In order to explain the effects of hydrogen on the electrical properties of bulk indium phosphide crystals, we have performed a series of high temperature annealing studies with both undoped and iron-doped indium phosphide crystals. Our samples were annealed at 900 deg for 6, 36, and 72 hours, respectively, under a phosphorus overpressure of five atmospheres. Samples were characterized at 10 K by Fourier transform infrared absorption spectroscopy which allowed us to measure the concentrations of both the Fe~(2+) and V_(In)-H_4 defects simulataneously. Undoped samples were further characterized by the Hall effect measruements. We find in the iron-doped samples that the [Fe~(2+)]/[Fe~(3+)] ratio decreases gradually with increasing annealing time, indicating a reductionin the number of donors in the samples. In the undoped samples, annealing leads to a reduction of the free electron concentration accompanied by an increase in the 77 K mobility. The increase of the sample's mobility eliminates the possibility that the reduction of the free electron concentration is due to an increase in the concentration of the compensating acceptors. Our explanation for the observed behavior in all samples is that hydrogen acts as a donor and it diffuses out of the crystal during the annealing process. Based on our experimental data, we propose a calibration equation of [V_(In)-H_4]=4.2X10~(16) cm~(-1) x Absorbance (cm~(-1)) which is used to correlate the hydrogen-vacancy complex concentrations with the changes of the V_(In)-H_4 absorption peak in both the iron-doped and the undoped samples. Our results confirm the donor nature of the hydrogen-vacancy complex and provide strong evidence regarding the reduction mechanism of free carrier concentrations in bulk indium phosphide crystals during high temperature annealing under a phosphorus atmosphere.
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