Publications

In reactive ion etching (RIE) of GaN, the ion bombardment can damage the material, so it is necessary to develop plasma etch processes. This paper reports etching of GaN in an ECR (electron cyclotron resonance) etch system using both the ECR/RIE mode and the RIE-only mode. Group III (Ga, In, Al) nitride ECR etching is reviewed as a function of plasma chemistry, power, temperature, and pressure; as the ECR microwave power increased, the ion density and etch rates increased, with the etch rate increasing the most for InN. GaN etch rates > 6500 {angstrom}/min have been observed in the ECR/RIE mode. 2 figs, 6 refs.

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.

Etch rates for binary nitrides in ECR Cl{sub 2}/CH{sub 4}/H{sub 2}/Ar are reported as a function of temperature, rf-bias, microwave power, pressure and relative gas proportions. GaN etch rates remain relatively constant from 30 to 125{degrees}C and then increase to a maximum of 2340 {angstrom}-min{sup {minus}1} at 170{degrees}C. The AlN etch rate decreases throughout the temperature range studied with a maximum of 960 {angstrom}-min{sup {minus}1} at 30{degrees}C. When CH{sub 4} is removed from the plasma chemistry, the GaN and InN etch rates are slightly lower, with less dramatic changes with temperature. The surface composition of the III-V nitrides remains unchanged over the temperatures studied. The GaN and InN rates increase significantly with rf power, and the fastest rates for all three binaries are obtained at 2 mTorr. Surface morphology is smooth for GaN over a wide range of conditions, whereas InN surfaces are more sensitive to plasma parameters.

The chemical inertness and high bond strengths of the 3-5 nitrides lead to slower plasma etching rates than for more conventional 3-5 semiconductors under the same conditions. High ion density conditions (greater than 3 x 10(exp 11) cm(exp {minus}3)) such as those obtained in ECR or magnetron reactors produce etch rates up to an order of magnitude higher than for RIE, where the ion densities are in the 10(exp 9) cm(exp {minus}3) range. The authors have developed smooth anisotropic dry etches for GaN, InN, AlN and their alloys based on Cl2/CH4/H2/Ar, BCl3/Ar, Cl2/H2, Cl2/SF6, HBr/H2 and HI/H2 plasma chemistries achieving etch rates up to approx. 4,000 A/min at moderate dc bias voltages (less than or equal to {minus}150 V). Ion-induced damage in the nitrides appears to be less apparent than in other 3-5`s. One of the key remaining issues is the achievement of high selectivities for removal of one layer from another.

Quantum well microdisk laser structures have been fabricated in the GaN/InGaN, GaAs/AlGaAs and GaAs/InGaP systems using a combination of ECR dry etching Cl2/CH4/H2/Ar, BCl3/Ar or CH4/H2/Ar plasma chemistries respectively, and subsequent wet chemical etching of a buffer layer underlying the quantum wells. While wet etchants such as HF/H2O and HCl/HNO3/H2O are employed for AlGaAs and InGaP, respectively, a new KOH based solution has been developed for AlN which is completely selective over both GaN and InGaN. Typical mask materials include PR or SiN(x), while the high surface recombination velocity of exposed AlGaAs (approximately) 10(exp 5)cm(center dot)/sec requires encapsulation with ECR-CVD SiN(x) to stabilize the optical properties of the modulators.