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Electron cyclotron resonance (ECR) plasma etching with additional rf-biasing produces etch rates ≥ 2,500 A/min for InGaP and AlInP in CH4/H2/Ar. These rates are an order of magnitude or much higher than for reactive ion etching conditions (RIE) carried out in the same reactor. N2 addition to CH4/H2/Ar can enhance the InGaP etch rates at low flow rates, while at higher concentrations it provides an etch-stop reaction. The InGaP and AlInP etched under ECR conditions have somewhat rougher morphologies and different stoichiometries up to ≈200 A from the sur face relative to the RIE samples.

Electron cyclotron resonance (ECR) BCl3 discharges with additional rf biasing of the sample position have been used to etch a variety of III–V semiconductors. GaAs and AlxGa1−xAs (x = 0−1) etch at equal rates in BCl3 or BCl3/Ar discharges, whereas SF6 addition produces high selectivities for etching GaAs over AlGaAs. These selectivities are in excess of 600 for dc biases of ≤−150 V, and fall to ≤6 for biases of −300 V. If the dc biases are kept to ≤ − 100 V, there is no measurable degradation of the optical properties of the GaAs and AlGaAs. The AlF3 formed on the AlGaAs surface during exposure to BCl3/SF6 plasmas can be removed by sequential rinsing in dilute NH4OH and water. In-based materials (InP, InAs, InSb, InGaAs) etch at slow rates with relatively rough morphologies in BCl3 plasmas.

Vinyl iodide (C2H3I) microwave discharges with additions of H2 and Ar are found to provide faster etch rates than conventional CH4/H2/Ar discharges for InP, InGaAs, GaAs, and AlGaAs. This is a result of the relatively high volatilities of indium, gallium, and aluminum iodide species. The etched features are smooth and anisotropic over a wide range of do self-biases (−150 to −350 V), process pressures (1–20mTorr), and microwave powers (150–500 W). The polymer that forms on the mask during the plasma exposure can be readily removed in O2 discharges. Electron spectroscopy for chemical analysis (ESCA) showed that the etched surfaces are slightly deficient in the group V elements under most conditions, but changes to the optical properties of the semiconductors are minimal. No defects are visible by transmission electron microscopy (TEM) in GaAs or InP samples etched at dc biases ≤ −250 V.

A systematic study has been performed of the dry etching characteristics of GaAs, Al0.3Ga0.7As, and GaSb in chlorine-based electron cyclotron resonance (ECR) discharges. The gas mixtures investigated were CCl2F2/O2, CHCl2F/O2, and PCl3. The etching rates of all three materials increase rapidly with applied RF power, while the addition of the microwave power at moderate levels (150 W) increases the etch rates by 20–80%. In the microwave discharges, the etch rates decrease with increasing pressure, but at 1 m Torr it is possible to obtain usable rates for self-bias voltages ≤ 100 V. Of the Freon-based mixtures, CHCl2F provides the least degradation of optical (photoluminescence) and electrical (diode ideality factors and Schottky barrier heights) properties of GaAs as a result of dry etching. Smooth surface morphologies are obtained on all three materials provided the microwave power is limited to ≤ 200 W. Above this power, there is surface roughening evident with all of the gas mixtures investigated.

The reactive ion etching of GaAs, InP, InGaAs, and InAlAs in CF3Br/Ar discharges was investigated as a function of both plasma power density (0.56-1.3 W - cm−2) and total pressure (10-40 mTorr) The etch rate of GaAs in 19CF3Br:1Ar discharges at 10 m Torr increases linearly with power density, from 600 A min−1 at 0.56 W · cm−2, to 1550 A · min at 1.3 W · cm−2. The in-based materials show linear increases in etch rates only for power densities above − 1.0 W · cm−2. These etch rates are comparable to those obtained with CCI2F2:O2 mixtures under the same conditions. Smooth surface morphologies and vertical sidewalls are obtained over a wide range of plasma parameters. Reductions in the near-surface carrier concentration in n-type GaAs are evident for etching with power densities of >0.8 W cm−2, due to the introduction of deep level trapping centers. At 1.3 W· cm−2, the Schottky barrier height of TiPtAu contacts on GaAs is reduced from 0.74 to 0.53 eV as a result of this damage, and the photoluminescent intensity from the material is degraded. Alter RIE, we detect the presence of both F and Br on the surface of all of the semiconductors. This contamination is worse than with CCl2F2-based mixtures. High-power etching with CF3Br/Ar together with Al-containing electrodes can lead to the presence of a substantial layer of aluminum oxide on the samples if the moisture content in the reactor is appreciable.