Near-surface (∼1000 Å) modification in the net carrier concentration in n-type InP (n=6×1015–1.5×1017 cm−3) was observed after reactive ion etching (RIE) in Cl-based (CCl2F2/O2) or organic-based (C2H6/H2) discharges. The carrier loss is slightly more pronounced in the latter case, due possibly to the creation of deep level, compensating acceptors at greater depths as a result of implantation of the light hydrogen ions. Near-complete recovery of the initial carrier density occurs after annealing at 500 °C for 30 s. Structural disorder is detected by ion channeling to depths of ∼400 Å after C2H6/H2 RIE with a self-bias of 380 V. This disorder shows significant recovery after 400 °C, 30 s annealing. Current-voltage measurements on Au Schottky diodes showed ohmic behavior after etching of the InP in a C2H6/H2 discharge, due to the nonstoichiometric surface remaining after RIE. Diodes fabricated on CCl2F2/O2 etched material show only a slight increase in reverse current compared to unetched control samples.
Specular, crack-free thin films of the refractory conductor zirconium boride have been deposited for possible applications in combined contact/diffusion barrier metallization schemes. Films were deposited by dc triode sputtering, which allowed the independent study of the effects of sputtering pressure, target voltage, and current on the film properties. The mole ratio of boron in the films increased (composition tending to ZrB2) and the resistivity decreased with increasing deposition rates which at a fixed target voltage and sputtering pressure increased almost linearly with target current. Decrease in sputtering pressure, with only a minor change in deposition rate, dramatically decreased resistivity and caused stress in the films to change from tensile to compressive. X-ray photoelectron spectroscopy correlated reduced oxygen content to reduced resistivity. Triode sputtering permitted deposition of films at 2 mTorr with a resistivity of 162 μΩ cm which is the lowest reported value for as-deposited films.
Near-surface damage created by Ar+ ion milling in InP and GaAs was characterized by capacitance-voltage, current-voltage, photoluminescence, ion channeling, and transmission electron microscopy. We find no evidence of amorphous layer formation in either material even for Ar+ ion energies of 800 eV. Low ion energies (200 eV) create thin (≤100 Å) damaged regions which can be removed by annealing at 500 °C. Higher ion energies (≥500 eV) create more thermally stable damaged layers which actually show higher backscattering yields after 500 °C annealing. Heating to 800 °C is required to restore the near-surface crystallinity, although a layer of extended defects forms in GaAs after such a treatment. No dislocations are observed in InP after this type of annealing. The electrical characteristics of both InP and GaAs after ion milling at ≥500 eV cannot be restored by annealing, and it is necessary to remove the damaged surface by wet chemical etching. For the same Ar+ ion energies the damaged layers are deeper for InP than for GaAs after 500 eV ion milling at 45° incidence angle. Removal of ∼485 and ∼650 Å from GaAs and InP, respectively, restores the initial current-voltage characteristics of simple Schottky diodes.
Structural and electrical damage imparted to InP and In0.72Ga0.28As0.6P0.4 (λg≂1.3 μm) surfaces during CH4/H2 reactive ion etching (RIE) have been examined. X-ray photoelectron spectroscopy was used to monitor changes in the surface chemistry, Rutherford backscattering spectrometry was used to measure crystallographic damage, and current-voltage and capacitance-voltage measurements were made to examine electrically active damage and its depth. Two classes of damage are observed: crystallographic damage originating from preferential loss of P (As) and/or ion bombardment-induced collision cascade mixing and, for p-type material, hydrogen passivation of Zn acceptors. Etching at 13.6 MHz, 60–90 mTorr, 10% CH4/H2, and bias voltages of ∼300 V contains gross (≳1%) damage as measured by RBS to within 40 Å and electrically active damage to within 200 Å of the surface. This is a factor of 3–6 shallower than other RIE processes operated below 10 mT with comparable or higher bias voltages. Acceptor passivation of both InP and InGaAsP, arising from the association of hydrogen with Zn sites, occurs to a depth of 2000 Å after RIE and causes a decrease in carrier concentration in this layer. The effect is reversed, however, by rapid thermal processing at temperatures between 350 and 500 °C.
The characteristics of ion implantation induced damage in InAs, GaSb, and GaP, and its removal by rapid thermal annealing have been investigated by Rutherford backscattering and transmission electron microscopy. There is relatively poor regrowth of these materials if they were amorphized during the implantation, leaving significant densities of dislocation loops, microtwins, and in the case of GaSb, polycrystalline material. For implant doses below the amorphization threshold, rapid annealing produces good recovery of the lattice disorder, with backscattering yields similar to unimplanted material. The redistribution of the implanted acceptor Mg is quite marked in all three semiconductors, whereas the donor Si shows no measurable motion after annealing of InAs or GaP. In GaSb, however, where it appears to predominantly occupy the group III site, it shows redistribution similar to that of Mg.
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