures and properties of the AlN ceramics were studied. When the AlN ceramics are sintered at 1650 or 1675°C, CaO and Y₂O₃ from the sintering additives react with Al₂O₃ in the AlN powder to generate CaAl₄O₇ and Y₃Al₅O₁₂. Part of Y₃Al₅O₁₂ reacts with CaO and Al₂O₃ to form CaYAl₃O₇ at 1700°C. At 1800°C, CaYAl₃O₇ decomposes into CaAl₄O₇ and Y₃Al₅O₁₂. Finally, CaAl₄O₇ volatilises and only Y₃Al₅O₁₂ remains. As the sintering temperature increases, the AlN grains grow continuously and the bending strength and thermal conductivity of the AlN ceramics increase first and then decrease. The AlN ceramics sintered at 1700°C are fully dense and have the highest bending strength and thermal conductivity of 373·7 MPa and 136·7 W m^?1 K^?1 in this work.     

Mechanical performances of AlN/Al metallized ceramic substrates fabricated by transient liquid phase bonding and pre-oxidation treatment

For the miniaturization of high-power electronic components, AlN/Al is a promising metallized ceramic substrate due to its superior mechanical and thermal performances. Numerous bonding processes have been proposed for fabricating the metallized ceramic substrate. Unfortunately, the influences of various bonding techniques on the mechanical performance of AlN/Al metallized ceramic substrate remain undetermined to date. The objective of this study was thus to investigate the effects of the transient liquid phase (TLP) technique and pre-oxidation treatment on the bonding, microstructure, and mechanical strength of the AlN/Al metallized ceramic substrate.The results indicated that the three-layered AlN/Al/AlN specimen could be effectively bonded by the TLP process and pre-oxidation treatment. However, the bending strengths of the specimens fabricated by the two techniques were obviously divergent. The bending strength of raw AlN substrate was 333 MPa. In contrast, the bending strengths of the three-layered specimens with AlN substrates pre-oxidized at 1050 °C, 1150 °C, and 1250 °C were 292 MPa, 250 MPa, and 224 MPa, respectively. Raising the pre-oxidation temperature of the AlN substrate from 1050 °C to 1250 °C obviously increased the thickness of the Al₂O₃ layer and deteriorated the bending strength, for the fracture propagated along the Al₂O₃ layer and the Al₂O₃/AlN interface. For the TLP bonding, the Cu film deposited on the AlN substrate contributed to the generation of Al–Cu transient liquid and to bonding. The bending strength of the three-layered specimens fabricated by TLP at 650 °C was 417 MPa, which was 25% and 43% better than those of the raw AlN substrate and the three-layered specimens prepared by the pre-oxidation treatment, respectively.     

Effects of doping Al-metal powder on thermal,mechanical and dielectric properties of AlN ceramics

In this work, the influence of Al-metal powder addition upon that thermal, mechanical and dielectric properties of aluminium nitride (AlN) ceramic was studied. The findings show that adding Al-metal powder improves not only the mechanical and thermal properties of the AlN ceramic but also has no negative impact on its dielectric properties. Based on Y₂O₃ as sintering aid, the AlN ceramic with 1.0 wt% Al doping were 14.35% higher thermal conductivity, 11.73% higher flexural strength and 59.50% higher fracture toughness than those doped without Al, respectively. This study showed that the addition of Al-metal powder may favor the purifying of the AlN lattice and the formation of homogenous and isolated second phase, which would increase the AlN–AlN interfaces and improve the thermal conductivity. Furthermore, the grain boundaries of AlN ceramics might be strengthened by the isolated second phases due to the thermal mismatch between the second phases and AlN grains, thus strengthening and toughening the AlN ceramic doped with Al. However, the large additive amount of Al powder (>1.0 wt%) was not help the isolation and homogenization of the second phase, giving a deterioration in an AlN ceramic's mechanical and thermal properties. These results suggest that the introduction of an appropriate dose of aluminium metal powder is a simple method that can be used to improve the AlN ceramic's mechanical and thermal properties simultaneously.     

AlN with high strength and high thermal conductivity based on an MCAS-Y2O3-YSZ multi-additive system

The additive composition of an AlN ceramic substrate material was optimized to achieve high strength and thermal conductivity. MgO-CaO-Al₂O₃-SiO₂ (MCAS) glass and Y₂O₃ were used as basic additives for improved sintering properties and thermal conductivity, thereby allowing for AlN to be sintered at a relatively low temperature of 1600 °C without pressurization. Yttria-stabilized zirconia (YSZ) was added (0–3 wt%) to further improve the strength of the AlN ceramic. YSZ and Y₂O₃ reacted with AlN to produce ZrN, Y₄Al₂O₉, and Y₃Al₅O₁₂ secondary phases. The formation of these yttrium aluminate phases improved the thermal conductivity by removing oxygen impurities, while ZrN formed at the AlN grain boundaries provided resistance to grain boundary fractures for improved strength. Overall, the AlN ceramic with 1 wt% MCAS, 3 wt% Y₂O₃, and 1 wt% YSZ exhibited excellent thermal and mechanical properties, including a thermal conductivity of 109 W/mK and flexural strength of 608 MPa.     

Balancing thermal conductivity and strength of hot-pressed AlN ceramics via pre-sintering and annealing process

The heat dissipation requirements of the new generation of semiconductors are placing higher demands on the overall performance of aluminum nitride (AlN) ceramics. This has led to an increasing emphasis on AlN ceramics that combine thermal conductivity and strength. AlN ceramics are often strengthened by hot-press sintering, but their thermal conductivity is typically modest. In this study, pre-sintering and annealing processes are introduced to optimize the thermal conductivity of hot-pressed AlN ceramics to avoid the detrimental effects of oxygen impurities in the AlN lattice. The effect of the oxide layer on the surface of commercial AlN particles is investigated, including density, phase composition, microstructure, and fracture behavior. The effect of annealing on the improvement of thermal conductivity and flexural strength is also verified. Electron paramagnetic resonance (EPR) analysis is performed to examine the concentration of intercrystalline defects under various conditions. Finally, AlN ceramics with a thermal conductivity of 204 W m⁻¹ K⁻¹ and a flexural strength of 376 MPa are obtained.     

Fabrication and characterization of aluminum nitride thick film coated on aluminum substrate for heat dissipation

For effective heat dissipation in high-power LED applications, aluminum nitride (AlN) thick films as thermally conductive dielectric layers were developed, which were deposited on an Al substrate by aerosol deposition (AD). The aerosol-deposited AlN thick films on Al substrates have advantages over conventional polymer-based dielectric substrates or ceramic substrate mounted heatsink systems including an epoxy adhesive, such as excellent heat dissipation capacity and low thermal resistance. AD is an effective method to fabricate high-quality AlN thick film without the Al₂O₃ phase because the film is formed at room temperature. Highly dense and well-adhered, pure AlN thick films with thicknesses up to 30 µm were deposited on an Al substrate. AlN-Al₂O₃ and AlN-polyvinylidene fluoride (PVDF) composite films were also deposited on an Al substrate in order to investigate the effect of Al₂O₃ and polymer on the microstructure and thermal properties. Among the films, pure AlN thick film exhibited the highest dielectric strength, the highest thermal conductivity, and the lowest thermal resistance. Therefore, it can be expected that the aerosol-deposited AlN thick film on Al substrate could be used as a powerful heatsink.     

Dielectric and thermal properties of AlN ceramics

The effects of slow-cooling and annealing conditions on dielectric loss, thermal conductivity and microstructure of AlN ceramics were investigated. Y₂O₃ from 0.5 to 1.25 mol% at 0.25% increments was added as a sintering additive to AlN powder and pressureless sintering was carried out at 1900 °C for 2 h in a nitrogen flowing atmosphere. To improve the properties, AlN samples were slow-cooled at a rate of 1 °C min⁻¹ from 1900 to 1750 °C, subsequently cooled to 970 °C at a rate of 10 °C min⁻¹ and then annealed at the same temperature for 4 h. AlN and YAG (5Al₂O₃/3Y₂O₃) were the only identified phases from XRD. AlN doped with 0.5 and 0.75 mol% Y₂O₃ had a low loss of <2.0 × 10⁻³ and a high thermal conductivity of >160 W m⁻¹ °C⁻¹.     

Improvement in fracture strength in electrically conductive AlN ceramics with high thermal conductivity

It is possible to impart electrical conductivity to insulating aluminum nitride (AlN) ceramics by precipitating a yttrium oxycarbide grain boundary phase with electrical conductivity. However, previously, sintering at high temperature was required to increase the electrical conductivity through the transformation of the grain boundary phase from yttrium aluminum oxide (Al₂Y₄O₉) to rare-earth oxycarbide. As a result, the increase in electrical conductivity was accompanied with a considerable decrease in the fracture strength due to grain growth of AlN. In this study, sintering temperature and additive compositions were investigated to maintain the high strength of electrically conductive AlN without losing the high thermal conductivity.     

Improvement on thermophysical and mechanincal properties of LaMgAl11O19 magnetoplumbite by Nd2O3 and Sc2O3 co-doping

LaMgAl₁₁O₁₉-type magnetoplumbite holds great promise to be used above 1300 °C as thermal barrier coatings (TBCs), but its practical application has been restricted because of inferior thermophysical properties. Herein, we focus on optimizing the thermophysical properties of LaMgAl₁₁O₁₉ by simultaneously substituting La³⁺ and Al³⁺ ions with Nd³⁺ and Sc³⁺ ions, respectively. Results show that the effects of co-substitution on reducing thermal conductivity are pronounced. The thermal conductivities of La_1-xNd_xMgAl_11-xSc_xO₁₉ (x = 0, 0.1, 0.2, 0.3) ceramics decrease progressively with dopant concentration and a lowest thermal conductivity of 2.04 W/(m·K) is achieved with x = 0.3 at 1000 °C, which is a value superior to pure LMA and even lower than YSZ. The mechanisms behind the lowered thermal conductivity are investigated. Increase of the thermal expansion coefficient is also realized (8.53 × 10⁻⁶ K⁻¹ for pure LMA, 9.07 × 10⁻⁶ K⁻¹ for x = 0.3, 1300 °C). Most importantly, Nd³⁺ and Sc³⁺ combination doping indeed facilitates mechanical properties of La_1-xNd_xMgAl_11-xSc_xO₁₉ solid solutions as well. It should be noted that Sc³⁺ doping at Al³⁺ site plays more effective role in improving thermal properties than Nd³⁺ does at La³⁺ site. This work provides a path to simultaneously integrate low thermal conductivity, good phase stability, moderate thermal expansion behavior and excellent mechanical properties on LMA for the next generation TBCs.     

Effects of SmF3 addition on aluminum nitride ceramics via pressureless sintering

Aluminum nitride (AlN) ceramics with dense structure, high thermal conductivity, and exceptional mechanical properties were fabricated by pressureless sintering with a novel non-oxide sintering additive, samarium fluoride (SmF₃). The results showed that the use of a moderate amount of SmF₃ promoted significant densification of AlN and removed the oxygen impurity. This led to the formation of fine and isolated secondary phase that cleaned the grain boundaries and increased the contact between AlN grains, remarkably enhancing thermal conductivity. Furthermore, SmF₃ also exhibited grain refinement and grain boundary strengthening effects similar to traditional sintering additive, samarium oxide (Sm₂O₃), leading to high mechanical properties in SmF₃-doped AlN samples. The most optimal characteristics (thermal conductivity of 190.67 W·m⁻¹·K⁻¹, flexural strength of 403.86 ± 18.27 MPa, and fracture toughness of 3.71 ± 0.19 MPa·m^1/2) were achieved in the AlN ceramic with 5 wt% SmF₃.     

Powder injection molding of complex-shaped aluminium nitride ceramic with high thermal conductivity

Aluminum nitride (AlN) is a promising material for heat sinks and microelectronic applications because of the advantages of high theoretical thermal conductivity, high mechanical strength, good electrical insulation, low dielectric constant and low thermal expansion coefficient. However, the difficulties in shaping complex-shaped parts with a high thermal conductivity have retarded the wide applications of AlN ceramic. Herein, we design a new binder system containing resin components and adopt the powder injection molding technology to fabricate complex-shaped AlN parts. After the debinding process, the special binder system would produce residual carbon, which could react with Al₂O₃ and result in decreasing oxygen impurity and forming the yttrium-rich aluminates. The yttrium-rich aluminates can accelerate the densification of AlN ceramic and fasten the oxygen on the triangular grain boundary, leaving the clean grain boundary beneficial for high thermal conductivity. The as-prepared AlN parts with complex shape possess a high thermal conductivity of 248 W m⁻¹ K⁻¹.     

Densification and properties of AlN ceramic bonded carbon

To obtain light and tough materials with high thermal conductivity, AlN ceramic bonded carbon (AlN/CBC) composites were fabricated at temperatures from 1600 to 1900 °C in a short period of 5 min by the spark plasma sintering technique. All AlN/CBCs (20 vol% AlN) have unique microstructures containing carbon particles of 15 μm in average size and continuous AlN boundary layers of 0.5-3 μm in thickness. With an increase in sintering temperature, AlN grains grow and anchor into carbon particles, resulting in the formation of a tight bonding layer. The AlN/CBC sintered at 1900 °C exhibited a light weight (2.34 g/cm³), high bending strength (100 MPa), and high thermal conductivity (170 W/mK).     

Novel in-situ constructing approach for vertically aligned AlN skeleton and its thermal conductivity enhancement effect on epoxy

As one of the key components of electronic devices, thermal management materials (TMMs) with high thermal conductivity are essential to ensure their safety and long service life. For polymer-based TMMs, AlN is one of the preferred fillers, but it has some drawbacks such as high cost and easy hydrolysis. Herein, a controllable and continuously oriented three-dimensional AlN skeleton (3D-AlNNS) was in-situ transformed from a low-cost 3D Al-containing skeleton (3D-AlNS) by combining the ice-templating and nitriding reaction sintering. Subsequently, AlN/epoxy composites were obtained by a vacuum infiltration. The composite containing 39.69 vol% AlN had the highest thermal conductivity of 4.29 W m^?1·K^?1, which was 21.45 times higher than that of pure epoxy. The composite substrates showed excellent heat dissipation performance in practical applications due to their high thermal conductivity. The continuous directional alignment of AlN powders in the 3D skeleton and intersection of AlN whiskers between the skeleton walls produced in-situ contributed to the formation of effective multichannel heat transferring paths and improvement in thermal conductivity. This novel approach has the advantages of low-cost, short processing time, simple operation and repeatability, and provides a new idea for developing heat-conducting polymer composites, which can also be extended to the preparation of similar TMMs.     

Growth of AlN Crystals on SiC Substrates by Thermal Nitridation of Al2O3

The growth of AlN crystals on c‐plane 6H–SiC substrates by thermal nitridation of Al₂O₃ pellets in the presence of graphite and ZrO₂ was demonstrated. Addition of graphite and ZrO₂ effectively accelerated the evaporation of Al₂O₃, yielding c‐axis oriented AlN films on SiC substrates. The SiC substrate was severely deteriorated at 2173 K, which produced a porous interface between the AlN film and substrate, resulting in low‐quality AlN crystals. The deterioration of SiC was successfully suppressed by introducing a pre‐deposited homo‐buffer layer, allowing two‐dimensional‐like growth of AlN. The buffer layer promoted the formation of a high‐quality AlN film. At 2173 K, the full‐width at half maximum of the X‐ray rocking curves of the (0002) and (10–10) planes of the AlN film was 360 and 425 arcsec, respectively.     

Formation of (Al2OC)1−x(AlN)x solid solution starting from Al–Si–Al2O3 powder matrix at 1300°C in flowing nitrogen

(Al₂OC)_1−x(AlN)_x solid solution-reinforced Si–Al₂O₃ composite was successfully synthesized by designed heating of the Al–Si–Al₂O₃ composite to 580°C and held for 8 hours, followed by heating to 1300°C at a rate of 12°C/h in flowing nitrogen. The reaction mechanism is as follows: after the Al–Si–Al₂O₃ composite is heated to 580°C and held for 8 hours, an AlN cladding is formed on the surface of the Al powder, thus the composite is preconverted into (Al–AlN cladding structure)–Si–Al₂O₃ system. With increasing temperature, the AlN cladding ruptures and the reactive Al(l) flows out. The Al(l) preferentially undergoes active oxidation to form metastable Al₂O(g), which lowers P_O2 inside the composite and inhibits the active oxidation of Si. Moreover, ultrafine carbon is produced by the pyrolysis of the phenolic resin binder. Both metastable Al₂O(g) and ultrafine carbon are highly reactive. Therefore, under the induction of AlN and N₂, (Al₂OC)_1−x(AlN)_x solid solution is formed by the reaction which easily occurs at a relatively low temperature. In the presence of a large amount of Al₂O(g), the P_O2 in the composite does not satisfy the condition required for both Si nitridation and active oxidation, so the free Si remains stable in the composite, forming a metal-non-oxide-oxide composite. The cold crushing strength of the composites is up to 305 MPa, and the composites do not show hydration after 20 months of storage in the environment.     

Using graphene networks to build SiC(rGO,Gx) bulk ceramics from polymeric precursors

Unique properties of graphene open new opportunities for preparing composites with favorable functional capabilities. Herein, an ingenious synthesis route via re-pyrolysis process of ball-milling-induced SiC(rGO, Gx)_p fillers/polycarbosilane-vinyltriethoxysilane-graphene oxide (PCS-VTES-GO, PVG) precursors blends is proposed to obtain structural-functional integrated SiC(rGO, Gx) bulk polymer-derived ceramics (PDCs). The introduction of SiC(rGO, Gx)_p provides favorable moldability, ceramic yield and linear shrinkage. Attractively, graphene networks with more free-moving electrical-charge carriers and wider phonon-channel prominently enhance electrical and thermal conductivities of products. Particularly, SiC(rGO, G_20%) bulk PDCs generated at 1300 °C own satisfactory ceramic yield (90.74%), linear shrinkage (5.00%), fracture toughness (2.07 MPa m^1/2), bending strength (35.37 MPa), electrical conductivity (25.72 S cm^?1) and thermal conductivity (6.72 W m^?1·K^?1), realizing outstanding values to the best of our knowledge. This fabrication method favors mass production of larger-sized PDCs and possess potential emerging uses.     

Low-temperature hot-press sintering of AlN ceramics with MgO–CaO–Al2O3–SiO2 glass additives for ceramic heater applications

Aluminum nitride (AlN) is used a ceramic heater material for the semiconductor industry. Because extremely high temperatures are required to achieve dense AlN components, sintering aids such as Y₂O₃ are typically added to reduce the sintering temperature and time. To further reduce the sintering temperature, in this study, a low-melting-temperature glass (MgO–CaO–Al₂O₃–SiO₂; MCAS) was used as a sintering additive for AlN. With MCAS addition, fully dense AlN was obtained by hot-press sintering at 1500 °C for 3 h at 30 MPa. The mechanical properties, thermal conductivity, and volume resistance of the sintered AlN–MCAS sample were evaluated and compared with those of a reference sample (AlN prepared with 5 wt% Y2O3 sintering aid sintered at 1750 °C for 8 h at 10 MPa). The thermal conductivity of AlN prepared with 0.5 wt% MCAS was 91.2 W/m?K, which was 84.8 W/m?K lower than that of the reference sample at 25 °C; however, the difference in thermal conductivity between the samples was only 14.2 W/m?K at the ceramic-heater operating temperature of 500 °C. The flexural strength of AlN–MCAS was 550 MPa, which was higher than that of the reference sample (425 MPa); this was attributed to the smaller grain size achieved by low-temperature sintering. The volume resistance of AlN–MCAS was lower than that of the reference sample in the range of 200–400 °C. However, the resistivity of the proposed AlN–MCAS sample was higher than that of the reference sample (500 °C) owing to grain-boundary scattering of phonons. In summary, the proposed sintering strategy produces AlN materials for heater applications with low production cost, while achieving the properties required by the semiconductor industry.     

Synthesis and properties of AlN/MAS/Si3N4 ternary glass-ceramic composites with in-situ grown rod-like β-Si3N4 crystals

The AlN/MAS/Si₃N₄ ternary composites with in-situ grown rod-like β-Si₃N₄ were obtained by a two-step sintering process. The microstructure analysis, compositional investigation as well as properties characterization have been systematically performed. The AlN/MAS/Si₃N₄ ternary composites can be densified at 1650 °C in nitrogen atmosphere. The in-situ grown rod-like β-Si₃N₄ grains are beneficial to the improvement of thermal, mechanical, and dielectric properties. The thermal conductivity of the composites was increased from 14.85 to 28.45 W/(m K) by incorporating 25 wt% α-Si₃N₄. The microstructural characterization shows that the in-situ growth of rod-like β-Si₃N₄ crystals leads to high thermal conductivity. The AlN/MAS/Si₃N₄ ternary composite with the highest thermal conductivity shows a low relative dielectric constant of 6.2, a low dielectric loss of 0.0017, a high bending strength of 325 MPa, a high fracture toughness of 4.1 MPa m^1/2, and a low thermal expansion coefficient (α_{25–300 °C}) of 5.11 × 10^?6/K. This ternary composite with excellent comprehensive performance is expected to be used in high-performance electronic packaging materials.