Given the added complexity in flux calibration and composition evaluation inherent to quinary alloy growth, what motivates compounding the challenges of III-V-Bi growth with the goal of producing a quinary alloy of GaInAsSbBi for mid- and long-wave infrared sensing applications? Each elemental constituent provides some additional design freedom to achieve the ultimate goal of producing a lattice-matched, bulk random alloy mid-wave infrared III-V material with smooth surface morphology and high optoelectronic quality to enable high performance elevated operating temperatures. This paper reviews the evolution of Bi-containing semiconductor research, focusing on mid- and long-wave infrared materials and highlighting key research findings that motivated the decisions to accept the added complexity in going from binaries like InAs or InSb, to InAsBi, to InAsSbBi, and, finally, to GaInAsSbBi to meet the performance demands of advanced infrared sensing applications.

The impact of unintentional incorporation of Sb in the tensile InAs layer of type-II strain-balanced InAs/InAsSb superlattices is investigated. Several coherently strained midwave and longwave superlattices are grown on (100) GaSb substrates by molecular beam epitaxy and examined using x-ray diffraction and temperature-dependent photoluminescence spectroscopy. The zero-order diffraction angle provides the average Sb mole fraction of the strain-balanced superlattice period. Analysis of the higher order diffraction angles, along with the individual layer growth times and strain, provides the InAs and InAsSb layer thicknesses. Analysis of the photoluminescence measurements provides the ground-state bandgap of the superlattice, which along with simulations of the ground-state energies of the electrons and holes using a Kronig–Penney model, specify how the Sb is distributed between the tensile and compressive layers of the period and ultimately the quantity of unintentional Sb in the InAs layer. The unintentional Sb mole fractions observed in the tensile InAs layers are 1.9% for midwave and 1.2% for longwave. When compared to superlattices with the same period and no Sb in the tensile layer, the presence of unintentional Sb blue-shifts the 77 K temperature cutoff wavelength from 6.3 to 5.3 μm for midwave and from 18.8 to 12.0 μm for longwave.

InAsSbBi nBn photodetectors are demonstrated that are lattice-matched to the underlying GaSb substrate with a 4.32 μm wavelength cutoff at 150 K that is 0.3 μm longer than that of lattice-matched InAsSb at this temperature reflecting a 0.5% Bi mole fraction in the InAsSbBi active region. A low growth temperature was utilized to facilitate the incorporation of Bi, resulting in a minority carrier lifetime on the order of 24 ns in the InAsSbBi active region. Nevertheless, the detectors exhibit a quantum efficiency of 17% at 3.3 μm wavelength with a dark current density of 50 μA/cm2 at 150 K and −0.4 V bias and the strong photoresponse turn-on characteristic of a random alloy at 4.32 μm wavelength and 150 K. A shot noise-equivalent irradiance analysis indicates that this detectors' dark-current-limited noise-equivalent irradiance of 1012 cm−2 s−1 is two orders of magnitude greater than the Rule 07 expectation for this cutoff, and dark-current-limited shot noise-equivalent irradiance performance transitions to photon-limited at 1.7 × 1015 photons/cm2 s.

Quinary GaInAsSbBi is grown by molecular beam epitaxy, and the alloy is demonstrated with a bandgap energy of 291 meV (λcutoff ∼ 4.3 μm) and a minority carrier lifetime of 0.34 μs at 120 K. The GaInAsSbBi epilayer is grown to a thickness of 1 μm at 400 °C and lattice-matched to the GaSb substrate with a Bi mole fraction of 0.13% measured by Rutherford backscattering spectroscopy. Steady-state and time-resolved photoluminescence measurements are performed to gauge the comparative bandgaps and optical quality of GaInAsSbBi as well as InAsSbBi and GaInAsSb reference samples. A recombination rate analysis is performed on the low-injection temperature-dependent minority carrier lifetime to extract the Shockley–Read–Hall defect level and intrinsic doping concentration of the GaInAsSbBi.

Type-II superlattice nBn photodetectors based on mid-wave infrared III-V materials have progressed considerably in terms of noise and quantum efficiency. While these traits lend feasibility towards space-based applications, it is necessary to examine the consequences of proton irradiation and investigate strategies for mitigating performance degradation.

Gallium is incorporated into the strain-balanced In(Ga)As/InAsSb superlattice system to achieve the same mid-wave infrared cutoff tunability as conventional Ga-free InAs/InAsSb type-II superlattices, but with an additional degree of design freedom to enable optimization of absorption and transport properties. Time-resolved photoluminescence measurements of InGaAs/InAsSb superlattice characterization- and doped device structures are reported from 77 to 300 K and compared to InAs/InAsSb. The low-injection photoluminescence decay yields the minority carrier lifetime, which is analyzed with a recombination rate model, enabling the determination of the temperature-dependent Shockley–Read–Hall, radiative, and Auger recombination lifetimes and extraction of defect energy levels and capture cross section defect concentration products. The Shockley–Read–Hall-limited lifetime of undoped InGaAs/InAsSb is marginally reduced from 2.3 to 1.4 μs due to the inclusion of Ga; however, given that Ga improves the vertical hole mobility by a factor of >10×, a diffusion-limited InGaAs/InAsSb superlattice nBn could expect a lower bound of 2.5× improvement in diffusion length with significant impact on photodetector quantum efficiency and radiation hardness. At temperatures below 120 K, the doped device structures are Shockley–Read–Hall limited at 0.5 μs, which shows promise for detector applications.

Three InAsSbBi samples are grown by molecular beam epitaxy at 400 °C on GaSb substrates with three different offcuts: (100) on-axis, (100) offcut 1° toward [011], and (100) offcut 4° toward [011]. The samples are investigated using X-ray diffraction, Nomarski optical microscopy, atomic force microscopy, transmission electron microscopy, and photoluminescence spectroscopy. The InAsSbBi layers are 210 nm thick, coherently strained, and show no observable defects. The substrate offcut is not observed to influence the structural and interface quality of the samples. Each sample exhibits small lateral variations in the Bi mole fraction, with the largest variation observed in the on-axis growth. Bismuth rich surface droplet features are observed on all samples. The surface droplets are isotropic on the on-axis sample and elongated along the [011¯] step edges on the 1° and 4° offcut samples. No significant change in optical quality with offcut angle is observed.

The growth of Bi-containing III-V alloys requires careful control over temperature and group-V fluxes due to the low equilibrium solubility of Bi and its tendency to surface segregate into Bi-rich droplet features. A model for molecular beam epitaxy growth based on the kinetics of atomic desorption, incorporation, surface accumulation, and droplet formation is applied to the bismide alloy InAsSbBi grown on GaSb substrates. A steady-state solution is derived for the Bi, Sb, and As mole fractions and surface layer coverages based on the Bi, Sb, and As fluxes. A nonlinear least-squares algorithm is used to fit the growth model parameters to experimentally measured Bi mole fractions in bulk and quantum well InAsSbBi samples grown at 400 °C and 420 °C. The Bi mole fraction ranges from 0.12% to 1.86% among 17 samples examined. The results indicate that as the growth temperature increases, the rate of Bi incorporation decreases and the rate of Bi self-desorption increases. A strong interaction is observed between Bi and As that plays a role in the desorption of excess Bi from the growth surface, thus reducing the likelihood of Bi-rich droplet formation when an excess As flux is present. Significantly, the model predicts that the incorporation of Bi is limited to mole fractions of 1.43% at 400 °C and 0.30% at 420 °C in lattice-matched bulk InAsSbBi grown on GaSb substrates.

The structural and optical properties of two 210 nm thick InAsSbBi epilayers grown on (100) GaSb substrates by molecular beam epitaxy at 400 and 280 °C are investigated using X-ray diffraction, Rutherford backscattering spectroscopy, transmission electron microscopy, and photoluminescence spectroscopy. Both samples are free of observable defects. The higher temperature growth results in reduced Bi incorporation, good optical performance, smooth interfaces, and lateral composition modulation of the Bi mole fraction. The lower temperature growth results in near unity Bi incorporation, poor optical performance, interface roughness, and CuPtB -type atomic ordering on the {111}B planes.

Time-resolved photoluminescence measurements are reported for InAsSbBi alloys grown by molecular beam epitaxy with Bi mole fractions ranging from 0 to 0.8%, yielding minority carrier lifetimes on the order of hundreds of nanoseconds. The minority carrier lifetimes extracted from the time-resolved photoluminescence measurements are comparable to those of lattice-matched InAsSb grown at the same respective temperatures. Nomarski imaging shows that smooth, droplet-free surface morphologies are obtained in 1 μm thick InAsSbBi epilayers grown at temperatures between 360 and 380 °C. The alloy composition-dependent bandgap energies for the InAsSbBi samples are determined from temperature-dependent steady-state photoluminescence measurements and compared with the tetragonal distortion measured by x-ray diffraction to determine the Sb and Bi mole fractions of each sample. The minority carrier lifetime and the achievable extension of the InAsSb(Bi) cut-off wavelength are analyzed as functions of alloy composition and compared with the performance of InAsSb layers with similar growth parameters.

The physical characteristics of the fundamental absorption edge of semi-insulating GaAs and unintentionally doped GaSb, InAs, and InSb are examined using spectroscopic ellipsometry. A five parameter model is developed to describe the key characteristics of the absorption edge. Among these parameters are the bandgap energy, the characteristic energy of the Urbach tail, and the absorption coefficient at the bandgap energy. The results indicate that the Coulomb interaction strongly influences the shape of the band edge with progressively less influence as the bandgap energy decreases. The energy dependence of the optical transition strength is observed to be nearly constant in narrow bandgap InSb.

The physical and chemical properties of 210 nm thick InAsSbBi layers grown by molecular beam epitaxy at temperatures between 400 and 430 °C on (100) GaSb substrates are investigated using Rutherford backscattering, X-ray diffraction, transmission electron microscopy, Nomarski optical microscopy, and atomic force microscopy. The results indicate that the layers are nearly lattice matched, coherently strained, and contain dilute Bi mole fractions. Large surface droplets with diameters on the order of 1 μm and densities on the order of 106 cm−2 are observed when the InAsSbBi growth is performed with lean As overpressures around 1%. Surface droplets are not observed when the As overpressure is increased to 4%. Small crystalline droplets with diameters on the order of 70 nm and densities on the order of 1010 cm−2 are observed between the large droplets for InAsSbBi grown at 430 °C. Analysis of one of the small droplets indicates a misoriented zinc blende crystal structure composed primarily of In, Sb, and Bi, with a lattice constant of 6.543 ± 0.038 Å. Lateral modulation in the Bi mole fraction is observed in InAsSbBi layers grown at 400 °C.

The molecular beam epitaxy growth and optical properties of the III-V semiconductor alloy InAsSbBi are investigated over a range of growth temperatures and V/III flux ratios. Bulk and quantum well structures grown on the (100) on-axis and offcut GaSb substrates are examined. Bismuth readily incorporates at growth temperatures around 300 °C but results in materials with limited optical quality. Conversely, higher growth temperatures around 400 °C yield improved optical performance but with limited Bi incorporation. Photoluminescence spectroscopy is used to examine the optical properties and bandgap energies of InAsSbBi layers grown at temperatures from 400 to 430 °C using 0.91 and 0.94 As/In flux ratios, 0.10 and 0.12 Sb/In flux ratios, and 0.05 and 0.10 Bi/In flux ratios. Emission is observed from low to room temperature with peaks ranging from 3.7 to 4.6 μm. The relationships between Bi incorporation, surface morphology, growth temperature, and group-V flux are examined. Large concentrations of Bi-rich surface features are observed on samples where the incident Bi flux neither fully incorporates nor desorbs but instead accumulates on the surface and coalesces into droplets.

The conditions for molecular beam epitaxy growth of InAsBi are explored for optoelectronic applications. X-ray diffraction measurements of thick InAsBi on GaSb samples show a diffraction sideband near the main (004) diffraction peak, indicating lateral variation of Bi mole fraction in the layer. By modeling the main and sideband diffraction peaks, the average InAsBi unstrained lattice constant is determined. By comparing these results with the Bi mole fraction for each sample determined using random Rutherford backscattering, the lattice constant of zinc blende InBi is determined to be 6.6107 Å. The bandgap of InAsBi is expressed as a function of the Bi mole fraction using the band anticrossing model and a characteristic coupling strength of 1.529 eV between Bi impurity state and the InAs valence band. A software tool is programmed to identify optimal InAs/InAsBi and GaSb/InAsBi superlattice designs with maximum electron-hole wavefunction overlap as a function of transition energy.

Density functional theory is used to determine the electronic band structure and eigenstates of dilute InAsBi bulk materials. The results serve as input for fully microscopic many-body models calculating the composition and carrier density dependent losses due to Auger recombination. At low to intermediate carrier concentrations, the Auger loss coefficients are found to be in the range of 10−27cm6/s for a low Bi content and around 10−25cm6/s for compositions suitable for long wavelength emission. It is shown that due to the fact that in InAsBi, the spin-orbit splitting is larger than the bandgap for all Bi contents, the Bi-dependent increase in the spin-orbit splitting does not lead to a significant suppression of the losses. Instead, unlike in GaAsBi, a mostly exponential increase in the losses with the decreasing bandgap is found for all compositions.

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Bandstructure properties of dilute bismide bulk systems are calculated using density functional theory. An extended band anti-crossing model is introduced to fit the obtained results. Using these as inputs for a fully microscopic many-body theory, absorption and photoluminescence spectra are computed for bulk and quantum-well systems. Comparison to experimental results identifies the applicability range of the new anti-crossing model.

Strain-balanced InAs/InAsSb superlattices can be tuned to absorb and emit across the mid- to long-wave infrared, and exhibit appropriate minority carrier lifetimes for high performance infrared photodetectors. The optical quality of this material has been shown to improve with the use of Bi as a surfactant. Specifically, InAs/InAsSb superlattices grown at 425 °C and 430 °C exhibit improved photoluminescence intensity for Bi/In flux ratios up to 1.0%, and optical quality improves further with increasing growth temperature and increasing Bi/In flux ratios up to 5.0%. The identification of optimal growth conditions for InAs/InAsSb superlattices with Bi surfactant, as well as further exploration of the impact of Bi surfactant is an important component to further developing and optimizing this infrared material system. Several strain-balanced InAs/InAsSb superlattices are grown using molecular beam epitaxy at temperatures ranging from 425 °C to 475 °C using Bi/In flux ratios ranging from 0.0% to 10.0%. The structural and optical properties of the samples are evaluated using X-ray diffraction, secondary ion mass spectrometry, and photoluminescence spectroscopy. Analysis of the mass spectrometry data indicates that surfactant Bi incorporates into the InAs/InAsSb material system with a sticking coefficient of 0.3% at 450 °C, yielding dopant-level concentrations for typical Bi/In surfactant flux ratios. Analysis of the integrated photoluminescence intensity indicates that photoluminescence efficiency is greatest with a 1.0% Bi/In flux ratio for growth at 425-430 °C, and a 5.0% Bi/In flux ratio for growth at 450-475 °C. The improvement in photoluminescence efficiency is associated with a longer Shockley-Read-Hall lifetime in the superlattices grown with Bi surfactant.

The introduction of Bismide in InAs leads to a strong bandgap reduction on the order of 40-50meV per percent Bi-admixture. This allows InAsBi to be able to reach mid-IR wavelengths in the 3-5 μm range with less than about three percent Bi. Typically, materials for this wavelength range suffer from very strong Auger losses. These have so far limited room-temperature CW operation in devices based on type-I quantum wells to wavelength shorter than about 3.5 μm.

The structural and optical properties of pseudomorphic InAsSbBi grown on GaSb are examined using reflection high-energy electron diffraction, X-ray diffraction, Rutherford backscattering spectrometry, and spectroscopic ellipsometry. The layer studied is 210 nm thick and was grown by molecular beam epitaxy at 280 °C under a (2 × 3) surface reconstruction using near-stoichiometric fluxes. The material is homogeneous and single crystal with no observable defects or surface Bi droplets. The group-V mole fractions are determined using Rutherford backscattering measurements of the Bi mole fraction and X-ray diffraction measurements of the lattice tetragonal distortion. The bandgap energy is determined from the room temperature optical constants measured using spectroscopic ellipsometry. These and measurements from pseudomorphic InAsSb and InAsBi on GaSb are utilized to describe the bandgap energy of InAsSbBi as a function of mole fraction using a bandgap bowing model.