Luminescence,vibrational and XANES studies of AlN nanomaterials

The paper reports comparative studies on synthesized aluminium nitride nanotubes, nanoparticles and commercially available micron-sized AlN powder using different spectroscopic techniques: cathodoluminescence measurements (CL), X-ray absorption near edge spectroscopy (XANES) and Fourier-transform infrared spectroscopy (FTIR). Crucial distinctions in CL spectra are observed for nano- and microsized aluminium nitride powders; systematic shift of the IR absorption maximum has been detected for nanostructured aluminium nitride as compared to commercial samples. Through XANES experiments on Al K-edge structural differences between nano- and bulk AlN are revealed, intensity of features in absorption spectra has been found to be a function of wurtzite and zincblend phases amount in nanostructured samples.     

Cubic BN Sintered with A1 under High Temperature and High Pressure

Sintering of cubic boron nitride （cBN） with addition of A1 is carried out in the temperature range 1300-1500℃ and under the pressure 5.5 GPa. When sintered at 1300℃, a weak diffractive peak of hexagonal BN （hBN） is observed in the Al-cBN sample, indicating the transformation from cBN to hBN. No nitrides or borides of A1 are observed, which indicated that A1 does not react with cBN obviously. When the sintering temperature is increased to 1400℃, the diffractive peak of hBN disappears and new phases of A1N and A1B2 are observed, due to reactions between A1 and cBN. When the sintering temperature is further increased to 1500℃, the contents of A1N and A1B2 phases increase and the A1 phase disappears completely.     

氮化铝铬的制备及其光学性质

利用直接氮化法得到了氮化铝和氮化铬,并用两种途径得到Cr³⁺掺杂的氮化铝样品。用X射线衍射仪分析了样品晶相并测试了两种样品的激发和发射光谱,计算了晶体场劈裂参数D_q和Racah参数B及D_q/B分别为1 800,693.69和2.59。光谱数据表明,Cr³⁺在氮化铝中属于强场环境,光发射来自于最低激发态²E能级,与在氧化铝中的环境相似。根据光谱数据给出了Cr³⁺在氮化铝晶体场中的能级。     

Formation and properties of rocksalt-type AlN and implications for high pressure phase relations in the system Si–Al–O–N

Pressure-dependent thermodynamic properties of the ambient and high pressure phases of aluminum nitride (w-AlN and rs-AlN) were calculated from first principles in order to determine their phase boundary in the p? T phase diagram. These predictions were checked by static HP/HT experiments, using a multianvil press and an Al/N/H precursor with low decomposition temperature as educt. The experimental data show that at temperatures between 1000 and 2000 K, the boundary line between the two phases is situated between 11 and 12 GPa, which is ～1.3 GPa lower than the theoretical result and generally lower than previously assumed. The hardness of rs-AlN – measured for the first time – is ～30 GPa (Knoop indenter at loads of 25–50 g), twice as hard as w-AlN. Shock wave recovery experiments on nano w-AlN allowed testing of the chemical and thermal stability of rs-AlN, and determination of its infrared absorption and ²⁷Al NMR data. The shock wave technique will eventually enable the synthesis of larger amounts of rs-AlN, making it available for technological use. Finally, implications on the high pressure stability of phases in the Si–Al–O–N system are discussed in the light of thermoelastic properties of AlN.     

Surface nanostructural modifications of Ti implanted by N+ ions as a function of energy

The surface modification of titanium foil/sheet samples (0.5?mm thickness) implanted by nitrogen ions of different energy and fluence of 1?×?10^18?N^+?cm^?2 was studied using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy and secondary-ion mass spectrometry (SIMS). XRD patterns showed the development of titanium nitride with different compositions in the implanted samples, and the presence of different titanium compositions such as titanium oxides was also observed. AFM images at 16 and 20?keV showed the formation of grains, which were attributed to the initial sputtering of grain boundaries. The morphology of the surface changed at 25?keV showing granular structure with an almost uniform background and lowest surface roughness relative to lower and higher implantation energies. A correlation was obtained between all results for XRD, SIMS and AFM except the titanium nitride maximum intensity at 25?keV N⁺ implantation. In order to achieve more detailed information about the role of N⁺ energy in this kind of work it is proposed that a further investigation is needed on both N⁺ energy and substrate temperature as well as some theoretical studies.     

Luminescence of thulium-activated cubic boron nitride

Under high pressure and temperature conditions, we have obtained samples of thulium-activated cubic boron nitride in the form of micropowders, ceramics, and polycrystals activated by thulium in the presence of aluminum. We studied the cathodoluminescence (CL), photoluminescence (PL), and photoluminescence excitation spectra of the samples. In the luminescence spectra we observe structured bands with maxima at ∼370, ∼475, ∼660, and ∼ 800 nm, assigned to electronic transitions in the triply charged thulium ions. We have established that the most efficient method for excitation of “blue” luminescence at ∼475 nm for thulium ions in cBN is excitation by an electron beam. The cBN samples synthesized in the presence of Al have photoluminescence spectra with a more complex structure compared with samples not containing Al, with the band of dominant intensity at about 660 nm. Hypothetically, this is a consequence of incorporation of thulium ions into the crystalline phases cBN and AlN, which are equally likely to be formed during synthesis. The observed photoluminescence spectrum of the indicated samples is the superposition of the photoluminescence spectra of the Tm³⁺ ions located in the crystal fields of cBN and AlN of different symmetries. The presence in the photoluminescence excitation spectra (at 450, 490, and 660 nm) of structure, with features at wavelengths shorter than the excited photoluminescence, suggests a nonresonant mechanism for its excitation. We have established that luminescence of Tm³⁺ ions is less intense than for other rare earth elements incorporated into cubic boron nitride. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 547–555, July–August, 2008.     

Dependence of surface nano-structural modifications of Ti implanted by N ions on temperature

The surface modification of titanium thin foil/sheet samples (0.5 mm) implanted by nitrogen ions of 30 keV energy and a fluence of 1 × 10¹⁸ N⁺ cm⁻² at different temperatures is studied using XRD, AFM, SEM, and SIMS. XRD patterns showed the development of titanium nitride with different compositions in the implanted samples, while the presence of different titanium compositions such as titanium oxides was also observed. AFM images at 654 K showed the formation of grains, that after initial sputtering of the grain boundary at 728 K temperature, the morphology of the surface changed from small grains to a bimodal distribution of grains at 793 K which consisted of larger grains with bright hillocks within them. This was considered to be due to phase transformation/compositional changes, explained by correlating XRD and SIMS results. The SIMS results showed a maximum at about 730 K and a minimum at about 790 K for both N⁺ density and depth of N⁺ penetration in the Ti sample. The variation of these results with temperature was explained on the basis of the residual gas, substrate temperature, dissociation of water in the chamber and the gettering property of titanium.     

Strain modification of AlGaN layers using swift heavy ions

Epitaxial AlGaN/GaN layers grown by molecular beam epitaxy (MBE) on SiC substrates were irradiated with 150 MeV Ag ions at a fluence of 5×10¹² ions/cm². The samples used in this study are 50 nm Al_0.2Ga_0.8N/1 nm AlN/1 μ m GaN/0.1 μ m AlN grown on SI 4H-SiC. Rutherford backscattering spectrometry/channeling strain measurements were carried out on off-normal axis of irradiated and unirradiated samples. In an as-grown sample, AlGaN layer is partially relaxed with a small tensile strain. After irradiation, this strain increases by 0.22% in AlGaN layer. Incident ion energy dependence of dechanneling parameter shows E ^1/2 dependence, which corresponds to the dislocations. Defect densities were calculated from the E ^1/2 graph. As a result of irradiation, the defect density increased on both GaN and AlGaN layers. The effect of irradiation induced-damages are analyzed as a function of material properties. Observed results from different characterization techniques such as RBS/channeling, high-resolution XRD and AFM are compared and complemented with each other to deduce the information. Possible mechanisms responsible for the observations have been discussed in detail.     

Influence of substrate crystallography on the room temperature synthesis of AlN thin films by reactive sputtering

A pulsed DC reactive ion beam sputtering system has been used to synthesize aluminium nitride (AlN) thin films at room temperature by reactive sputtering. After systematic study of the processing variables, high-quality polycrystalline films with preferred c-axis orientation have been grown successfully on silicon and Au/Si substrates with an Al target under a N₂/(N₂ + Ar) gas flow ratio of 55%, 2 mTorr processing pressure and keeping the temperature of the substrate holder at room temperature. The crystalline quality of the AlN layer as well as the influence of the substrate crystallography on the AlN orientation has been characterized by high-resolution X-ray diffraction (HR-XRD). Best ω-FWHM (Full Width at Half Maximum) values of the (0 0 0 2) reflection rocking curve in the 1 μm thick AlN layers are 1.3°. Atomic Force Microscopy (AFM) measurements have been used to study the surface morphology of the AlN layer and Transmission Electron Microscopy (TEM) measurements to investigate the AlN/substrate interaction. AlN grew off-axis from the Si substrate but on-axis to the surface normal. When the AlN thin film is deposited on top of an Au layer, it grows along the [0 0 0 1] direction but showing a two-domain structure with two in-plane orientations rotated 30° between them.     

CMOS-compatible light-emitting devices based on thin aluminum nitride film containing Al nanocrystals

Electroluminescence (EL) from Al-rich AlN thin films grown on p-type Si substrate by radio frequency (RF) magnetron sputtering has been observed at room temperature. The light-emitting structure based on the thin films can be driven by an electrical pulse as short as 10⁻⁵ s. No obvious change in the light emission intensity was observed after 10⁶ pulse cycles. It has been found that the light emission intensity increases with the Al concentration. It is shown that the phenomenon is due to the enhancement of the percolative conduction via the Al nanocrystals distributed in the AlN matrix as a result of the increase in Al concentration.     

Study of field emission and dielectric properties of AlN films prepared by DC sputtering technique at different substrate temperatures

Nanocrystalline AlN thin films were prepared via DC sputtering technique at different substrate temperature. The crystal orientation and particle size of aluminum nitride thin films were investigated by XRD analysis. Study indicated that the sample contained pure phase hexagonal AlN nanoparticles with a single peak corresponding to the (100) planes. The peak at 665 cm⁻¹ in the FTIR spectrum of film was assigned to the LO phonon of hexagonal AlN. The particle size of the film, prepared at substrate temperature 200°C was about 9.5 nm, as investigated by atomic force microscope. Field emission study indicated that it can be used as a good field emitter. Turn-on field (E_to) of 15.02 V/μm was observed for the AlN films synthesized at substrate temperature 200°C. Dielectric constant of the AlN film was found nearly independent of frequencies in the measured frequency range 1 KHz to 1 MHz, i.e. in the audio frequency range. The values of dielectric constant (ε) were 10.07, 9.46 and 8.65 for the film prepared at 70°C, 150°C and 200°C, respectively, at frequency 1 KHz.     

Deposition of aluminum nitride thin film on Si(1 1 1) by KrF excimer laser and its characterizations

We present the deposition of aluminum nitride (AlN) thin film by KrF excimer laser sputtering and the study of the effects of substrate temperature and laser fluences. Deposition rate of AlN thin film at 0.3 Å/pulse has been achieved with laser fluence of 1500 mJ/cm² and at substrate temperature of 250 K, and this shows the enhancement of the deposition rate at low substrate temperature. Surface morphology of the deposited films is characterized by atomic force microscopy (AFM). In addition, the electrical performance of the MIS devices with AlN thin films prepared in this experiment has been characterized.     

AlN thin films prepared by ArF plasma assisted PLD. Role of process conditions on electronic and chemical–morphological properties

Aluminium nitride thin films were deposited on n-Si <100> substrates by RF plasma activated reactive pulsed laser deposition (PLD). An ArF excimer pulsed laser, 10 Hz and 2.5 J/cm² energy fluence, has been used to ablate a pure Al target in a reactive atmosphere of N₂ plasma (generated by a RF source), at varying processing parameters (substrate temperature, time, and N₂ plasma configuration). We studied the dependence and correlation of structural and electronic properties with the experimental conditions. The chemical composition of deposited material has been determined by both Raman and X-ray photoelectron spectroscopy (XPS). Electrical resistivity has been evaluated by the sheet resistance method. Both spectroscopic characterizations (Raman and XPS) show a strong dependence in the formation of AlN on the deposition temperature. At low temperatures, there is little formation of nitride, with a prevalence of aluminium oxide, while at higher temperatures the N uptake increases, with AlN formation. Raman analysis also highlights the formation of nano-structures, for temperatures ≥400^°C. These material characteristics have a fundamental influence on the electronic properties. Indeed, electrical resistivity properties have been found to be strongly dependent on the film structure, nitrogen incorporation, and presence of mixed oxide compounds, closely related to deposition temperature.     

Structural characterisation of aluminium layered double hydroxides by Al solid-state NMR

²⁷Al solid-state NMR has been applied to study the local structure of pristine and chemically modified aluminium layered double hydroxides (LDH). The pristine LDH only shows six-fold coordinated, octahedral, aluminium, while the calcined and subsequently surfactant treated LDH sample shows a significant fraction of four-fold coordinated tetrahedral aluminium. The co-existence of two types of octahedral sites with different quadrupolar parameters is clearly observed in both samples. Quadrupolar coupling constants and isotropic chemical shifts have been measured from the ²⁷Al triple-quantum MAS NMR allowing to fit the ²⁷Al MAS spectra and quantify the different species in the samples. The quantitative analysis reveals that 30% of the aluminium is in four-fold coordination in the surfactant-modified LDH. We show that this chemical modification retains the two types of AlO₆ sites with a decreased intensity of the site showing the lowest quadrupolar coupling constant.     

The formation of V–Al–N thin films by reactive ion beam mixing of V/Al interfaces

The reactive ion beam mixing (IBM) of V/Al interfaces by low-energy N₂⁺ ions at room temperature leads to the formation of V–Al–N ternary nitride thin films. The kinetics, growth mechanisms, composition and electronic structure of those films have been studied using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, Factor Analysis and Monte Carlo TRIDYN simulations. The comparison of experimental results with those obtained from TRIDYN simulations suggests that the chemical reaction with the nitrogen partial pressure and processes driven by residual defects are the rate-controlling mechanisms during the reactive IBM of V/Al interfaces. The kinetics of mixing is characterized by two stages. During the first stage (≤4×10¹⁶ ions/cm²), the formation of vanadium nitride is observed. In the second stage, vanadium nitride is transformed into a V–Al–N ternary nitride due to Al incorporation in the near surface region. Moreover, the V/Al ratio can be varied in a broad range, whereas the nitrogen concentration slightly decreases with increasing the aluminium content of the film.     

Synthesis,structural, optical and magnetic properties of Cu-doped ZnO nanorods prepared by a simple direct thermal decomposition route

Cu-doped ZnO nanorods (i.e. Cu = 1.75, 3.55, 5.17 and 6.39 at.%) have been successfully synthesized by simple, direct, thermal decomposition of zinc and copper acetates in air at 300 °C for 6 h. The prepared samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy. The XRD results indicate that the 1.75 at.% Cu-doped ZnO sample has a pure phase with the ZnO wurtzite structure, while the impurity phases are detected with increasing Cu concentrations. It was found that the doping of Cu results in a reduction of the preparation temperature. The optical properties of the samples were also investigated by UV–visible spectroscopy and photoluminescence measurements. The results show that the Cu doping causes the change in energy-band structures and effectively adjusts the intensity of the luminescence properties of ZnO nanorods. X-ray photoelectron spectroscopy analysis implies that there are some oxygen vacancies in the samples and also indicates that all the doped samples are associated with the mixture of Cu ion states (Cu²⁺ and Cu¹⁺/Cu⁰). Magnetic measurements by vibrating sample magnetometry indicate that undoped ZnO is diamagnetic, whereas all of the Cu-doped ZnO samples exhibit room temperature ferromagnetic behavior. We suggest that Cu substitution and density of oxygen vacancies (V _o) may play a major role in the room temperature magnetism of the Cu-doped ZnO samples.     

Ultrathin amorphous Ti–Al film used as a diffusion barrier for copper metallization

The viability of ultrathin amorphous Ti–Al film (～4 nm) as a diffusion barrier layer between Cu and Si for the application in Si-based ultra-large scale integration (ULSI) has been investigated. The Cu/Ti–Al/Si heterostructures are annealed in a high vacuum at various temperatures. There is no impurity peaks in the X-ray diffraction patterns for the samples up to annealing temperature of 800 ^°C, although the island-like grains were observed on the surface of the 800 ^°C annealed sample due to dewetting and agglomeration of the Cu film. No inter-reactions can be found from the images of transmission electron microscopy and Ti–Al is still amorphous after high-temperature annealing. These results indicate that Ti–Al film can effectively separate Cu from Si at high temperatures, and that the amorphous ultrathin Ti–Al film can be a very good barrier layer for Cu metallization.     

Fabrication of nanopatterned sapphire substrates by annealing of patterned Al thin films by Laser Interference Lithography

Nanopatterned sapphire substrates were fabricated by annealing of patterned Al thin films. Square-patterned Al thin films with the diagonal length of 600 nm, period of 1 um and height of ～200 nm were obtained by the Laser Interference Lithography and Reactive Ion Etching. Patterned Al thin films were subsequently subjected to dual stage annealing due to the melting temperature of Al thin films (660 ^°C). The first comprised a low temperature oxidation anneal. The hillocks formation on Al thin films was minimized with an oxidation annealing at 450 ^°C for 24 h. The little change in the morphology of patterned Al thin films was observed at 450 ^°C for 24 h. This was followed by a high temperature annealing to induce growth of the underlying sapphire single crystal to consume the oxide layer. The SEM results show the patterns were retained on sapphire substrates after high temperature annealing at less than 1200 ^°C. The XRD and Raman results reveal that the orientation of island patterns by dual stage annealing of patterned Al thin films for 24 h at 450 ^°C, and 1 h at 1000 ^°C, was the same as that of the sapphire (0001) substrates.     

Comparative study between melted and mechanically alloyed samples of the Fe50Mn10Al40 nanostructured system

Nanostructured powders of melted and 48 h-mechanically alloyed (MA) samples of the Fe₅₀Mn₁₀Al₄₀ system were studied by XRD, SEM and Mössbauer spectroscopy (MS), and their properties were compared. The samples present BCC structure with similar mean lattice parameter (near 2.92 Å) and grain size (around 22 nm). The MA sample presents additionally the α-Fe phase. Mössbauer spectra of the samples present a hyperfine field distribution (HFD), a broad paramagnetic (P) site and a sextet showing that the BCC ternary phase is disordered with Fe sites in environments rich in Fe (HFD) and rich in Al and Mn (P), respectively. The mean hyperfine magnetic field vs. temperature curve of melted sample presents two kinks, one at 28 K and other at 210 K and a Curie temperature at 340 K. A similar curve is observed for the milled sample but the kinks occur at 65 and 265K. Mössbauer spectra at different temperatures with and without applied field permit to conclude that the low temperature anomaly corresponds to the freezing temperature of a re-entrant spin-glass phase (RSG) and that of the second one corresponds to a blocking temperature of a superparamagnetic (SP) phase. These phases are possible in the samples due to their disordered character induced by the preparation conditions and the competitive interactions of the Fe and Mn atoms. The enhancement of the magnetic behaviour of the MA sample is due its larger disorder induced by the preparation method that can also explain the increase of the RSG and SP transition temperatures.     

Physical and mechanical properties of C60 under high pressures and high temperatures

The physical and mechanical properties of a C₆₀ fullerene sample have been investigated under high pressure–high temperature conditions using a designer Diamond Anvil Cell. Electrical resistance measurements show evidence of C₆₀ cage collapse at 20 GPa, which leads to the formation of an insulating phase at higher pressure. Energy dispersive X-ray diffraction (EDXD) data indicated that the characteristic fcc reflections gradually decrease in intensity and eventually disappear above 28 GPa. A C₆₀ sample was laser-heated at a pressure of 35 GPa to a temperature of 1910±100 K and, subsequently, decompressed to ambient conditions. The photoluminescence spectra and the Raman spectrum of the pressure–temperature-treated sample were measured at a low temperature of 80 K. Raman peak at 1322.3 cm^?1 with full-width half-maximum of 2.9 cm^?1 was observed from the sample, which is attributed to the hexagonal diamond phase in the sample. The room temperature photoluminescence spectra showed a symmetric emission band centered in the red spectral range with a peak at 690 nm. The structural analysis of the pressure–temperature-processed C₆₀ sample using EDXD method showed strong internal structure orientation and a phase close to hexagonal diamond. Mechanical properties such as hardness and Young’s modulus were measured by nanoindentation technique and the values were found to be 90±7 and 1215±50 GPa, respectively and these values are characteristic of sp³-bonded carbon materials.