Study of group-III binary and ternary nitrides using X-ray absorption fine structure measurements

It is demonstrated that the NEXAFS spectra are a “fingerprint” of the symmetry and the composition of the binary nitrides GaN, AlN and InN, as well as of their ternary alloys In_0.16Ga_0.84N and Al_yGa_1−yN. From the angular dependence of the N-K-edge NEXAFS spectra, the hexagonal symmetry of the under study compounds is deduced and the (p_x, p_y) or p_z character of the final state is identified. The energy position of the absorption edge (E_abs) of the binary compounds GaN, AlN and InN is found to red-shift linearly with the atomic number of the cation. The E_abs of the Al_yGa_1−yN alloys takes values in between those corresponding to the parent compounds AlN and GaN. Contrary to that, the E_abs of In_0.16Ga_0.84N is red-shifted relative to that of GaN and InN, probably due to ordering and/or phase separation phenomena. The EXAFS analysis results reveal that the first nearest-neighbour shell around the N atom, which consists of Ga atoms, is distorted in both GaN and Al_xGa_1−xN for x<0.5.     

MBE growth of cubic AlyGa1−yN/GaN heterostructures—structural, vibrational and optical properties

Cubic Al_yGa_1−yN/GaN heterostructures on GaAs(0 0 1) substrates were grown by radio-frequency plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction, micro-Raman, spectroscopic ellipsometry, and cathodoluminescence measurements were used to characterize the structural, optical and vibrational properties of the Al_yGa_1−yN epilayers. The AlN mole fraction y of the alloy was varied between 0.07<y<0.20. X-ray diffraction reciprocal space maps demonstrate the good crystal quality of the cubic Al_yGa_1−yN films. The measured Raman shift of the phonon modes of the Al_yGa_1−yN alloy was in excellent agreement with theoretical calculations. Both SE and CL of the Al_yGa_1−yN epilayer showed a linear increase of the band gap with increasing Al-content.     

AlGaN-based UV photodetectors

Al_xGa_1−xN alloys are very attractive materials for application to ultraviolet photodetection. AlGaN photoconductors, Schottky photodiodes, metal–semiconductor–metal photodiodes, p–n junction photodetectors and phototransistors have been recently developed. In this work we analyse the performance of AlGaN-based photodetectors, discussing present achievements, and comparing the characteristics of the various photodetector structures developed to date.     

Indium content determination related with structural and optical properties of InGaN layers

We studied the structural and optical properties of a set of nominally undoped epitaxial single layers of In_xGa_1−xN (0<x0.2) grown by MOCVD on top of GaN/Al₂O₃ substrates. A comparison of composition values obtained for thin (tens of nanometers) and thick (≈0.5 μm) layers by different analytical methods was performed. It is shown that the indium mole fraction determined by X-ray diffraction, measuring only one lattice parameter strongly depend on the assumptions made about strain, usually full relaxation or pseudomorphic growth. The results attained under such approximations are compared with the value of indium content derived from Rutherford backscattering spectrometry (RBS). It is shown that significant inaccuracies may arise when strain in In_xGa_1−xN/GaN heterostructures is not properly taken into account. Interpretation of these findings, together with the different criteria used to define the optical bandgap of In_xGa_1−xN layers, may explain the wide dispersion of bowing parameters found in the literature. Our results indicate a linear, E_g(x)=3.42−3.86x eV (x0.2), “anomalous” dependence of the optical bandgap at room temperature with In content for In_xGa_1−xN single layers.     

A study of the chemical reactions involved in Li–Ca–N system

The chemical reactions and phases involved in the potential flux system of Li–Ca–N for the growth of bulk GaN crystals have been investigated under varying conditions. It is found that no preferential nitrification of Li or Ca by N₂ in Li–Ca melts at 500 °C. Only the ternary compound LiCaN is identified in the Li–Ca–N system under the present experimental conditions. Static N₂ pressures are found to enhance the formation of LiCaN compared to an N₂ stream. LiCaN forms from two possible pathways: one is a modified metathesis chemical reaction represented by Li₃N+Ca→LiCaN+2Li, and the other is a combination chemical reaction represented by Li₃N+Ca₃N₂→3LiCaN. The formation of LiCaN by the metathesis reaction is thermodynamically favored over the other pathway. In addition, the formation of LiCaN might benefit from a slightly larger initial amount of Li₃N compared with Ca or Ca₃N₂.     

AlGaN photodetectors grown on Si(1 1 1) by molecular beam epitaxy

The fabrication and characterisation of Al_xGa_1−xN (0x0.35) photodetectors grown on Si(1 1 1) by molecular beam epitaxy are described. For low Al contents (<10%), photoconductors show high responsivities (10A/W), a non-linear dependence on optical power and persistent photoconductivity (PPC). For higher Al contents the PPC decreases and the photocurrent becomes linear with optical power. Schottky photodiodes present zero-bias responsivities from 12 to 5 mA/W (x=0−0.35), a UV/visible contrast higher than 10³, and a time response of 20 ns, in the same order of magnitude as for devices on sapphire substrate. GaN-based p–n ultraviolet photodiodes on Si(1 1 1) are reported for the first time.     

Impedance spectroscopy analysis of AlGaN/GaN HFET structures

For HFET application a series of samples with 30 nm Al_xGa_1−xN (x=0.02–0.4) layers deposited at 1040°C onto optimised 2 μm thick undoped GaN buffers were fabricated. The Al_xGa_1−xN/GaN heterostructures were grown on c-plane sapphire in an atmospheric pressure, single wafer, vertical flow MOVPE system. Electrical properties of the Al_xGa_1−xN/GaN heterostructures and thick undoped GaN layers were evaluated by impedance spectroscopy method performed in the range of 80 Hz–10 MHz with an HP 4192A impedance meter using a mercury probe. The carrier concentration distribution through the layer thickness and the sheet carrier concentration were evaluated. A non-destructive, characterisation technique for verification of device heterostucture quality from the measured C–V and G–V versus frequency characteristics of the heterostructure is proposed.     

In situ optical monitoring of AlGaN thickness and composition during MOVPE growth of AlGaN/GaN microwave HFETs

Real-time spectral reflectometry has been implemented to monitor the MOVPE growth of AlGaN/GaN microwave HFET structures. The aim is to monitor and control the thickness and composition of the thin AlGaN layer during growth. In order to extract useful information from the in situ spectra the optical constants of AlGaN as a function of alloy composition are required at the growth temperature (1050°C). As the first step to obtaining the high temperature optical constants, a room temperature spectroscopic ellipsometry study (energy range 1.65–4.95 eV) has been carried out on thin AlGaN films of various thickness (30 and 100 nm) and aluminium content (0.15 and 0.25). The multilayer model of each sample from the ellipsometry study is used to generate a reflectance spectrum which is compared with the in situ spectral reflectometry spectrum of the same sample acquired at room temperature to verify the technique. Further work is in progress to model the bandgap and optical constants of GaN and AlGaN at growth temperature.     

Defect reduction in GaN epilayers and HFET structures grown on (0 0 0 1)sapphire by ammonia MBE

The quality of GaN epilayers grown by molecular beam epitaxy on substrates such as sapphire and silicon carbide has improved considerably over the past few years and in fact now produces AlGaN/GaN HEMT devices with characteristics among the best reported for any growth technique. However, only recently has the bulk defect density of MBE grown GaN achieved levels comparable to that obtained by MOVPE and with a comparable level of electrical performance. In this paper, we report the ammonia-MBE growth of GaN epilayers and HFET structures on (0 0 0 1)sapphire. The effect of growth temperature on the defect density of single GaN layers and the effect of an insulating carbon doped layer on the defect density of an overgrown channel layer in the HFET structures is reported. The quality of the epilayers has been studied using Hall effect and the defect density using TEM, SEM and wet etching. The growth of an insulating carbon-doped buffer layer followed by an undoped GaN channel layer results in a defect density in the channel layer of 2×10⁸ cm⁻². Mobilities close to 490 cm²/Vs at a carrier density of 8×10¹⁶ cm⁻³ for a 0.4 μm thick channel layer has been observed. Growth temperature is one of the most critical parameters for achieving this low defect density both in the bulk layers and the FET structures. Photo-chemical wet etching has been used to reveal the defect structure in these layers.     

Nanocrystalline Pr-doped ZnO insulator for metal–insulator–Si Schottky diodes

Pr-doped ZnO (ZnO:Pr) insulating thin films were prepared on glass and Si substrates by oxidation in air. The films were characterised by X-ray diffraction (XRD), energy dispersion X-ray fluorescence (EDXRF), and optical absorption spectroscopy. The molar ratio Pr/Zn of the samples was determined by the EDXRF method. The XRD study shows the formation of nanocrystalline (26–50 nm) nc-Pr-doped ZnO. The optical and electrical conduction were explained by a slight change of stoichiometric composition. The nc-ZnO:Pr/Si heterojunctions are being Schottky barrier diodes (SBDs) and exhibited high rectification behaviour. The parameters describe the current pass through those SBDs were determined according to the available models.     

Hydride-assisted growth of GaN nanowires on Au/Si(0 0 1) via the reaction of Ga with NH3 and H2

High quality, straight GaN nanowires (NWs) with diameters of 50 nm and lengths up to 3 μm have been grown on Si(0 0 1) using Au as a catalyst and the direct reaction of Ga with NH₃ and N₂:H₂ at 900 °C. These exhibited intense, near band edge photoluminescence at 3.42 eV in comparison to GaN NWs with non-uniform diameters obtained under a flow of Ar:NH₃, which showed much weaker band edge emission due to strong non-radiative recombination. A significantly higher yield of β-Ga₂O₃ NWs with diameters of ≤50 nm and lengths up to 10 μm were obtained, however, via the reaction of Ga with residual O₂ under a flow of Ar alone. The growth of GaN NWs depends critically on the temperature, pressure and flows in decreasing order of importance but also the availability of reactive species of Ga and N. A growth mechanism is proposed whereby H₂ dissociates on the Au nanoparticles and reacts with Ga giving Ga_xH_y thereby promoting one-dimensional (1D) growth via its reaction with dissociated NH₃ near or at the top of the GaN NWs while suppressing at the same time the formation of an underlying amorphous layer. The higher yield and longer β-Ga₂O₃ NWs grow by the vapor liquid solid mechanism that occurs much more efficiently than nitridation.     

Anomalous behavior of excess energy curves of InxGa1−xN grown on GaN and InN

We worked out the excess energies for bulk In_xGa_1−xN and In_xGa_1−xN thin films on GaN and InN in order to investigate their thermodynamic stabilities. It has been found that the excess energy maximum shifted toward x0.80 for InGaN/GaN and x0.10 for InGaN/InN due to the lattice constraint in contrast with x0.50 for bulk. Moreover, it has been revealed that the excess energy for InGaN/GaN is larger than that for bulk at x>0.65. This suggests that In-rich films are less stable on GaN than bulk state. These results indicate that the lattice constraint has a significant influence on thermodynamic stabilities of thin films.     

Low temperature II–VI nanowire growth using Au–Sn catalysts

Epitaxial lateral overgrowth is reported for semi-polar (Al,Ga)N(1 1 .2) layers. The mask pattern consisted of periodic stripes of SiO₂ oriented parallel to either the GaN[1 1 .0] or the GaN[1 1 .1] direction. Lateral growth occurred either along GaN[1 1 .1] or along GaN[1 1 .0]. For growth along the [1 1 .0] direction, coalescence was achieved for layer thicknesses >4 μm. However, planarization was not observed yielding extremely corrugated surfaces. For growth in [1 1 .1] direction, coalescence was delayed by a diminishing lateral growth rate. Growth of AlGaN during ELOG resulted in coalescence. Improvement in crystal quality of such buffer layers for the growth of InGaN/GaN quantum wells was confirmed by X-ray diffraction and photoluminescence spectroscopy.     

A comparison of commercial sources of epitaxial material for GaN HFETs fabrication

This paper describes a comparison of material and device results obtained from AlGaN/GaN epitaxial HFET wafers from three commercial sources. Although all three sources supplied material to the same nominal specification, X-ray diffraction, Hall effect and C–V profiling revealed significant differences between them. Wafers from two of the suppliers showed poor inter-device isolation characteristics, indicative of a conducting buffer layer. Wafers from the third supplier showed excellent inter-device isolation, but C–V measurements showed that the AlGaN was about twice as thick as specified, resulting in devices with high pinch-off voltages (−16 V). For the wafers with poor buffer isolation, RF measurements on 1.2 μm gate length devices gave values of f_T 5.0 GHz and values of f_max from 8.0 to 11.7 GHz (exact values depending on DC bias conditions), while for the wafer with over-thick AlGaN the corresponding values were 8.0 and 20.0 GHz.     

AlGaN epitaxial lateral overgrowth on Ti-evaporated GaN/sapphire substrate

AlGaN growth using epitaxial lateral overgrowth (ELO) by metalorganic chemical vapor deposition on striped Ti, evaporated GaN on sapphire, has been investigated. AlGaN/AlN films growth on GaN/AlGaN superlattices (SLs) structure on the Ti masks, with various SLs growth temperature (1030, 1060 and 1090 °C) were grown. With increasing the growth temperature, AlGaN surface became flat. The AlGaN film had a cathodoluminescence peak around 345 nm. However, in secondary ion mass spectrometry (SIMS) measurement, Ti signal was detected on the top of AlGaN surface when GaN/AlGaN SLs was grown on Ti striped masks. By inserting the AlN blocking layer on SLs, Ti diffusion was stopped at the AlN layer, and the AlGaN crystalline quality was improved.     

Optical and electrical properties of Be doped GaN bulk crystals

Highly resistive GaN : Be was obtained by means of synthesis of Ga+Be with atomic nitrogen under high nitrogen pressure. Activation energy of resistivity is about 1.5 eV. This material exhibits features very different from those observed in highly resistive bulk GaN : Mg. Up to 300 K strong yellow band dominates photoluminescence spectrum in resistive GaN : Be crystals. Positron annihilation studies point to the presence of gallium vacancies, V_Ga. In highly resistive GaN:Mg neither yellow band with considerable intensity, nor detectable concentration of V_Ga was found. We also discuss the puzzling findings in highly resistive bulk GaN : Be of morphological features typical for highly conducting bulk n-GaN material.     

Investigation of Ni/Au-contacts on p-GaN annealed in different atmospheres

We investigated the effect of different annealing atmospheres on contact behaviour of Ni/Au contacts on moderately doped p-GaN layers. We used the annealing gases N₂, O₂, Ar, and forming gas (N₂/H₂) at varying annealing temperatures from 350°C to 650°C in steps of 50°C. The p-GaN samples were either metalorganic chemical vapor deposition or molecular beam epitaxy grown. Contact characterization was done after each annealing step by using the circular transmission line model. Specific contact resistances were determined to be in the low 10⁻⁴ Ω cm² range for oxidized contacts. Accompanying chemical analysis using depth resolved Auger electron spectroscopy revealed that NiO was formed and Au diffused towards the interface, whereas annealing in forming gas prevented oxidation and did not lead to Ohmic behaviour.     

XPS and electroluminescence studies on SrS1−xSex and ZnS1−xSex thin films deposited by atomic layer deposition technique

SrS_1−xSe_x and ZnS_1−xSe_x thin films were deposited by the atomic layer deposition (ALD) technique using elemental selenium as the Se source, thus avoiding use of H₂Se or organometallic selenium compounds. X-ray diffraction (XRD) analysis showed that the films were solid solutions and X-ray photoelectron spectroscopy (XPS) data showed that the surface of both ZnS_1−xSe_x and SrS_1−xSe_x were covered with an oxide and carbon-containing contaminants from exposure to air. The oxidation of SrS_1−xSe_x extended into the film and peak shifts from sulfate were found on the surface. Luminance measurements showed that emission intensity of the ZnS_1−xSe_x:Mn alternating current thin film electroluminescent (ACTFEL) devices at fixed voltage was almost the same as that of the ZnS:Mn device, while emission intensity of the SrS_1−xSe_x:Ce devices decreased markedly as compared to the SrS:Ce device. Emission colors of the devices were altered only slightly due to selenium addition.     

Photoluminescence of InGaN/GaN multiple quantum wells grown by mass transport

We report on studies of an In_0.12Ga_0.88N/GaN structure with three 35 Å thick quantum wells (QWs) grown by metalorganic vapor phase epitaxy with employment of mass transport. The mass-transport regions demonstrate a threading dislocation density less than 10⁷ cm⁻². The photoluminescence (PL) spectrum is dominated by a 40 meV—narrow line centered at 2.97 eV at 2 K. This emission has a typical PL decay time of about 5 ns at 2 K within the PL contour. An additional line with longer decay time (about 200 ns) is observed at an energy about 2.85 eV. The position of this line shifts towards higher energies with increasing excitation power. The data are consistent with a model, where the PL originates from at least two nonequivalent QWs, which could be realized due to a potential gradient across the layers.     

Growth of GaN/AlN and AlGaN by MOCVD using triethylgallium and tritertiarybutylaluminium

Films of aluminium nitride (AIN) with thicknesses in the range from 200 to 3600 Å have been deposited at 1050°C by low-pressure MOCVD. Using an alternative precursor, tritertiarybutylaluminium (^tBu₃Al), and ammonia (NH₃), we have grown AlN on sapphire (c-Al₂O₃). At a growth rate of 0.35 μm/h, the FWHM of the rocking curve measured by X-ray diffraction was 150 arcsec. Therefore, we used the thin AlN films as buffer layers for the deposition of gallium nitride (GaN) at 950°C using triethylgallium (Et₃Ga). Aluminium gallium nitride (Al_xGa_1−xN) with aluminium contents x from 0 to 0.5 were grown using a mixture of Et₃Ga and ^tBu₃Al. The strctural and optical properties of GaN, AlGaN and AlN were verified by X-ray diffraction (XRD), spectrally resolved photoconductivity (SPC), photothermal deflection (PDS) and photoluminescence spectroscopies.