Publications

GaN etching can be affected by a wide variety of parameters including plasma chemistry and plasma density. Chlorine-based plasmas have been the most widely used plasma chemistries to etch GaN due to the high volatility of the GaCl{sub 3} and NCl etch products. The source of Cl and the addition of secondary gases can dramatically influence the etch characteristics primarily due to their effect on the concentration of reactive Cl generated in the plasma. In addition, high-density plasma etch systems have yielded high quality etching of GaN due to plasma densities which are 2 to 4 orders of magnitude higher than reactive ion etch (RIE) plasma systems. The high plasma densities enhance the bond breaking efficiency of the GaN, the formation of volatile etch products, and the sputter desorption of the etch products from the surface. In this study, the authors report GaN etch results for a high-density inductively coupled plasma (ICP) as a function of BCl{sub 3}:Cl{sub 2} flow ratio, dc-bias, chamber-pressure, and ICP source power. GaN etch rates ranging from {approximately}100 {angstrom}/min to > 8,000 {angstrom}/min were obtained with smooth etch morphology and anisotropic profiles.

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 AlN 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 ({lt} OR = 2) BECAUSE OF THE HIGH ION ENERGIES NEEDED TO INITIATE ETCHING. IMPROVED N-TYPE OHMIC CONTACT RESISTANCES ARE OBTAINED BY SELECTIVE AREA SI+ IMPLANTATION FOLLOWED BY VERY HIGH TEMPERATURE ({gt}1300 deg C) anneals in which the thermal budget is minimized and AlN encapsulation prevents GaN surface decomposition. Implant isolation is effective in GaN, AlGaN and AlInN, but marginal in InGaN. Candidate gate insulators for GaN include AlN, AlON and Ga(Gd)O(x), but interface state densities are still to high to realize state-of-the-art MIS devices.

We have sputter-deposited 500-1200 Å thick WSi0.45 metallization onto n+ GaN (n≥1019 cm-3) doped either during MOCVD growth or by direct Si+ ion implantation (5×1015 cm-2, 100 keV) activated by RTA at 1100°C for 30 secs. In the epi samples Rc values of ∼10-14 ω cm2 were obtained, and were stable to ∼1000°C. The annealing treatments up to 600°C had little effect on the WSix/GaN interface, but the beta/-W2N phase formed between 700-800°C, concomitant with a strong reduction (approximately a factor of 2) in near-surface crystalline defects in the GaN. Spiking of the metallization down the threading and misfit dislocations was observed at 800°C, extending >5000 Å in some cases. This can create junction shorting in bipolar or thyristor devices, Rc values of <10-6 ωcm2 were obtained on the implanted samples for 950°C annealing, with values of after 1050°C anneals. The lower Rc values compared to epi samples appear to be a result of the higher peak doping achieved, ∼5×1020 cm-3. We observed wide spreads in Rc values over a wafer surface, with the values on 950°C annealed material ranging from 10-7 to 10-4 ω cm2. There appear to be highly nonuniform doping regions in the GaN, perhaps associated with the high defect density (1010 cm-2) in heteroepitaxial material, and this may contribute to the variations observed. We also believe that near-surface stoichiometry is variable in much of the GaN currently produced due to the relative ease of preferential N2 loss and the common use of HT containing growth (and cool-down) ambients. Finally the ohmic contact behavior of WSix on abrupt and graded composition InxAl1-xN layers has been studied as a function of growth temperature, InN mole fraction x=0.5-1) and post WSix deposition annealing treatment. Rc values in the range 10-3/-10sup-5/ ω cm2 are obtained for auto-doped n+ alloys, with the n-type background being little affected by growth conditions (n∼1020 cm-3). InN is the least temperature-stable alloy (les/700°C), and WSix contact morphology is found to depend strongly on the epi growth conditions.

Mass spectrometry of the plasma effluent during Reactive Ion Beam Etching (RIBE) of GaAs using an Inductively Coupled Plasma (ICP) source and a Cl{sub 2}/Ar gas chemistry shows that AsCl{sub 3}, AsCl{sub 2} and AsCl are all detected as etch products for As, while GaCl{sub 2} is the main signal detected for the Ga products. The variation in selective ion currents for the various etch products has been examined as a function of chuck temperature (30--100 C), percentage Cl{sub 2} in the gas flow, beam current (60--180 mA) and beam voltage (200--800 V). The results are consistent with AsCl{sub 3} and GaCl{sub 3} being the main etch product species under their conditions, with fragmentation being responsible for the observed mass spectra.

The temperature dependence of the specific contact resistance of W and WSi{sub 0.44} contacts on n{sup +} In{sub 0.65}Ga{sub 0.35}N and InN was measured in the range -50 {degrees}C to 125 {degrees}C. The results were compared to theoretical values for different conduction mechanisms, to further elucidate the conduction mechanism in 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, e{sup c} {approximately} 10{sup -7} {Omega} {center_dot} cm{sup 2} for W and e{sub c} of 4x 10{sup -7} {Omega} {center_dot} cm{sup 2} for WSi{sub x}. InN metallized with W produced ohmic contacts with e{sub c} {approximately} 10{sup -7} {Omega} {center_dot} cm{sup 2} and e{sub c} {approximately} 10{sup -6} {Omega} {center_dot} cm{sup 2} for WSi{sub x} at room temperature.

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 CoSi{sub x} 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.

Inductively coupled plasma etching of GaN, AlN, InN, InGaN and InAlN was investigated in CH{sub 4}/H{sub 2}/Ar plasmas as a function of dc bias, and ICP power. The etch rates were generally quite low, as is common for III-nitrides in CH{sub 4} based chemistries. The etch rates increased with increasing dc bias. At low rf power (150 W), the etch rates increased with increasing ICP power, while at 350 W rf power, a peak was found between 500 and 750 W ICP power. The etched surfaces were found to be smooth, while selectivities of etch were {le} 6 for InN over GaN, AlN, InGaN and InAlN under all conditions.

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, and thus contact resistances will be greatly improved provided the metallization is stable and reliable. Some recent work with CoSi{sub x} 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 wide band gap group-III nitride materials continue to generate interest in the semiconductor community with the fabrication of green, blue, and ultraviolet light emitting diodes (LEDs), blue lasers, and high temperature transistors. Realization of more advanced devices requires pattern transfer processes which are well controlled, smooth, highly anisotropic and have etch rates exceeding 0.5 μm/min. The utilization of high-density chlorine-based plasmas including electron cyclotron resonance (ECR) and inductively coupled plasma (ICP) systems has resulted in improved etch quality of the group-III nitrides over more conventional reactive ion etch (RIE) systems.

High-density plasma etching has been an effective patterning technique for the group-III nitrides due to ion fluxes which are 2 to 4 orders of magnitude higher than more conventional reactive ion etch (RIE) systems. GaN etch rates exceeding 0.68 μm/min have been reported in Cl2/H2/Ar inductively coupled plasmas (ICP) at -280 V dc-bias. Under these conditions, the etch mechanism is dominated by ion bombardment energies which can induce damage and minimize etch selectivity. High selectivity etch processes are often necessary for heterostructure devices which are becoming more prominent as growth techniques improve. In this study, we will report high-density ICP etch rates and selectivities for GaN, AlN, and InN as a function of cathode power, ICP-source power, and chamber pressure. GaN:AlN selectivities >8:1 were observed in a Cl2/Ar plasma at 10 m Torr pressure, 500 W ICP-source power, and 130 W cathode rf-power, while the GaN:InN selectivity was optimized at approximately 6.5:1 at 5 m Torr, 500 W ICP-source power, and 130 W cathode rf-power.

Plasma-induced-damage often degrades the electrical and optical properties of compound semiconductor devices. Despite the fact that the binding energy of GaN is larger than that for more conventional III--V compounds, etch damage is still a concern. Photoluminescence measurements and atomic force microscopy have been used to determine the damage induced in GaN by exposure to both electron cyclotron resonance (ECR) and inductively coupled plasmas (ICP) generated Ar plasmas.

Deep etching of GaAs is a critical process step required for many device applications including fabrication of through-substrate via holes for monolithic microwave integrated circuits (MMICs). Use of high-density plasmas, including inductively coupled plasmas (ICP), offers an alternative approach to etching vias as compared to more conventional parallel plate reactive ion etch systems. This paper reports ICP etching of GaAs vias at etch rates of about 5.3 {mu}m/min with via profiles ranging from highly anistropic to conical.

Inductively Coupled Plasma (ICP) sources are extremely promising for large-area, high-ion density etching or deposition processes. In this review the authors compare results for GaAs and GaN etching with both ICP and Electron Cyclotron Resonance (ECR) sources on the same single-wafer platform. The ICP is shown to be capable of very high rates with excellent anisotropy for fabrication of GaAs vias or deep mesas in GaAs or GaN waveguide structures.

The group III-nitrides continue to generate interest due to their wide band gaps and high dielectric constants. These materials have made significant impact on the compound semiconductor community as blue and ultraviolet light emitting diodes (LEDs). Realization of more advanced devices; including lasers and high temperature electronics, requires dry etch processes which are well controlled, smooth, highly anisotropic and have etch rates exceeding 0.5 {mu}m/min. In this paper, we compare electron cyclotron resonance (ECR), inductively coupled plasma (ICP), and reactive ion etch (RIE) etch results for GaN. These are the first ICP etch results reported for GaN. We also report ECR etch rates for GaN as a function of growth technique.

W, WSi{sub 0.44} and Ti/Al contacts were examined on n{sup +} In{sub 0.65}Ga{sub 0.35}N, InN and In{sub 0.75}Al{sub 0.25}N. W was found to produce low specific contact resistance ({rho}{sub c} {approximately} 10{sup {minus}7} {Omega} {center_dot}cm{sup 2}) ohmic contacts to InGaN, with significant reaction between metal and semiconductor at 900 {degrees}C mainly due to out diffusion of In and N. WSi{sub x} showed an as-deposited {rho}{sub c} of 4{times}10{sup {minus}7} {Omega} {center_dot}cm{sup 2} but this degraded significantly with subsequent annealing. Ti/Al contacts were stable to {approximately} 600 {degrees}C ({rho}{sub c} {approximately} 4{times}10{sup {minus}7} {Omega} {center_dot}cm{sup 2} at {le}600 {degrees}C). The surfaces of these contacts remain smooth to 800 {degrees}C for W and WSi{sub x} and 650 {degrees}C for Ti/Al. InN contacted with W and Ti/Al produced ohmic contacts with {rho}{sub c} {approximately} 10{sup {minus}7} {Omega} {center_dot}cm{sup 2} and for WSi{sub x} {rho}{sub c} {approximately} 10{sup {minus}6} {Omega} {center_dot}cm{sup 2}. All remained smooth to {approximately} 600 {degrees}C, but exhibited significant interdiffusion of In, N, W and Ti respectively at higher temperatures. The contact resistances for all three metalization schemes were {ge} 10{sup {minus}4} {Omega} {center_dot}cm{sup 2} on InAlN, and degrades with subsequent annealing. The Ti/Al was found to react with the InAlN above 400 {degrees}C, causing the contact resistance to increase rapidly. W and WSi{sub x} proved to be more stable with {rho}{sub c} {approximately} 10{sup {minus}2} and 10{sup {minus}3} {Omega} {center_dot}cm{sup 2} up to 650 {degrees}C and 700 {degrees}C respectively.

The electrical properties of the light ion impurities H, O and C in GaN have been examined in both as-grown and implanted material. H is found to efficiently passivate acceptors such as Mg, Ca and C. Reactivation occurs at {ge} 450 C and is enhanced by minority carrier injection. The hydrogen does not leave the GaN crystal until > 800 C, and its diffusivity is relatively high ({approximately} 10{sup {minus}11} cm{sup 2}/s) even at low temperatures (< 200 C) during injection by wet etching, boiling in water or plasma exposure. Oxygen shows a low donor activation efficiency when implanted into GaN, with an ionization level of 30--40 meV. It is essentially immobile up to 1,100 C. Carbon can produce low p-type levels (3 {times} 10{sup 17} cm{sup {minus}3}) in GaN during MOMBE, although there is some evidence it may also create n-type conduction in other nitrides.

Etch rates up to 7,000 {angstrom}/min. for GaN are obtained in Cl{sub 2}/H{sub 2}/Ar or BCl{sub 3}/Ar ECR discharges at 1--3mTorr and moderate dc biases. Typical rates with HI/H{sub 2} are about a factor of three lower under the same conditions, while CH{sub 4}/H{sub 2} produces maximum rates of only {approximately}2,000 {angstrom}/min. The role of additives such as SF{sub 6}, N{sub 2}, H{sub 2} or Ar to the basic chlorine, bromine, iodine or methane-hydrogen plasma chemistries are discussed. Their effect can be either chemical (in forming volatile products with N) or physical (in breaking bonds or enhancing desorption of the etch products). The nitrides differ from conventional III-V`s in that bond-breaking to allow formation of the etch products is a critical factor. Threshold ion energies for the onset of etching of GaN, InGaN and InAlN are {ge} 75 eV.

Etch rates up to 7000{angstrom}/min for InP and 3500{angstrom}/min for GaAs are obtained for high microwave power (1000W) CH{sub 4}/H{sub 2}/Ar Electron Cyclotron Resonance plasma etching. Preferential loss of the group V element leads to nonstoichiometric, unacceptably rough surfaces on In-based binary semiconductors at microwave powers {ge}400W, regardless of plasma composition. Both Ga- and Al-based materials retain smooth, stoichiometric surfaces even at I000W, but the rates are still much slower than for C1{sub 2} plasma chemistries. The results suggest that CH{sub 4}/H{sub 2} plasmas are not well suited to ECR systems operating at high powers.

Electron cyclotron resonance (ECR) etching of GaP, GaAs, InP, and InGaAs are reported as a function of percent chlorine-containing gas for Cl2/Ar, Cl2/N2, BCl3/Ar, and BCl3/N2 plasma chemistries. GaAs and GaP etch rates were faster than InP and InGaAs, independent of plasma chemistry due to the low volatility of the InClx etch products. GaAs and GaP etch rates increased as %Cl2 was increased for Cl2/Ar and Cl2/N2 plasmas. The GaAs and GaP etch rates were much slower in BCl3-based plasmas due to lower concentrations of reactive Cl, however enhanced etch rates were observed in BCl3/N2 at 75% BCl3. Smooth etched surfaces were obtained over a wide range of plasma chemistries.

Electron cyclotron resonance (ECR) etching of GaN in Cl{sub 2}/H{sub 2}/Ar, C1{sub 2}/SF{sub 6}/Ar, BCl{sub 3}/H{sub 2}/Ar and BCl{sub 3}/SF{sub 6}/Ar plasmas is reported as a function of percent H{sub 2} and SF{sub 6}. GaN etch rates were found to be 2 to 3 times greater in Cl{sub 2}/H{sub 2}/Ar discharges than in BCl{sub 3}/H{sub 2}/Ar discharges independent of the H{sub 2} concentration. In both discharges, the etch rates decreased as the H{sub 2} concentration increased above 10%. When SF{sub 6} was substituted for H{sub 2}, the GaN etch rates in BCl{sub 3}-based plasmas were greater than those for the Cl{sub 2}-based discharges as the SF{sub 6} concentration increased. GaN etch rates were greater in Cl{sub 2}/H{sub 2}/Ar discharges as compared to Cl{sub 2}SF{sub 6}/Ar discharges whereas the opposite trend was observed for BCl{sub 3}-based discharges. Variations in surface morphology and near-surface stoichiometry due to plasma chemistries were also investigated using atomic force microscopy and Auger spectroscopy, respectively.

The light ion impurities C, 0 and H have been implanted or diffused into GaN and related compounds and their effect on the electrical properties of these materials measured by Hall, C-V and SIMS as a function of annealing temperatures from 300--11OO{degree}C. While C in as-grown GaN appears to create an acceptor under MOMBE conditions, implanted C shows no measurable activity. Similarly, implanted 0 does not show any shallow donor activity after annealing at {le}700{degree}C, but can create high resistivity regions (10{sup 6} {Omega}/{open_square}) in GaN, AlInN and InGaN for device isolation when annealed at 500--70O{degree}C. Finally, hydrogen is found to passivate shallow donor and acceptor states in GaN, InN. InAlN and InGaN, with dissociation of the neutral complexes at >450{degree}C. The liberated hydrogen does not leave the nitride films until much higher annealing temperatures (>800{degree}C). Typical reactivation energies are {approximately}2.0 eV for impurity-hydrogen complexes.

Hydrogen is readily incorporated into GaN and related alloys during wet and dry etching, chemical vapor deposition of dielectric overlayers, boiling in water and other process steps, in addition to its effects during MOCVD or MOMBE growth. The hydrogen is bound at defects or impurities and passivates their electrical activity. Reactivation occurs at 450-550{degrees}C, but evolution from the crystal requires much higher temperatures ({ge} 800{degrees}C).

Due to their wide band gaps and high dielectric constants, the group III-nitrides have made significant impact on the compound semiconductor community as blue and ultraviolet light emitting diodes (LEDs) and for their potential use in laser structures and high temperature electronics. Processing of these materials, in particular wet and dry etching, has proven to be extremely difficult due to their inert chemical nature. We report electron cyclotron resonance (ECR) etch rates for GaN, InN, AlN, In{sub (x)}Ga{sub (1-x)}Ni and In{sub (x)}Al{sub (1-x)}N as a function of temperature, rf-power, pressure, and microwave power. Etch conditions are characterized for rate, profile, and sidewall and surface morphology. Atomic force microscopy (AFM) is used to quantify RMS roughness of the etched surfaces. We observe consistent trends for the InAlN films where the etch rates increase with increasing concentration of In. The trends are far less consistent for the InGaN with a general decrease in etch rate as the In concentration is increased.

New developments in dry and wet etching, ohmic contacts and epitaxial growth of Ill-V nitrides are reported. These make possible devices such as microdisk laser structures and GaAs/AlGaAs heterojunction bipolar transistors with improved InN ohmic contacts.

Hydrogen is found to readily diffuse into InGaN, InAlN and InGaAlN epitaxial layers during plasma exposures at 170-250{degree}C for 40 sec-30 min. The diffusivity of hydrogen is > 10{sup -11} cm{sup 2} {center_dot} s{sup -1} at 170{degree}C, and the native donor species are passivated by association with the hydrogen. Reactivation of these species occurs at 450-500{degree}C, but the hydrogen remains in the material until {ge} 800{degree}C.