Aluminum nitride having a dense hexagonal structure is used as a high-temperature material because of its excellent heat resistance and high mechanical strength; its excellent piezoelectric properties are also attracting attention. The structure and residual stress of AlN thin films formed on glass substrate using TFT sputtering system are examined by XRD. The deposition conditions are nitrogen gas pressures of 1 × 102, 6 × 103, and 3 × 103, substrate temperature of 523 K, and sputtering time of 120 min. The structure of the AlN thin film is columnar, having a c-axis, i.e., a <00·1> orientation, which is the normal direction of the glass substrate. An X-ray stress measurement method for crystalline thin films with orientation properties such as columnar structure is proposed and applied to the residual stress measurement of AlN thin films with orientation <00·1>. Strength of diffraction lines other than 00·2 diffraction is very weak. As a result of stress measurement using AlN powder sample as a comparative standard sample, tensile residual stress is obtained when the nitrogen gas pressure is low, but the gas pressure increases as the residual stress is shifts toward compression. At low gas pressure, the unit cell expands due to the incorporation of excess nitrogen atoms.
We investigate the effects of Yb2O3 and calcium aluminosilicate (CAS) glass as sintering additives on the sintering behavior of AlN. The AlN specimens are sintered at temperatures between 1700oC and 1900oC for 2 h in a nitrogen atmosphere. When the Yb2O3 content is low (within 3 wt.%), an isolated shape of secondary phase is observed at the AlN grain boundary. In contrast, when 3 wt.% Yb2O3 and 1 wt.% CAS glass are added, a continuous secondary phase is formed at the AlN grain boundary. The thermal conductivity decreases when the CAS glass is added, but the sintering density does not decrease. In particular, when 10 wt.% Yb2O3 and 1 wt.% CAS glass are added to AlN, the flexural strength is the highest, at 463 MPa. These results are considered to be influenced by changes in the microstructure of the secondary phase of AlN.
In this study, we investigate the effect of Al/N source ratios and growth rates on the growth and structural properties of AlN films on c-plane sapphires by plasma-assisted molecular beam epitaxy. Both growth rates and Al/N ratios affect crystal qualities of AlN films. The full width at half maximum (FWHM) values of (1015) X-ray rocking curves (XRCs) change from 0.22 to 0.31° with changing of the Al/N ratios, but the curves of (0002) XRCs change from 0.04 to 0.45° with changing of the Al/N ratios. This means that structural deformation due to dislocations is slightly affected by the Al/N ratio in the (1015) XRCs but affected strongly for the (0002) XRCs. From the viewpoint of growth rate, the AlN films with high growth rate (HGR) show better crystal quality than the low growth rate (LGR) films overall, as shown by the FWHM values of the (0002) and (1015) XRCs. Based on cross-sectional transmission electron microscope observation, the HGR sample with an Al/N ratio of 3.1 shows more edge dislocations than there are screw and mixed dislocations in the LGR sample with Al/N ratio of 3.5.
Aluminum nitride (AlN) has excellent electrical insulation property, high thermal conductivity, and a low thermal expansion coefficient; therefore, it is widely used as a heat sink, heat-conductive filler, and heat dissipation substrate. However, it is well known that the AlN-based materials have disadvantages such as low sinterability and poor mechanical properties. In this study, the effects of addition of various amounts (1-6 wt.%) of sintering additives Y2O3 and Sm2O3 on the thermal and mechanical properties of AlN samples pressureless sintered at 1850oC in an N2 atmosphere for a holding time of 2 h are examined. All AlN samples exhibit relative densities of more than 97%. It showed that the higher thermal conductivity as the Y2O3 content increased than the Sm2O3 additive, whereas all AlN samples exhibited higher mechanical properties as Sm2O3 content increased. The formation of secondary phases by reaction of Y2O3, Sm2O3 with oxygen from AlN lattice influenced the thermal and mechanical properties of AlN samples due to the reaction of the oxygen contents in AlN lattice.
Aluminum nitride (AlN) has versatile and intriguing properties, such as wide direct bandgap, high thermal conductivity, good thermal and chemical stability, and various functionalities. Due to these properties, AlN thin films have been applied in various fields. However, AlN thin films are usually deposited by high temperature processes like chemical vapor deposition. To further enlarge the application of AlN films, atomic layer deposition (ALD) has been studied as a method of AlN thin film deposition at low temperature. In this mini review paper, we summarize the results of recent studies on AlN film grown by thermal and plasma enhanced ALD in terms of processing temperature, precursor type, reactant gas, and plasma source. Thermal ALD can grow AlN thin films at a wafer temperature of 150~550 oC with alkyl/amine or chloride precursors. Due to the low reactivity with NH3 reactant gas, relatively high growth temperature and narrow window are reported. On the other hand, PEALD has an advantage of low temperature process, while crystallinity and defect level in the film are dependent on the plasma source. Lastly, we also introduce examples of application of ALD-grown AlN films in electronics.
The electrical and interfacial properties of HfO2/Al2O3 and Al2O3/HfO2 dielectrics on AlN/p-Ge interface prepared by thermal atomic layer deposition are investigated by capacitance–voltage(C–V) and current–voltage(I–V) measurements. In the C–V measurements, humps related to mid-gap states are observed when the ac frequency is below 100 kHz, revealing lower mid-gap states for the HfO2/Al2O3 sample. Higher frequency dispersion in the inversion region is observed for the Al2O3/HfO2 sample, indicating the presence of slow interface states A higher interface trap density calculated from the high-low frequency method is observed for the Al2O3/HfO2 sample. The parallel conductance method, applied to the accumulation region, shows border traps at 0.3~0.32 eV for the Al2O3/HfO2 sample, which are not observed for the Al2O3/HfO2 sample. I–V measurements show a reduction of leakage current of about three orders of magnitude for the HfO2/Al2O3 sample. Using the Fowler-Nordheim emission, the barrier height is calculated and found to be about 1.08 eV for the HfO2/Al2O3 sample. Based on these results, it is suggested that HfO2/Al2O3 is a better dielectric stack than Al2O3/HfO2 on AlN/p-Ge interface.
In this study, the effect of the content of MgO-CaO-Al2O3-SiO2 (MCAS) glass additives on the properties of AlN ceramics is investigated. Dilatometric analysis and isothermal sintering for AlN compacts with MCAS contents varying between 5 and 20 wt% are carried out at temperatures ranging up to 1600℃. The results showed that the shrinkage of the AlN specimens increases with increasing MCAS content, and that full densification can be obtained irrespective of the MCAS content. Moreover, properties of the AlN-MCAS specimens such as microhardness, thermal conductivity, dielectric constant, and dielectric loss are analyzed. Microhardness and thermal conductivity decrease with increasing MCAS content. An acceptable candidate for AlN application is obtained: an AlN-MCAS composite with a thermal conductivity over 70 W/m·K and a dielectric loss tangent (tan δ) below 0.6 × 10−3, with up to 10 wt% MCAS content.
In this study, MgO–CaO–Al2O3–SiO2 (MCAS) nanocomposite glass powder having a mean particle size of 50 nm and a specific surface area of 40 m2/g is used as a sintering additive for AlN ceramics. Densification behaviors and thermal properties of AlN with 5 wt% MCAS nano-glass additive are investigated. Dilatometric analysis and isothermal sintering of AlN-5wt% MCAS compact demonstrates that the shrinkage of the AlN specimen increases significantly above 1,300oC via liquid phase sintering of MCAS additive, and complete densification could be achieved after sintering at 1,600oC, which is a reduction in sintering temperature by 200oC compared to conventional AlN-Y2O3 systems. The MCAS glass phase is satisfactorily distributed between AlN particles after sintering at 1,600oC, existing as an amorphous secondary phase. The AlN specimen attained a thermal conductivity of 82.6 W/m·K at 1,600oC.
An Al2O3/AlN bilayer deposited on GaN by atomic layer deposition (ALD) is employed to prepare Al2O3/AlN/GaN metal-insulator-semiconductor (MIS) diodes, and their interfacial properties are investigated using X-ray photoelectron spectroscopy (XPS) with sputter etch treatment and current-voltage (I-V) measurements. XPS analyses reveal that the native oxides on the GaN surface are reduced significantly during the early ALD stage, indicating that AlN deposition effectively clelans up the GaN surface. In addition, the suppression of Al-OH bonds is observed through the ALD process. This result may be related to the improved device performance because Al-OH bonds act as interface defects. Finally, temperature dependent I-V analyses show that the barrier height increases and the ideality factor decreases with an increase in temperature, which is associated with the barrier inhomogeneity. A Modified Richardson plot produces the Richardson constant of A** as 30.45 Acm−2K−2, which is similar to the theoretical value of 26.4 Acm−2K−2 for n-GaN. This indicates that the barrier inhomogeneity appropriately explains the forward current transport across the Au/Al2O3/AlN/GaN interface.
Recently, the use of an aluminum nitride(AlN) buffer layer has been actively studied for fabricating a high quality gallium nitride(GaN) template for high efficiency Light Emitting Diode(LED) production. We confirmed that AlN deposition after N2 plasma treatment of the substrate has a positive influence on GaN epitaxial growth. In this study, N2 plasma treatment was performed on a commercial patterned sapphire substrate by RF magnetron sputtering equipment. GaN was grown by metal organic chemical vapor deposition(MOCVD). The surface treated with N2 plasma was analyzed by x-ray photoelectron spectroscopy(XPS) to determine the binding energy. The XPS results indicated the surface was changed from Al2O3 to AlN and AlON, and we confirmed that the thickness of the pretreated layer was about 1 nm using high resolution transmission electron microscopy(HR-TEM). The AlN buffer layer deposited on the grown pretreated layer had lower crystallinity than the as-treated PSS. Therefore, the surface N2 plasma treatment on PSS resulted in a reduction in the crystallinity of the AlN buffer layer, which can improve the epitaxial growth quality of the GaN template.
Aluminum nitride (AlN) powder specimens are treated by high-energy bead milling and then sintered at various temperatures. Depending on the solvent and milling time, the oxygen content in the AlN powder varies significantly. When isopropyl alcohol is used, the oxygen content increases with the milling time. In contrast, hexane is very effective at suppressing the oxygen content increase in the AlN powder, although severe particle sedimentation after the milling process is observed in the AlN slurry. With an increase in the milling time, the primary particle size remains nearly constant, but the particle agglomeration is reduced. After spark plasma sintering at 1400℃, the second crystalline phase changes to compounds containing more Al2O3 when the AlN raw material with an increased milling time is used. When the sintering temperature is decreased from 1750℃ to 1400℃, the DC resistivity increases by approximately two orders of magnitude, which implies that controlling the sintering temperature is a very effective way to improve the DC resistivity of AlN ceramics.
Ti alloys are extensively used in high-technology application because of their strength, oxidation resistance at high temperature. However, Ti alloys tend to be classified very difficult to cut material. In this paper, The powder synthesis, spark plasma sintering (SPS), bulk material properties such as electrical conductivity and thermal conductivity are systematically examined on Ti2AlN and Ti2AlC materials having most light-weight and oxidation resistance among the MAX phases. The bulk samples mainly consisted of Ti2AlN and Ti2AlC materials with density close to theoretical value were synthesized by a SPS method. Machining characteristics such as machining time, surface quality are analyzed with measurement of voltage and current waveform according to machining condition of micro-electrical discharge machining with micro-channel shape.
Aluminum nitride, a compound semiconductor, has a Wurtzite structure; good material properties such as high thermal conductivity, great electric conductivity, high dielectric breakdown strength, a wide energy band gap (6.2eV), a fast elastic wave speed; and excellent in thermal and chemical stability. Furthermore, the thermal expansion coefficient of the aluminum nitride is similar to those of Si and GaAs. Due to these characteristics, aluminum nitride can be applied to electric packaging components, dielectric materials, SAW (surface acoustic wave) devices, and photoelectric devices. In this study, we surveyed the crystallization and preferred orientation of AlN thin films with an X-ray diffractometer. To fabricate the AlN thin film, we used the magnetron sputtering method with N2, NH3 and Ar. According to an increase in the partial pressures of N2 and NH3, Al was nitrified and deposited onto a substrate in a molecular form. When AlN was fabricated with N2, it showed a c-axis orientation and tended toward a high orientation with an increase in the temperature. On the other hand, when AlN was fabricated with NH3, it showed a-axis orientation. This result is coincident with the proposed mechanism. We fabricated AlN thin films with an a-axis orientation by controlling the sputtering electric power, NH3 pressure, deposition speed, and substrate temperature. According to the proposed mechanism, we also fabricated AlN thin films which demonstrated high aaxis and c-axis orientations.
Aluminum nitride(AlN) films were grown on the C-face and on the Si-face of (0001) silicon carbide(SiC) substrates using plasma-assisted molecular-beam epitaxy(PA-MBE). This study was focused on first-stage growth manipulation prior to the start of AlN growth. Al pre-exposure, N-plasma pre-exposure, and simultaneous exposure(Al and N-plasma) procedures were used in the investigation. In addition, substrate polarity and, first-stage growth manipulation strongly affected the growth and properties of the AlN films. Al pre-exposure on the C-face and on the Si-face of SiC substrates prior to initiation of the AlN growth resulted in the formation of hexagonal hillocks on the surface. However, crack formation was observed on the C-face of SiC substrates without Al pre-exposure. X-ray rocking-curve measurements revealed that the AlN epilayers grown on the Si-face of the SiC showed relatively lower tilt and twist mosaic than did the epilayers grown on the C-face of the SiC. The results from the investigations reported in this paper indicate that the growth conditions on the Si-face of the SiC without Al pre-exposure was highly preferred to obtain the overall high-quality AlN epilayers formed using PA-MBE.
AlN epilayers were grown on a c-plane sapphire substrate using hydride vapor phase epitaxy (HVPE). A series of AlN epilayers were grown at 1120˚C with V/III ratios 1.5, 2.5 and 3.5, and the influence of V/III ratio on their properties was investigated. As the V/III ratio was increased, the surface roughness (RMS roughness), Raman shift of E2 high peaks and full-width at half-maximum (FWHM) of symmetrical (002) & asymmetrical (102) of the AlN epilayers increased. However, the intensities of the Raman E2 high peaks were reduced. This indicates that the crystal quality of the grown AlN epilayers was degraded by activation of the parasitic reaction as the V/III ratio was increased. Smooth surface, stress free and high crystal quality AlN epilayers were obtained at the V/III ratio of 1.5. The crystal quality of AlNepilayers is worsened by the promotion of three-dimensional (3D) growth mode when the flow of NH3 is high.
Ti2AlN composites are a laminated compounds that posses unique combination of typical ceramic proper- ties and typical metallic(Ti alloy) properties. In this paper, the powder synthesis, SPS sintering, composite characteristics and machinability evaluation were systematically conducted. The random orientation characteristics and good crystalli- zation of the Ti2AlN phase are observed. The electrical and thermal conductivity of Ti2AlN is higher than that of Ti6242 alloy. A machining test was carried out to compare the effect of material properties on micro electrical discharge drilling for Ti2AlN composite and Ti6242 alloy. Also, mixture table as a kind of tables of orthogonal arrays was used to know how parameter is main effective at experimental design. Consequently, hybrid Ti2AlN ceramic composites showed good machining time and electrode wear shape under micro ED-drilling process. This conclusion proves the feasibility in the industrial applications.
In the DBC (direct bonding of copper) process the oxygen partial pressure surrounding the AlN/Cu bonding pairs has been controlled by Ar gas mixed with oxygen. However, the direct bonding of Cu with sound interface and good adhesion strength is complicated process due to the difficulty in the exact control of oxygen partial pressure by using Ar gas. In this study, we have utilized the in-situ equilibrium established during the reaction of + 1/2 by placing powder bed of CuO or around the Cu/AlN bonding pair at . The adhesion strength was relatively better in case of using CuO powder than when powder was used. Microstructural analysis by optical microscopy and XRD revealed that the interface of bonding pair was composed of , Cu and small amount of CuO phase. Thus, it is explained that the good adhesion between Cu and AlN is attributed to the wetting of eutectic liquid formed by reaction of Cu and .
We have grown AlN nanorods and AlN films using plasma-assisted molecular beam epitaxy by changing the Al source flux. Plasma-assisted molecular beam epitaxy of AlN was performed on c-plane Al2O3 substrates with different levels of aluminum (Al) flux but with the same nitrogen flux. Growth behavior of AlN was strongly affected by Al flux, as determined by in-situ reflection high energy electron diffraction. Prior to the growth, nitridation of the Al2O3 substrate was performed and a two-dimensionally grown AlN layer was formed by the nitridation process, in which the epitaxial relationship was determined to be [11-20]AlN//[10-10]Al2O3, and [10-10]AlN//[11-20]Al2O3. In the growth of AlN films after nitridation, vertically aligned nanorod-structured AlN was grown with a growth rate of 1.6μm/h, in which the growth direction was<0001>, for low Al flux. However, with high Al flux, Al droplets with diameters of about 8μm were found, which implies an Al-rich growth environment. With moderate Al flux conditions, epitaxial AlN films were grown. Growth was maintained in two-dimensional or three-dimensional growth mode depending on the Al flux during the growth; however, final growth occurred in three-dimensional growth mode. A lowest root mean square roughness of 0.6 nm (for 2μm×2μm area) was obtained, which indicates a very flat surface.
In this study, a high energy ball milling process was employed in order to improve the densification of direct nitrided AlN powder. The densification behavior and the sintered microstructure of the milled AlN powder were investigated. Mixture of AlN powder doped with 5 wt.% as a sintering additive was pulverized and dispersed up to 50 min in a bead mill with very small beads. Ultrafine AlN powder with a particle size of 600 nm and a specific surface area of 9.54 was prepared after milling for 50 min. The milled powders were pressureless-sintered at for 4 h under atmosphere. This powder showed excellent sinterability leading to full densification after sintering at for 4 h. However, the sintered microstructure revealed that the fraction of yitttium aluminate increased with milling time and sintering temperature and the newly-secondary phase of ZrN was observed due to the reaction of AlN with the impurity.
We report growth of epitaxial AlN thin films on c-plane sapphire substrates by plasma-assisted molecular beam epitaxy. To achieve two-dimensional growth the substrates were nitrided by nitrogen plasma prior to the AlN growth, which resulted in the formation of a two-dimensional single crystalline AlN layer. The formation of the two-dimensional AlN layer by the nitridation process was confirmed by the observation of streaky reflection high energy electron diffraction (RHEED) patterns. The growth of AlN thin films was performed on the nitrided AlN layer by changing the Al beam flux with the fixed nitrogen flux at 860˚C. The growth mode of AlN films was also affected by the beam flux. By increasing the Al beam flux, two-dimensional growth of AlN films was favored, and a very flat surface with a root mean square roughness of 0.196 nm (for the 2 μm × 2 μm area) was obtained. Interestingly, additional diffraction lines were observed for the two-dimensionally grown AlN films, which were probably caused by the Al adlayer, which was similar to a report of Ga adlayer in the two-dimensional growth of GaN. Al droplets were observed in the sample grown with a higher Al beam flux after cooling to room temperature, which resulted from the excessive Al flux.