Structural properties of 10 μm thick InN grown on sapphire (0001)

The structural properties of a 10 μm thick In-face InN film, grown on Al₂O₃ (0001) by radio-frequency plasma-assisted molecular beam epitaxy, were investigated by transmission electron microscopy and high resolution x-ray diffraction. Electron microscopy revealed the presence of threading dislocations of edge, screw and mixed type, and the absence of planar defects. The dislocation density near the InN/sapphire interface was 1.55×10¹⁰ cm⁻², 4.82×10⁸ cm⁻² and 1.69×10⁹ cm⁻² for the edge, screw and mixed dislocation types, respectively. Towards the free surface of InN, the density of edge and mixed type dislocations decreased to 4.35×10⁹ cm⁻² and 1.20×10⁹ cm⁻², respectively, while the density of screw dislocations remained constant. Using x-ray diffraction, dislocations with screw component were found to be 1.2×10⁹ cm⁻², in good agreement with the electron microscopy results. Comparing electron microscopy results with x-ray diffraction ones, it is suggested that pure edge dislocations are neither completely randomly distributed nor completely piled up in grain boundaries within the InN film.     

Blue cathodoluminescence from thulium implanted AlxGa1−xN and InxAl1−xN

Room temperature cathodoluminescence (RTCL) was obtained from Tm implanted Al_xGa_1−xN with different AlN contents (in the range 0≤x≤0.2) and from implanted In_xAl_1−xN with different InN contents (x=0.13 and 0.19) close to the lattice match with GaN. The Tm³⁺ emission spectrum depends critically on the host material. The blue emission from Al_xGa_1−xN:Tm peaks in intensity for an AlN content of x0.11. The emission is enhanced by up to a factor of 50 times with an increase of annealing temperature from 1000 to 1300 C. The blue emission from In_0.13Al_0.87N:Tm, annealed at 1200 C, is more than ten times stronger than that from Al_xGa_1−xN:Tm, x≤0.2. However, the intensity decreases significantly as the InN fraction increases from 0.13 to 0.19.     

Growth and characterisation of GaN with reduced dislocation density

Two GaN MOVPE growth methods to reduce the threading dislocation (TD) density have been explored. The combined effects of (1) in situ SiN_x masking of the sapphire substrate and (2) starting the epitaxial growth at low V-to-III ratio on the GaN film quality were studied by atomic force microscopy, transmission electron microscopy and high-resolution X-ray diffraction. It was found that the annealing condition of the low-temperature nucleation layer after in situ SiN_x masking is critical in order to decrease the density of nucleation sites and hence increase the average grain size to about 5 μm. However, the coalescence of large grains with vertical side facets results in the formation of dense bundles of TDs at the grain boundaries combined with large numbers of basal-plane dislocation loops throughout the film. The formation of these dislocations can be prevented by starting the epilayer growth at low V-to-III ratio, resulting in the formation of grains with inclined side facets. The interaction of the TDs with the inclined side facets causes the dislocations to bend 90 as the grains grow in size and coalesce. GaN films with dislocation densities as low as 1×10⁸ cm⁻², giving full-width at half-maximum values of 180 and 220 arcsec for respectively (002) and (302) omega scans, were achieved by the combination of in situ masking and low V–III ratio epilayer growth. Hall carrier mobility values in excess of 900 cm² V ⁻¹ s⁻¹ were deduced for Si-doped layers.     

Structural relation and epitaxial properties of hexagonal InN and oxidized cubic In2O3

The epitaxial properties and structural relation between hexagonal InN and cubic In₂O₃ phases were studied by synchrotron X-ray scattering and X-ray photoelectron spectroscopy. The cubic bixbyite In₂O₃ phase on the sapphire(0001) substrate was formed after an annealing time of 10 min at 10⁻⁵ Torr after the hexagonal InN film was grown at 550 °C, above the dissociation temperature of InN, by RF-magnetron sputtering. The crystal orientation was cubic In₂O₃(222), parallel to Al₂O₃(0001) and parallel to hexagonal InN(0002) before the oxidation process. The cubic In₂O₃ phase was believed to be formed layer by layer by the oxidation of the hexagonal InN phase.     

Raman scattering in InN films and nanostructures

Studies of lattice dynamics devoted to wurtzite InN are presented. Raman scattering experiments on both InN thin films and nanometric islands grown by Metal–Organic Vapor Phase Epitaxy (MOVPE) were performed at room temperature. From the Raman spectra recorded from InN films under hydrostatic pressure up to 13 GPa, linear pressure coefficients and the corresponding Grüneisen parameters for both E₂ and A₁(LO) phonons were extracted for the wurtzite structure up to 11 GPa, close to the starting pressure of the hexagonal to rock-salt phase transition of InN. Spectra at higher pressure suggest that InN undergoes a gradual phase transition, and the reverse transition exhibits a strong hysteresis effect during the downstroke. Then, we discuss recent results on large single InN islands grown on GaN buffer layers, obtained by spatially resolved micro-Raman measurements. The magnitude of the residual strain is estimated, using a recent determination of phonon deformation potentials. It is found to vary linearly as a function of island height.     

Correlation between structural and electrical properties of InN thin films prepared by molecular beam epitaxy

The strain-relaxation phenomena and the formation of a dislocation network in 2H-InN epilayers during molecular beam epitaxy are reported. The proposed growth model emphasizes the dominant role of the coalescence process in the formation of a dislocation network in 2H-InN. Edge type threading dislocations and dislocations of mixed character have been found to be the dominating defects in wurtzite InN layers. It is demonstrated that these dislocations are active suppliers of electrons and an exponential decay of their density with the thickness implies a corresponding decay in the carrier density. Room temperature mobility in excess of 1500 cm² V ⁻¹ s⁻¹ was obtained for 800 nm thick InN layers with dislocation densities of 3×10⁹ cm⁻².     

Characterisation of defects in rare earth implanted GaN by deep level transient spectroscopy

Deep level transient spectroscopy (DLTS) was used to investigate the electrical properties of GaN implanted with the rare earth (RE) ions erbium and thulium. The GaN layers have been grown by metal-organic chemical vapor deposition (MOCVD) onto (0001) sapphire substrates. We used the channeled implantation geometry to implant a dose of 5×10¹⁴ RE cm⁻² with an energy of 150 keV. For each species, two different annealing procedures were used in a nitrogen atmosphere for 120 s. Indeed, the annealing temperature plays an important role in the lattice recovery, even if RE-related defects remain present. After annealing at 1000 C, the appearance of two new peaks, for both studied RE ions, is associated with the lattice damage induced by the implantation, such as the presence of nitrogen vacancies. After annealing at 1100 C, the recovery of the lattice is observed while a hole trap appears for both implanted RE ions with corresponding energy values E_v+0.61 eV and E_v+1.59 eV, in the case of Er and Tm, respectively.     

Structure and morphology of the reaction fronts during the formation of MgAl2O4 thin films by solid state reaction between R-cut sapphire substrates and MgO films

The thin-film spinel-forming solid state reaction between Al₂O₃ and MgO has been studied under initially non-coherent conditions. MgO films in (001) orientation on -cut sapphire single crystals were heated at 1100°C for 30 min or 1h. The film/substrate reaction proceeds via cation counterdiffusion as was revealed by a marker experiment. The MgAl₂O₄ films formed were predominantly (001) oriented, with an additional systematic tilt of about 5° of the spinel lattice around the [010] axis. The structure of the Al₂O₃ /MgAl₂O₄(001) and MgAl₂O₄(001)/MgO(001) reaction fronts has been investigated on cross section samples by high-resolution electron microscopy. It appeared that after starting from an incoherent interface, the Al₂O₃ /MgAl₂O₄(001) front assumes an almost fully coherent structure during the reaction. As a result the lattice misfit is reduced to 1%, and interfacial ledges are formed. The latter most probably play an active role in the necessary c.p.h. f.c.c. reconstruction of the oxygen sublattice. The MgAl₂O₄(001)/MgO(001) reaction front consists of coherent regions divided by misfit dislocations. During the reaction the former run ahead whereas the latter lag behind. As a result the morphology of the reaction front is bowed. The results confirm earlier observations of Carter and Schmalzried of the semicoherent Al₂O₃(00.1)/CoAl₂O₄(111) interface, thus strongly supporting the conclusion of a fundamental new phase transformation mechanism specific to oxide systems.Presented at the workshop on High-Voltage and High-Resolution Electron Microscopy, February 21–24, 1994, Stuttgart, Germany.     

GaN/AlN quantum dot photodetectors at 1.3–1.5 μm

We have demonstrated GaN/AlN quantum dots (QD) photodetectors, relying on intraband absorption and in-plane carrier transport in the wetting layer. The devices operate at room temperature in the wavelength range 1.3–1.5 μm. Samples with 20 periods of Si-doped GaN QD layers, separated by 3 nm-thick AlN barriers, have been grown by plasma-assisted molecular-beam epitaxy on an AlN buffer on a c-sapphire substrate. Self-organized dots are formed by the deposition of 5 monolayers of GaN under nitrogen-rich conditions. The dot height is 1.2±0.6 to 1.3±0.6 nm and the dot density is in the range 10¹¹–10¹² cm⁻². Two ohmic contacts were deposited on the sample surface and annealed in order to contact the buried QD layers. The dots exhibit TM polarized absorption linked to the s–p_z transition. The photocurrent at 300 K is slightly blue-shifted with respect to the s–p_z intraband absorption. The responsivity increases exponentially with temperature and reaches a record value of 10 mA/W at 300 K for detectors with interdigitated contacts.     

Anisotropy of the dielectric function for wurtzite InN

A -plane InN film grown by molecular beam epitaxy on -plane sapphire substrate with an AlN nucleation layer and a GaN buffer was studied by spectroscopic ellipsometry. The data analysis yields both the ordinary and the extraordinary dielectric tensor components perpendicular and parallel to the optical axis, respectively. Strong optical anisotropy is demonstrated over the whole energy range from 0.72 up to 9.5 eV. The line shapes of the tensor components and the polarisation behaviour are in very good agreement with the results of recently published band structure and dielectric function calculations. Above the band gap, five van Hove singularities are evidenced from the ordinary component, while three are resolved from the extraordinary part. The polarisation dependence below 1 eV can be interpreted in terms of optical selection rules for three energetically split valence bands around the Γ-point of the Brillouin zone, similar to the well known behaviour of wurtzite GaN. This emphasises a band gap of hexagonal InN of about 0.7 eV.     

Free-to-bound radiative recombination in highly conducting InN epitaxial layers

We present a theoretical simulation of near-band-edge emission spectra of highly conducting n-InN assuming the model of ‘free-to-bound’ radiative recombination (FBRR) of degenerate electrons from the conduction band with nonequilibrium holes located in the valence band tails. We also study experimental photoluminescence (PL) spectra of highly conducting InN epitaxial layers grown by MBE and MOVPE with electron concentrations in the range (7.7×10¹⁷–6×10¹⁸) cm⁻³ and find that the energy positions and shape of the spectra depend on the impurity concentration. By modeling the experimental PL spectra of the InN layers we show that spectra can be nicely interpreted in the framework of the FBRR model with specific peculiarities for different doping levels. Analyzing simultaneously the shape and energy position of the InN emission spectra we determine the fundamental bandgap energy of InN to vary between E_g=692 meV for effective mass m_n0=0.042m₀ and E_g=710 meV for m_n0=0.1m₀.     

Preparation and characterization of GaN films by radio frequency magnetron sputtering and carbonized-reaction technique

Radio frequency magnetron sputtering/post-carbonized-reaction technique was adopted to prepare good-quality GaN films on Al₂O₃(0 0 0 1) substrates. The sputtered Ga₂O₃ film doped with carbon was used as the precursor for GaN growth. X-ray diffraction (XRD) pattern reveals that the film consists of hexagonal wurtzite GaN. X-ray photoelectron spectroscopy (XPS) shows that no oxygen can be detected. Electrical and room-temperature photoluminescence measurements show that good-quality polycrystalline GaN films were successfully grown on Al₂O₃(0 0 0 1) substrates.     

Epitaxial growth of ZnSiN2 single-crystalline films on sapphire substrates

A new family of wide band gap nitride semiconductors expressed as II–IV-N₂ have recently attracted attention due to their expected properties such as optical non-linearity. In addition, among these compounds, ZnGeN₂ and ZnSiN₂ have lattice parameters close to GaN and SiC respectively. Up to now, there is very little work reported on this class of materials and no systematic thin film growth study has been reported to date. In this paper we present the first study on the growth of ZnSiN₂ on c-sapphire and (100) silicon substrates using low pressure MOVPE technique. Triethylamine:dimethylzinc adduct, silane diluted in H₂ and ammonia were used as source materials. Single crystalline epitaxial ZnSiN₂ layers were obtained on nitridated c-sapphire substrates in the temperature range 873–973 K by using an adapted II/IV molar ratio ranging from 1.2 to 12. Assuming an orthorhombic unit cell, the lattice parameters calculated from the X-ray diffraction data are a=0.534 nm, b=0.617 nm and c=0.504 nm.     

Role of crystal orientation on the magnetic properties of CoFe2O4 thin films grown on Si (1 0 0) and Al2O3 (0 0 0 1) substrates using pulsed laser deposition

We report the influence of crystal orientation on the magnetic properties of CoFe₂O₄ (CFO) thin films grown on single crystal Si (1 0 0) and c-cut sapphire (Al₂O₃) (0 0 0 1) substrates using pulsed laser deposition technique. The thickness was varied from 200 to 50 nm for CFO films grown on Si substrates, while it was fixed at 200 nm for CFO films grown on Al₂O₃ substrates. We observed that the 200 and 100 nm thick CFO-Si films grew in both (1 1 1) and (3 1 1) directions and displayed out-of-plane anisotropy, whereas the 50 nm thick CFO-Si film showed only an (1 1 1) orientation and an in-plane anisotropy. The 200 nm thick CFO film grown on an Al₂O₃ substrate was also found to show a complete (1 1 1) orientation and a strong in-plane anisotropy. These observations pointed to a definite relation between the crystalline orientation and the observed magnetic anisotropy in the CFO thin films.     

Molecular beam epitaxy of GaN on a substrate of MoS2 layered compound

The feasibility of MoS₂ layered compound as a substrate for GaN growth was investigated. GaN films were successfully grown on MoS₂ by plasma-enhanced molecular beam epitaxy and the crystal quality of GaN on MoS₂ was compared with that on Al₂O₃. For GaN grown on MoS₂ substrate, it was found that the surface flatness observed by atomic force microscopy, stress in the film measured by Raman spectroscopy, optical properties measured by photoluminescence spectroscopy, and threading dislocation density observed by transmission electron microscopy show superior properties compared with that grown on Al₂O₃. These results suggest the layered compound such as MoS₂, which has no dangling bonds on the surface and has lattice mismatching of 0.9% to GaN, has high potential for a substrate of GaN growth. Received: 1 March 1999 / Accepted: 8 March 1999 / Published online: 26 May 1999     

Far-infrared dielectric functions and phonon spectra of alloys determined by spectroscopic ellipsometry

We have used spectroscopic ellipsometry to determine the complex dielectric function of a series of ternary Be_xZn_1−xTe thin films grown by molecular beam epitaxy. The II–VI semiconductor alloys were grown on InP substrates that had an InGaAs buffer layer. After the growth, X-ray diffraction experiments were performed in order to determine the alloy concentration. A standard inversion technique was used to obtain the dielectric functions from the measured ellipsometric spectra, obtained between 2000 nm (5000 cm⁻¹) and 40,000 nm (250 cm⁻¹). By modelling the dielectric function as a collection of oscillators, representing longitudinal and transverse optical phonons of the Be_xZn_1−xTe lattice, we were able to recover the phonon spectra for this alloy system. It is argued that the additional phonon modes that are obtained from ellipsometry are best understood from the recently-proposed percolation model.     

Epitaxial growth of InN on nearly lattice-matched (Mn,Zn)Fe2O4

We have grown InN films on nearly lattice-matched (Mn,Zn)Fe₂O₄ (111) substrates at low temperatures by pulsed laser deposition (PLD) and investigated their structural properties. InN films grown at substrate temperatures above 400 °C show poor crystallinity, and their in-plane epitaxial relationship is [10-10]InN//[11-2](Mn,Zn)Fe₂O₄, which means that their lattice mismatch is quite large (11%). By contrast, high quality InN films with flat surfaces can be grown at growth temperatures lower than 150 °C with the ideal in-plane epitaxial relationship of [11-20]InN//[11-2](Mn,Zn)Fe₂O₄, which produces lattice mismatches of as low as 2.0%. X-ray reflectivity measurements have revealed that the thickness of the interfacial layer between the InN and the substrates is reduced from 14 to 8.4 nm when the growth temperature is decreased from 400 °C to room temperature. This suppression of the interface reactions by reducing the growth temperature is probably responsible for the improvement in crystalline quality. These results indicate that the use of (Mn,Zn)Fe₂O₄ (111) substrates at low growth temperatures allows us to achieve nearly lattice matched epitaxial growth of InN.     

AlGaN/GaN HEMTs grown on silicon (001) substrates by molecular beam epitaxy

We report the realization of an AlGaN/GaN HEMT on silicon (001) substrate with noticeably better transport and electrical characteristics than previously reported. The heterostructure has been grown by molecular beam epitaxy. The 2D electron gas formed at the AlGaN/GaN interface exhibits a sheet carrier density of 8×10¹² cm⁻² and a Hall mobility of 1800 cm²/V s at room temperature. High electron mobility transistors with a gate length of 4 μm have been processed and DC characteristics have been achieved. A maximum drain current of more than 500 mA/mm and a transconductance g_m of 120 mS/mm have been obtained. These results are promising and open the way for making efficient AlGaN/GaN HEMT devices on Si(001).     

High-quality InAlN/GaN heterostructures grown by metal–organic vapor phase epitaxy

We fabricated high-quality InAlN/GaN heterostructures by metal–organic vapor phase epitaxy (MOVPE). X-ray diffraction measurements revealed that InAlN/GaN heterostructures grown under optimal conditions have flat surfaces and abrupt heterointerfaces. Electron mobility from 1200 to 2000 cm²/V s was obtained at room temperature. To our knowledge, this mobility is the highest ever reported for InAlN/GaN heterostructures. We also investigated the relationship between the Al composition and sheet electron density (N_s) for the first time. N_s increased from 1.0×10¹² to 2.7×10¹³ cm⁻² when the Al composition increased from 0.78 to 0.89.     

The role of a ZnO buffer layer in the growth of ZnO thin film on Al2O3 substrate

A ZnO buffer layer and ZnO thin film have been deposited by the pulsed laser deposition technique at the temperatures of 200 C and 400 C, respectively. Structural, electrical and optical properties of ZnO thin films grown on sapphire (Al₂O₃) substrate with 1, 5, and 9 nm thick ZnO buffer layers were investigated. A minute shift of the (101) peak was observed which indicates that the lattice parameter was changed by varying the thickness of the buffer layer. High resolution transmission electron microscopy (TEM) was used to investigate the thickness of the ZnO buffer layer and the interface involving a thin ZnO buffer between the film and substrate. Selected area electron diffraction (SAED) patterns show high quality hexagonal ZnO thin film with 30 in-plane rotation with respect to the sapphire substrate. The use of the buffer can reduce the lattice mismatch between the ZnO thin film and sapphire substrate; therefore, the lattice constant of ZnO thin film grown on sapphire substrate became similar to that of bulk ZnO with increasing thickness of the buffer layer.