Large area SiC substrates and epitaxial layers for high power semiconductor devices — An industrial perspective

We review the progress in the industrial production of SiC substrates and epitaxial layers for high power semiconductor devices. Optimization of SiC bulk growth by the sublimation method has resulted in the commercial release of 100 mm n-type 4H-SiC wafers and the demonstration of micropipe densities as low as 0.7 cm⁻² over a full 100 mm diameter. Modelling results link the formation of basal plane dislocations in SiC crystals to thermoelastic stress during growth. A warm-wall planetary SiC-VPE reactor has been optimized up to a 8×100 mm configuration for the growth of uniform 0.01–80-micron thick, specular, device-quality SiC epitaxial layers with low background doping concentrations of <1×10¹⁴ cm⁻³, and intentional p- and n-type doping from 1×10¹⁵ to >1×10¹⁹ cm⁻³. We address the observed degradation of the forward characteristics of bipolar SiC PiN diodes [H. Lendenmann, F. Dahlquist, J.P. Bergmann, H. Bleichner, C. Hallin, Mater. Sci. Forum 389–393 (2002) 1259], and discuss the underlying mechanism due to stacking fault formation in the epitaxial layers. A process for the growth of the epitaxial layers with a basal plane dislocation density <10 cm⁻² is demonstrated to eliminate the formation of these stacking faults during device operation [J.J. Sumakeris, M. Das, H.McD. Hobgood, S.G. Müller, M.J. Paisley, S. Ha, M. Skowronski, J.W. Palmour, C.H. Carter Jr., Mater. Sci. Forum 457–460 (2004) 1113].     

Correlation between morphological, electrical and optical properties of GaN at all stages of MOVPE Si/N treatment growth

GaN has been grown using Si/N treatment growth by MOVPE on sapphire (0001) in a home-made vertical reactor. The growth was monitored by in situ laser reflectometry. The morphological, electrical and optical properties of GaN are investigated at all the growth stages. To this aim, the growth was interrupted at different stages. The obtained samples are ex situ characterized by scanning electron microscopy (SEM), room temperature Van der Pauw–Hall electrical transport and low temperature (13 K) photoluminescence (PL) measurements. The SEM images show clearly the coalescence process. A smooth surface is obtained for a fully coalesced layer. During the coalescence process, the electron concentration (n) and mobility (μ) vary from 2×10¹⁹ cm⁻³ to 2×10¹⁷ cm⁻³ and 12 cm²/V s–440 cm²/V s, respectively. The PL maxima shift to higher energy and the FWHM decreases to about 4 meV. A correlation between PL spectra and Hall effect measurements is made. We show that the FWHM follows a n^2/3 power law for n above 10¹⁸ cm⁻³.     

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.     

Oxide ion conductivity and relaxation in CaREZrNbO7 (RE = La, Nd, Sm, Gd, and Y) system

CaREZrNbO₇ (RE = La, Nd, Sm, Gd and Y) system changed from fluorite (F)-type to pyrochlore (P)-type structure when the ionic radius ratios, r(Ca²⁺–RE³⁺)_av/r(Zr⁴⁺–Nb⁵⁺)_av were larger than 1.34. Thus, the La, Nd, and Sm compounds have a cubic P-type structure and the Gd and Y ones have a defect F-type structure. The electrical conductivity was measured using complex-plane impedance analysis over a wide temperature (300–750 °C) and frequency (1 Hz–1 MHz) ranges. The conductivity relaxation phenomenon was observed in these compounds and the relaxation frequencies were found to show Arrhenius-type behavior and activation energies were in good agreement with those obtained from high temperature conductivity plots. These results support the idea that the relaxation process and the conductivity have the same origin. The ionic conductivity of CaREZrNbO₇ (RE = La, Nd, Sm, Gd and Y) system showed the maximum at the phase boundary between the F-type and P-type phases. On the other hand, the activation energy for the conduction decreased in the F-type phase and increased in the P-type phase with increasing ionic radius ratio. Among the prepared compounds, CaGdZrNbO₇ showed the highest ionic conductivity of 9.47 × 10^− 3 S/cm at 750 °C which was about twice as high as that observed in Gd₂Zr₂O₇ (4.2 × 10^− 3 S/cm at 800 °C). The grain morphology observation by scanning electron microscope (SEM) showed well-sintered grains. AC impedance measurements in various atmospheres further indicated that they are predominantly oxide ion conductors at elevated temperatures (> 700 °C).     

Atomically flat GaMnN by diffusion of Mn into GaN()

The interaction of Mn thin films on atomically flat GaN() has been investigated by Scanning Tunneling Microscopy (STM) and Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS). GaN surfaces prepared by repeated sputtering/annealing cycles show various reconstructions but essentially the 6×6 one. A high density of small islands (height 0.6 nm, diameter 5 nm) nucleates upon deposition of 0.3 ML Mn. Upon annealing at 575 C, these islands coalesce into larger islands (height 4 nm, diameter 50 nm) between which the GaN surface is visible. Atomically resolved STM images between the islands show the (3×3) reconstruction of GaN. Annealing the sample further to 675 C leads to the restoration of a bare GaN surface. ToF-SIMS reveals that Mn diffused into the bulk of the sample.     

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).     

The structure of crystallographic damage in GaN formed during rare earth ion implantation with and without an ultrathin AlN capping layer

The crystallographic nature of the damage created in GaN implanted by rare earth ions at 300 keV and room temperature has been investigated by transmission electron microscopy versus the fluence, from 7×10¹³ to 2×10¹⁶ at/cm², using Er, Eu or Tm ions. The density of point defect clusters was seen to increase with the fluence. From about 3×10¹⁵ at/cm², a highly disordered ‘nanocrystalline layer’ (NL) appears on the GaN surface. Its structure exhibits a mixture of voids and misoriented nanocrystallites. Basal stacking faults (BSFs) of I₁, E and I₂ types have been noticed from the lowest fluence, they are I₁ in the majority. Their density increases and saturates when the NL is observed. Many prismatic stacking faults (PSFs) with Drum atomic configuration have been identified. The I₁ BSFs are shown to propagate easily through GaN by folding from basal to prismatic planes thanks to the PSFs.When implanting through a 10 nm AlN cap, the NL threshold goes up to about 3×10¹⁶ at/cm². The AlN cap plays a protective role against the dissociation of the GaN up to the highest fluences. The flat surface after implantation and the absence of SFs in the AlN cap indicate its high resistance to the damage formation.     

Bi-induced vibrational modes in GaAsBi

We have studied GaAs_1−xBi_x (up to x3%) using Raman scattering with two different polarization configurations. Two Bi-induced phonon modes are observed at 186 cm⁻¹ and 214 cm⁻¹ with increasing Raman intensity as the Bi concentration increases. By comparing Raman selection rules for the observed Bi-induced phonon modes with those for the substitutional N vibrational mode (GaN mode) in GaAsN, the phonon mode at 214 cm⁻¹ is identified as originating from substitutional Bi at the As site in GaAsBi.     

Three phonon processes in GaN

In the harmonic approximation the Hamiltonian of the vibrational states gives the picture of non-interacting phonons in a crystal. At finite temperatures all crystals contain anharmonic lattice forces. The effect of anharmonicity introduces the interactions of independent phonons in crystals. The number of independent vibrational modes originating from the high symmetry points and lines in the Brillouin zone is determined by lattice mode representation (LMR). The three phonon processes such as overtones and combinations are subjected to group theoretical selection rules. The overtones result from the Symmetrized Cubes of active species (irreducible representations (irrps)) and combinations from the complete reduction of the triple Kronecker product of different irrps according to which the vibrational states of crystals are classified. We have determined the symmetry allowed overtones, simple and general combinations of three phonon processes in GaN. The back-scattering Raman spectroscopy from GaN in the region 900–2200 cm⁻¹ yields several optically active transitions; these are analyzed in terms of the derived three phonon Raman selection rules.     

Temperature dependent energy relaxation time in AlGaN/AlN/GaN heterostructures

The two-dimensional (2D) electron energy relaxation in Al_0.25Ga_0.75N/AlN/GaN heterostructures was investigated experimentally by using two experimental techniques; Shubnikov-de Haas (SdH) effect and classical Hall Effect. The electron temperature (T_e) of hot electrons was obtained from the lattice temperature (T_L) and the applied electric field dependencies of the amplitude of SdH oscillations and Hall mobility. The experimental results for the electron temperature dependence of power loss are also compared with the current theoretical models for power loss in 2D semiconductors. The power loss that was determined from the SdH measurements indicates that the energy relaxation of electrons is due to acoustic phonon emission via unscreened piezoelectric interaction. In addition, the power loss from the electrons obtained from Hall mobility for electron temperatures in the range T_e > 100 K is associated with optical phonon emission. The temperature dependent energy relaxation time in Al_0.25Ga_0.75N/AlN/GaN heterostructures that was determined from the power loss data indicates that hot electrons relax spontaneously with MHz to THz emission with increasing temperatures.     

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.     

Quantification of the water boiling heat transfer in micro-structures by image analysis

The heat transfer performance of a micro-vaporizer has been measured by conventional methods (using temperatures, flow rates, effective power input). The study was carried out for laminar flow in channels (5 mm×3 cm×200 μm) micro-structured with square obstacles to increase the specific area. The results show that high heat transfer coefficients (1300– 2500 W m⁻²/C⁻¹) can be reached in such a micro-structured channel. Image analysis was done to estimate the volume vapour fraction, which can be converted into the mass vapour fraction using a slip ratio and avoids the need for any temperature or electric power input measurements. The estimation of this slip ratio is discussed in this paper.     

In-plane gate transistors in AlxGa1−xN/GaN heterostructures written by focused ion beams

Focused ion beam implantation of gallium and dysprosium was used to locally insulate the near-surface two-dimensional electron gas of Al_xGa_1−xN/GaN heterostructures. The threshold dose for insulation was determined to be 2×10¹⁰ cm⁻¹ for 90 keV Ga⁺ and 1×10⁹ cm⁻¹ for 200 keV Dy²⁺ at 4.2 K. This offers a tool not only for inter-device insulation but also for direct device fabrication. Making use of “open-T” like insulating line patterns, in-plane gate transistors have been fabricated by focused ion beam implantation. An exemplar with a geometrical channel width of 1.5 μm shows a conductance of 32 μS at 0 V gate voltage and a transconductance of around 4 μS, which is only slightly dependent on the gate voltage.     

Dependences of structural and electrical properties on thickness of polycrystalline Ga-doped ZnO thin films prepared by reactive plasma deposition

Polycrystalline Ga-doped (Ga content: 4 wt%) ZnO (GZO) thin films were deposited on glass substrates at 200 C by a reactive plasma deposition with DC arc discharge technique. The dependences of structural and electrical properties of GZO films on thickness, ranging from 30 to 560 nm, were investigated. Carrier concentration, n, and Hall mobility, μ, increases with increasing film thickness below 100 nm, and then the n remains nearly constant and the μ gradually increases until the thickness reaches 560 nm. The resistivity obtained of the order of 10⁻⁴ Ω cm for these films decreases with increasing film thickness: The highest resistivity achieved is 4.4×10⁻⁴ Ω cm with n of 7.6×10²⁰ cm⁻³ and μ of 18.5 cm²/V s for GZO films with a thickness of 30 nm and the lowest one is 1.8×10⁻⁴ Ω cm with n of 1.1×10²¹ cm⁻³ and μ of 31.7 cm²/V s for the GZO film with a thickness of 560 nm. X-ray diffraction pattern for all the films shows a hexagonal wurtzite structure with its strongly preferred orientation along the c-axis. Full width at half maximum of the (002) preferred orientation diffraction peak of the films decreases with increasing film thickness below 100 nm.     

Microstructural assessment of InN-on-GaN films grown by plasma-assisted MBE

The structural properties of InN thin films, grown by rf plasma-assisted molecular beam epitaxy on Ga-face GaN/Al₂O₃(0001) substrates, were investigated by means of conventional and high resolution electron microscopy. Our observations showed that a uniform InN film of total thickness up to 1 μm could be readily grown on GaN without any indication of columnar growth. A clear epitaxial orientation relationship of , was determined. The quality of the InN film was rather good, having threading dislocations as the dominant structural defect with a density in the range of 10⁹–10¹⁰ cm⁻². The crystal lattice parameters of wurtzite InN were estimated by electron diffraction analysis to be a=0.354 nm and c=0.569 nm, using Al₂O₃ as the reference crystal. Heteroepitaxial growth of InN on GaN was accomplished by the introduction of a network of three regularly spaced misfit dislocation arrays at the atomically flat interface plane. The experimentally measured distance of misfit dislocations was 2.72 nm. This is in good agreement with the theoretical value derived from the in-plane lattice mismatch of InN and GaN, which indicated that nearly full relaxation of the interfacial strain between the two crystal lattices was achieved.     

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.     

Ultra-fast dynamics of electron thermalization,cooling and transport effects in Ru(001)

Time-resolved two-photon photoelectron spectroscopy is used to study the dynamics of non-equilibrium electron and hole distributions at bare and D₂O-covered Ru(001) following optical excitation (55-fs, 800-nm pulses) with variable fluence (0.04–0.6 mJcm^-2). Within the first 0.5 ps we observe an ultra-fast transient of the excited-carrier population and energy density at the surface which is accompanied by pronounced deviations of the electron-energy distribution from a (thermalized) Fermi–Dirac distribution. Comparison of the transient energy density of the photoexcited electrons at the surface with predictions of the two-temperature model provides fair agreement up to 400 fs, but exhibits a systematically lower energy density at later times, where electrons and phonons are equilibrated. We propose that this reduced energy density at the surface originates from ultra-fast energy transport of non-thermal electrons into the bulk in competition to electron–phonon coupling at the surface. This is corroborated by extending the two-temperature model to account for non-thermal, photoexcited electrons, whereby quantitative agreement with experiment can only be achieved if ballistic transport and reduced electron–phonon coupling is incorporated for non-thermal electrons. Implications for surface femtochemistry are discussed. PACS 78.47.+p; 71.38.-k; 73.40.-c     

Macroscopic polarization and thermal conductivity of GaN

We theoretically investigated the effect of macroscopic polarization (sum of spontaneous and piezoelectric polarization) on the thermal conductivity of wurtzite GaN. Macroscopic polarization contributes to the effective elastic constant of the GaN and thus modifies the phonon group velocity. We used the revised phonon velocity to estimate the Debye frequency and temperature. Different phonon scattering rates were calculated as functions of the phonon frequency. The thermal conductivity of GaN was estimated using revised parameters such as the phonon velocity and phonon relaxation rate. The revised thermal conductivity at room temperature increased from 250 to 279 W m⁻¹ K⁻¹ due to macroscopic polarization. The method we developed can be used for thermal budget calculations for GaN optoelectronic devices.     

MBE growth of nitride-based photovoltaic intersubband detectors

In this work, we present the plasma-assisted molecular-beam epitaxial growth of quantum well infrared photodetector (QWIP) structures, including the Si-doped GaN/AlN short-period superlattice of the active region, conductive AlGaN claddings and integration of the final device. The growth of Si-doped GaN/AlN multiple quantum well (QW) structures is optimized by controlling substrate temperature, metal excess and growth interruptions. Structural characterization confirms a reduction of the interface roughness to the monolayer scale. P-polarized intersubband absorption peaks covering the 1.33–1.91 μm wavelength range are measured on samples with QW thickness varying from 1 to 2.5 nm. The absorption exhibits Lorentzian shape with a line width around 100 meV in QWs doped 5×10¹⁹ cm⁻³. To prevent partial depletion of the QWs owing to the internal electric field, we have developed highly-conductive Si-doped AlGaN cladding layers using In as a surfactant during growth. Complete ISB photodetectors with 40 periods of 1 nm-thick Si-doped GaN QWs with 2 nm-thick AlN barriers have been grown on conductive AlGaN claddings, the Al mole fraction of the cladding matching the average Al content of the active region. Temperature-dependent photovoltage measurements reveal a narrow (90 meV) detection peak at 1.39 μm.     

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.