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While recent work developing GaAsBi for opto-electronic applications has shown promise, it has also indicated that the large valence band offset of GaAsBi/GaAs may cause undesirable hole-trapping in GaAsBi quantum wells. In this work, hole-trapping is demonstrated to be the cause of the reduced depletion width of GaAsBi/GaAs multi-quantum well solar cell devices under illumination. Modelling of the quantum confinement energies in these devices shows how the carrier escape times vary as functions of temperature, providing a tool for the design for future GaAsBi based photovoltaic devices.

GaAsBi/GaAs multiple quantum well (MQW) p–i–n diodes are grown by molecular beam epitaxy. Transmission electron microscope images of the diodes show good agreement between the intended and measured MQW periods, but poor agreement between the intended and measured GaAsBi quantum well thicknesses. This is likely due to the incorporation of Bi from a physisorbed surface layer that takes a finite time to accumulate during growth. The diodes with more than 40 wells show dislocations that indicate strain relaxation. This is supported by x-ray diffraction analysis, which also suggests that the i-region of the 54 well diode is tilted with respect to the substrate.

The optical and structural properties of GaAsBi bulk and quantum well (QW) samples grown under various conditions were studied by photoluminescence (PL), high resolution x-ray diffraction (HR-XRD) and transmission electron microscopy (TEM). At 10 K, the 90 nm bulk sample shows two PL peaks at 1.18 and 1.3 eV. The temperature and power dependent PL data suggest that both PL peaks originate from the GaAsBi layer which consists of two regions with different Bi concentrations. The TEM images verify that the Bi concentration decreases monotonically across the layer, showing a high Bi concentration (~0.053) close to the bottom interface which then reduces to ~0.02 for thicknesses >25 nm. Besides, the high Bi content region cannot be detected by HR-XRD due to a broad and weak diffraction intensity. For multiple QW samples, a similar Bi profile was also observed in which the first well has a significantly higher Bi content compared to the other wells. The energy separation between the PL peaks is 0.12 eV and is consistent with the energy difference observed for the bulk sample. However, two PL peaks were not observed in the other GaAsBi bulk sample which was grown under different conditions, showing the importance of growth optimizations.

Photoreflectance (PR), photoluminescence (PL) and time-resolved PL were applied to study the optical properties, particularly the localized and delocalized states and carrier dynamics, in GaAs1−xBix/GaAs quantum wells. With increasing Bi concentration the ground state transition (i.e., the transition between the first heavy hole and the first electron subband) red shifts due to Bi-related reduction of the GaAs1−xBix energy gap. Additionally, the transition related to the excited states in the quantum wells is clearly observed for the sample with high Bi concentration of 5.6%, confirming these quantum wells are type I. The PL measurements show the S-shape behavior and indicate the strong localization effect below 150 K for all measured samples, while the PL emission above 150 K is related to delocalized states. The localized character of emission at low temperatures is confirmed by time-resolved PL studies. At 10 K the decay time has strong spectral dispersion (i.e. the decay time increases from ~10 ns to ~400 ns going from the high to low energy side of the PL peak). This dispersion disappears above 190 K. At room temperature the decay time is in the order of a few ns.

The absorption properties of GaAsBi have been investigated using GaAsBi based p–i–n diodes with different bismuth compositions (~2.1 and ~3.4%). The absorption behaviour of GaAsBi as a function of incident photon energy above the band gap follows that of a direct band gap material. With increasing bismuth content, the absorption of photons with energy lower than the band gap in GaAsBi is enhanced, probably due to localized states caused by Bi-related defects. A simplified analysis has been undertaken on the behaviour of absorption as a function of bias voltage. By undertaking photoresponsivity measurements as a function of reverse bias, the background doping type and the minority carriers diffusion lengths in GaAsBi have been determined.