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After substantial investment in research and development over the last decade, silicon carbide materials and devices are coming of age. The concerted efforts that made this possible have resulted in breakthroughs in our understanding of materials issues such as compensation mechanisms in high-purity crystals, dislocation properties, and the formation of SiC/SiO2 interfaces, as well as device design and processing. The progress accomplished over the last eight years in SiC-based electronic materials is summarized in this issue of MRS Bulletin.
Junction field effect transistors (JFET) were fabricated on a GaN epitaxial structure grown by metal organic chemical vapor deposition. The DC and microwave characteristics, as well as the high temperature performance of the devices were studied. These devices exhibited excellent pinch-off and a breakdown voltage that agreed with theoretical predictions. An extrinsic transconductance (gm) of 48 mS/mm was obtained with a maximum drain current (ID) of 270 mA/mm. The microwave measurement showed an fT of 6 GHz and an fmax of 12 GHz. Both the ID and the gm were found to decrease with increasing temperature, possibly due to lower electron mobility at elevated temperatures. These JFETs exhibited a significant current reduction after a high drain bias was applied, which was attributed to a partially depleted channel caused by trapped electrons in the semi-insulating GaN buffer layer.
Sputter-deposited W-based contacts on p-GaN (NA∼1018 cm−3) display non-ohmic behavior independent of annealing temperature when measured at 25°C. The transition to ohmic behavior occurs above ∼250°C as more of the acceptors become ionized. The optimum annealing temperature is ∼700°C under these conditions. These contacts are much more thermally stable than the conventional Ni/Au metallization, which shows a severely degraded morphology even at 700°C. W-based contacts may be ohmic as-deposited on very heavily doped n-GaN, and the specific contact resistance improves with annealing up to ∼900°C.
Anisotropic, smooth etching of the group-Ill nitrides has been reported at relatively high rates in high-density plasma etch systems. However, such etch results are often obtained under high dc-bias and/or high plasma flux conditions where plasma induced damage can be significant. Despite the fact that the group-III nitrides have higher bonding energies than more conventional III–V compounds, plasma-induced etch damage is still a concern. Attempts to minimize such damage by reducing the ion energy or increasing the chemical activity in the plasma often result in a loss of etch rate or anisotropy which significantly limits critical dimensions and reduces the utility of the process for device applications requiring vertical etch profiles. It is therefore necessary to develop plasma etch processes which couple anisotropy for critical dimension and sidewall profile control and high etch rates with low-damage for optimum device performance. In this study we report changes in sheet resistance and contact resistance for n- and p-type GaN samples exposed to an Ar inductively coupled plasma (ICP). In general, plasma-induced damage was more sensitive to ion bombardment energies as compared to plasma flux. In addition, p-GaN was typically more sensitive to plasma-induced damage as compared to n-GaN.
GaN implanted with donor(Si, S, Se, Te) or acceptor (Be, Mg, C) species was annealed at 900-1500 °C using AlN encapsulation. No redistribution was measured by SIMS for any of the dopants and effective diffusion coefficients are ≤2 × 10−13 cm2. s−1 at 1400 °C, except Be, which displays damage-enhanced diffusion at 900 °C and is immobile once the point defect concentration is removed. Activation efficiency of ∼90% is obtained for Si at 1400 °C. TEM of the implanted material shows a strong reduction in lattice disorder at 1400-1500 °C compared to previous results at 1100 °C. There is minimal interaction of the sputtered AlN with GaN under our conditions, and it is readily removed selectively with KOH.
Junction field effect transistors (JFET) were fabricated on a GaN epitaxial structure grown by metal organic chemical vapor deposition. The DC and microwave characteristics, as well as the high temperature performance of the devices were studied. These devices exhibited excellent pinch-off and a breakdown voltage that agreed with theoretical predictions. An extrinsic transconductance (gm) of 48 mS/mm was obtained with a maximum drain current (ID) of 270 mA/mm. The microwave measurement showed an fr of 6 GHz and an fmax of 12 GHz. Both the ID and the gm were found to decrease with increasing temperature, possibly due to lower electron mobility at elevated temperatures. These JFETs exhibited a significant current reduction after a high drain bias was applied, which was attributed to a partially depleted channel caused by trapped electrons in the semi-insulating GaN buffer layer.
The ionization levels of different donor and acceptor species implanted into GaN were measured by temperature-dependent Hall data after high temperature (1400 °C) annealing. The values obtained were 28 meV (Si), 48 meV (S), 50 meV (Te) for the donors, and 170 meV for Mg acceptor. P-type conductivity was not achieved with either Be or C implantation. Basically all of the implanted species show no distribution during activation annealing. For high implant doses (5×1015 cm−2) a high concentration of extended defects remains after 1100 °C anneals, but higher temperatures (1400 °C) produces a significant improvement in crystalline quality in the implanted region.
Si+ implant activation efficiencies above 90%, even at doses of 5×1015 cm−2, have been achieved in GaN by RTP at 1400–1500°C for 10 secs. The annealing system utilizes with MoSi2 heating elements capable of operation up to 1900 °C, producing high heating and cooling rates (up to 100 °C · s−1). Unencapsulated GaN show severe surface pitting at 1300 °C, and complete loss of the film by evaporation at 1400 °C. Dissociation of nitrogen from the surface is found to occur with an approximate activation energy of 3.8 eV for GaN (compared to 4.4 eV for AIN and 3.4 eV for InN). Encapsulation with either rf-magnetron reactively sputtered or MOMBE-grown AIN thin films provide protection against GaN surface degradation up to 1400 °C, where peak electron concentrations of ∼5×1020 cm-3 can be achieved in Si-implanted GaN. SIMS profiling showed little measurable redistribution of Si, suggesting Dsi ≤ 10-13 cm2 · s−1 at 1400 °C. The implant activation efficiency decreases at higher temperatures, which may result from SiGa to SiN site switching and resultant self-compensation.
GaN implanted with donor(Si, S, Se, Te) or acceptor (Be, Mg, C) species was annealed at 900-1500°C using AIN encapsulation. No redistribution was measured by SIMS for any of the dopants and effective diffusion coefficients are ≤2×10-13 cm2 s-1 at 1400°C, except Be, which displays damage-enhanced diffusion at 900°C and is immobile once the point defect concentration is removed. Activation efficiency of ∼90% is obtained for Si at 1400°C. TEM of the implanted material shows a strong reduction in lattice disorder at 1400-1500°C compared to previous results at 1100°C. There is minimal interaction of the sputtered AIN with GaN under our conditions, and it is readily removed selectively with KOH.
Sputter-deposited W-based contacts on p-GaN (NA∼1018cm-3) display non-ohmic behavior independent of annealing temperature when measured at 25°C. The transition to ohmic behavior occurs above ∼250°C as more of the acceptors become ionized. The optimum annealing temperature is ∼700°C under these conditions. These contacts are much more thermally stable than the conventional Ni/Au metallization, which shows a severely degraded morphology even at 700°C. W-based contacts may be ohmic as-deposited on very heavily doped n-GaN, and the specific contact resistance improves with annealing up to ∼900°C.
The activation annealing of Si-implanted GaN is reported for temperatures from 1100 to 1400 °C. Although previous work has shown that Si-implanted GaN can be activated by a rapid thermal annealing at ∼1100 °C, it was also shown that significant damage remained in the crystal. Therefore, both AlN-encapsulated and uncapped Si-implanted GaN samples were annealed in a metal organic chemical vapor deposition system in a N2/NH3 ambient to further assess the annealing process. Electrical Hall characterization shows increases in carrier density and mobility for annealing up to 1300 °C before degrading at 1400 °C due to decomposition of the GaN epilayer. Rutherford backscattering spectra show that the high annealing temperatures reduce the implantation induced damage profile but do not completely restore the as-grown crystallinity.
Heterostructure modulation doped transistors (MODFETs) based on AlGaN/GaN structures have demonstrated impressive DC and microwave performance often despite high transistor access resistance. One approach to reducing the access resistance is to use selective area Si-implantation. While several reports exist on Si-implantation in GaN, little work has been done on implantation in AlGaN. In addition, more information on the annealing of implantation damage in GaN is needed to optimize its use in FETs and thyristors.
We report the electrical and structural properties of Si-implanted Al0.15Ga0.85N based on Hall measurements and Rutherford Backscattering (RBS) spectra, respectively. Al0.15Ga0.85N shows less damage accumulation than GaN for a room temperature Si-implant dose of 5×1015 cm-2 based on the minimum channeling yield (26% for AlGaN as compared to 34% for GaN), however, as with GaN, this damage is difficult to remove by thermal annealing at °C.
In-situ optical reflectance is used to monitor the morphological evolution of the two-step GaN growth on sapphire. The amount of H2 carrier gas used in the growth is observed to strongly influence the morphological evolution of the low temperature buffer layer and the subsequent high temperature nucleation behavior, which in turn affects the structural and electrical properties of the GaN epitaxial films. The optical reflectance transients correlate with the sizes and distributions of nuclei as observed by AFM.
Recent progress in the development of dry and wet etching techniques, implant doping and isolation, thermal processing, gate insulator technology and high reliability contacts is reviewed. Etch selectivities up to 10 for InN over AIN are possible in Inductively Coupled Plasmas using a Cl2/Ar chemistry, but in general selectivities for each binary nitride relative to each other are low (≤2)b ecause of the high ion energies needed to initiate etching. Improved ntype ohmic contact resistances are obtained by selective area Si+ implantation followed by very high temperature (>1300°C) anneals in which the thermal budget is minimized and AIN encapsulation prevents GaN surface decomposition. Implant isolation is effective in GaN, AlGaN and AlInN, but marginal in InGaN. Candidate gate insulators for GaN include AIN, A1ON and Ga(Gd)Ox, but interface state densities are still to high to realize state-of-the-art MIS devices.
Wet chemical etching of GaN, InN, AIN, InAlN and InGaN was investigated in various acid and base solutions at temperatures up to 75°C. Only KOH-based solutions were found to etch AIN and InAlN. No etchants were found for the other nitrides, emphasizing their extreme lack of chemical reactivity. The native oxide on most of the nitrides could be removed in potassium tetraborate at 75°C, or HCl/H2O at 25°C.
Transient thermal processing is employed for implant activation, contact alloying, implant isolation and dehydrogenation during III-nitride device fabrication. We have compared use of InN, AlN and GaN powder as methods for providing a N2 overpressure within a graphite susceptor for high temperature annealing of GaN, InN, A1N and InAlN. The AlN powder provides adequate surface protection to temperatures of ∼1100°C for AlN, > 1050°C for GaN, ∼600°C for InN and ∼800°C for the ternary alloy. While the InN powder provides a higher N2 partial pressure than AlN powder, at temperatures above ∼750°C the evaporation of In is sufficiently high to produce condensation of In droplets on the surfaces of the annealed samples. GaN powder achieved better surface protection than the other two cases.
The wide gap materials SiC, GaN and to a lesser extent diamond are attracting great interest for high power/high temperature electronics. There are a host of device processing challenges presented by these materials because of their physical and chemical stability, including difficulty in achieving stable, low contact resistances, especially for one conductivity type, absence of convenient wet etch recipes, generally slow dry etch rates, the high temperatures needed for implant activation, control of suitable gate dielectrics and the lack of cheap, large diameter conducting and semi-insulating substrates. The relatively deep ionization levels of some of the common dopants (Mg in GaN; B, Al in SiC; P in diamond) means that carrier densities may be low at room temperature even if the impurity is electrically active - this problem will be reduced at elevated temperature, and thus contact resistances will be greatly improved provided the metallization is stable and reliable. Some recent work with CoSix on SiC and W-alloys on GaN show promise for improved ohmic contacts. The issue of unintentional hydrogen passivation of dopants will also be covered - this leads to strong increases in resistivity of p-SiC and GaN, but to large decreases in resistivity of diamond. Recent work on development of wet etches has found recipes for AlN (KOH), while photochemical etching of SiC and GaN has been reported. In the latter cases p-type materials is not etched, which can be a major liability in some devices. The dry etch results obtained with various novel reactors, including ICP, ECR and LE4 will be compared - the high ion densities in the former techniques produce the highest etch rates for strongly-bonded materials, but can lead to preferential loss of N from the nitrides and therefore to a highly conducting surface. This is potentially a major problem for fabrication of dry etched, recessed gate FET structures.
The temperature dependence of the specific contact resistance of W and WSi0.44 contacts on n+ In0.55Ga0.35N and InN was measured in the range -50 °C to 125 °C. The results were compared to theoretical values for different conduction mechanisms, to further elucidate the conduction mechanism in these contact structures. The data indicates the conduction mechanism is field emission for these contact schemes for all but as-deposited metal to InN where thermionic emission appears to be the dominant mechanism. The contacts were found to produce low specific resistance ohmic contacts to InGaN at room temperature, ϱc ∼ 10-7 Ω ·cm2 for W and ϱc of 4× 10-7 Ω ·cm for WSix. InN metallized with W produced ohmic contacts with ϱc ∼ 10-6 Ω ·cm and ϱc ∼ 10-6 Ω ·cm. for WSix at room temperature.
III-N photonic devices have made great advances in recent years following the demonstration of doping of GaN p-type with Mg and n-type with Si. However, the deep ionization energy level of Mg in GaN (∼160 meV) limits the ionized of acceptors at room temperature to less than 1.0% of the substitutional Mg. With this in mind, we used ion implantation to characterize the ionization level of Ca in GaN since Ca had been suggested by Strite  to be a shallow acceptor in GaN. Ca-implanted GaN converted from n-to-p type after a 1100°C activation anneal. Variable temperature Hall measurements give an ionization level at 169 meV. Although this level is equivalent to that of Mg, Ca-implantation may have advantages (shallower projected range and less straggle for a given energy) than Mg for electronic devices. In particular, we report the first GaN device using ion implantation doping. This is a GaN junction field effect transistor (JFET) which employed Ca-implantation. A 1.7 µm JFET had a transconductance of 7 mS/mm, a saturation current at 0 V gate bias of 33 mA/mm, a ft of 2.7 GHz, and a fmax of 9.4 GHz. 0-implantation was also studied and shown to create a shallow donor level (∼25 meV) that is similar to Si. SIMS profiles of as-implanted and annealed samples showed no measurable redistribution of either Ca or0inGaNat 1125°C.
Ion implantation doping and isolation is expected to play an enabling role for the realization of advanced Ill-Nitride based devices. In fact, implantation has already been used to demonstrate n- and p-type doping of GaN with Si and Mg or Ca, respectively, as well as to fabricate the first GaN junction field effect transistor.1-4 Although these initial implantation studies demonstrated the feasibility of this technique for the Ill-Nitride materials, further work is needed to realize its full potential.
After reviewing some of the initial studies in this field, we present new results for improved annealing sequences and defect studies in GaN. First, sputtered A1N is shown by electrical characterization of Schottky and Ohmic contacts to be an effective encapsulant of GaN during the 1100 °C implant activation anneal. The A1N suppresses N-loss from the GaN surface and the formation of a degenerate n+-surface region that would prohibit Schottky barrier formation after the implant activation anneal. Second, we examine the nature of the defect generation and annealing sequence following implantation using both Rutherford Backscattering (RBS) and Hall characterization. We show that for a Si-dose of l × l016 cm-2 50% electrical donor activation is achieved despite a significant amount of residual implantation-induced damage in the material.