Seventeen samples of CdGeAs2 have been extensively characterized by temperature-dependent Hall effect and resistivity measurements. Due to the anisotropic nature of the electrical properties, carefully matched sample sets were fabricated with the c-axis either in or out of the plane of the sample. The matched samples allowed determination of carrier concentration and both in-plane and out-of-plane mobilities as a function of temperature. The electrical properties of both undoped and lightly doped samples were dominated by either native defects or residual growth impurities, leading to compensated p-type material. N-type doped material was obtained only with heavy doping. An apparent variation in acceptor activation energy between 110 and 165 meV could be best explained in terms of two deep acceptor levels and at least one shallow donor. Room temperature absorption coefficient data and the relation to background doping is also reported.

This paper describes the reduction of the near-band-edge absorption of zinc germanium phosphide (ZGP) through thermal annealing. The effects of the annealing time, temperature and vapour atmosphere on the reduction of the optical absorption in the near infrared (NIR) region are reported. Results have shown that the optical absorption at 2µm is reduced by at least 50% upon thermal anneal of ZGP. The optimal annealing temperature was 600'C and the optimal annealing time ranged from 200 - 400 h. Annealing in vacuum yielded a larger reduction in the 2-µm optical absorption compared to annealing in the presence of additional zinc and phosphorus vapours. Re-annealing ZGP further reduced the absorption coefficient at 2-µm. However, the percentage decrease in the 2-µm absorption coefficient was much smaller compared to the first thermal anneal.

CdGeAs2 single crystals were prepared by low temperature crystallization from a nonstoichiometric melt. The results of the first study of the temperature dependencies of the electrical conductivity and the Hall coefficient of n-type CdGeAs2 single crystals prepared by this new technique are reported. All the as-grown crystals show n-type conductivity. These single crystals had free electron concentrations of (1 - 2) 1018 cm−3 and Hall mobilities of more than 10000 cm2/(Vs) at T=300 K. These room temperature electron mobility values are four times larger than previously reported. In the high temperature region (T> 150K), the temperature dependence of the Hall mobility exhibited a behavior characteristic of phonon scattering. Below 150 K, a deviation from this behavior indicated an increasing contribution of static lattice defects to scattering. The Hall mobility in these crystals was found to reach ∼ 36000 cm2/( V· s ) at 77 K. The first photosensitive n-type CdGeAs2/n-type InSe heterostructures were constructed by contact methods. Photosensitivities of 70-100 V/were observed. This is substantially better than for previous structures using conventionally grown CdGeAs2 and indicates the high quality of the crystals. It is concluded that the low temperature growth technique is promising for the preparation of more perfect CdGeAs2crystals.

Zinc germanium diphosphide (ZnGeP2) is a nonlinear optical material used in mid-infrared optical parametric oscillators. The near-infrared photoluminescence (PL) from single crystals of bulk ZnGeP2 has been studied as a function of excitation power, wavelength, temperature, and polarization. At 5 K, a broad PL band extending from 0.7 µm to beyond 1 µm is typically observed. Two distinct emissions with different polarization, power, and temperature behaviors have been resolved. These bands have peaks in intensity near 1.6 eV and 1.4 eV. The relative intensities of these two bands were found to correlate with the presence of phosphorus vacancies, as determined by electron paramagnetic resonance (EPR). A resonance in the intensity of the 1.6-eV band occurs when pumping into a level ∼90 meV below the minimum conduction band. This level is tentatively assigned to the shallow state.

Recent experiments in mid IR frequency conversion have revealed that older Sellmeir models for zinc germanium phosphide are inadequate. Erroneous predictions in phase matching angles based on older refractive index data have resulted in compromised device performance. We have conducted a complete study of the refractive indices of zinc germanium phosphide from 2 to 9 microns and calculated new Sellmeir coefficients. We have used these to explain the results of recent experiments with mid IR optical parametric oscillators. The phase matching calculations based on our new refractive index data predict much more closely the results of several different mid IR frequency conversion experiments.

The paper presents the results of TEM and optical transparency measurements on ZnGeP2 crystals grown by the vertical Bridgman technique from melts of differing compositions. The TEM study reveals the presence of nano-dimensional precipitates of second phases: zinc and ZnxPy precipitation occurs in material grown from Zn-rich melts and GeP from the deficient melts. The precipitation is associated with cooling through the retrograde solidus at a temperature below the melting point. Elastic stress fields are also observed. The relationships between the precipitates and elastic stresses and between precipitation and optical losses are investigated

The optical and electrical properties of chrome-doped CdGeAs2 (CGA), an important non-linear optical material, are reported. CGA, a chalcopyrite semiconductor of the pseudo- III-V type, is a close ternary analog to GaAs, possessing significant differences. To date, the electrical and optical properties of as-grown undoped CGA have been controlled by a somewhat shallow dominant residual acceptor which it is the source of significant undesirable optical absorption. Highly transparent semi-insulating CGA should be attainable using compensation and counterdoping schemes similar to those used for GaAs. However, identifying suitable deep and shallow n-type and p-type dopants will require extensive empirical studies. As a starting point of survey to find deep levels, the properties of CGA:Cr have been investigated. Cr is a reasonable choice as it has been used extensively to provide a deep level in GaAs. Thermal Admittance Spectroscopy was used to examine the electrically active levels in this material. These measurements were correlated with temperature dependent Hall effect measurements, and IR absorption measurements. SIMS analysis was utilized to estimate the Cr concentration as the segregation coefficient for Cr in CGA has not been reported.. The results show that there is a p-type level introduced into the band gap at about 0.16 eV above the valence band, a value nominally 50% deeper than that of the native acceptor. The background doping as measured by Capacitance-Voltage measurements was determined to be 8 × 1016 cm−3 near the surface, and 1.0 × 1017 cm−3 in the bulk. These results are compared to similar measurements in undoped material.

The results of a shell-model study on CdGeAs2 doped with Cu, Ag, B, Al, Ga, and In are presented here. The pairwise interatomic potential terms representing the interaction of dopants with the host lattice ions are derived using first principle methods while empirical fitting methods are used for the host-lattice potentials. Defect calculations based on Mott-Littleton methodology predict small binding energies for Cu and Ag substituting Cd in the lattice which are in agreement with the available experimental data. The group III dopants (i.e. B, Al, Ga and In) at the Ge site are predicted to have large binding energies for a hole placing acceptor levels in the middle of the band gap.

A novel technique for quantum-well intermixing has been developed using sputtered silica. The technique relies on the generation of point defects via plasma induced damage during the deposition of the sputtered silica. The presence of the defects before annealing allows the intermixing to take place at lower annealing temperatures (>200 C) than those needed for conventional impurity free vacancy disordering. The low annealing temperature has allowed the technique to be applied to InP based quantum well systems such as InGaAs/InGaAsP and InGaAs/InGaAlAs, and provides a simple and reliable process for the fabrication of both wavelength tuned lasers and monolithically integrated devices operating around 1550 nm.

Wavelength tuned broad area oxide stripe lasers have been demonstrated in InGaAs-InAlGaAs and InGaAs-InGaAsP quantum wells. Oxide stripe lasers with integrated intermixed slab waveguides have enabled the production of a narrow (3 degrees), single lobed far field pattern in InGaAs-InAlGaAs devices. Extended cavity ridge waveguide lasers operating around 1550 nm have been demonstrated with low loss (alpha = 4.1/cm) waveguides, the loss beinglimited by free carrier absorption in the waveguide cladding layers. Ridge waveguide, deeply etched surface grating DBR lasers were fabricated both with and without intermixing the grating section. Measurements show that a significant improvement in performance is obtained from the DBR lasers when the grating section is intermixed.

The intermixing technique has been further developed in order to realise 3 bandgaps on a chip in a single annealing step for the integration of amplifiers, passive waveguides and bandgap tuned electro-absorption modulators. Modulation depths of 25 dB were measured from the modulators.

The results illustrate that the technique can routinely be used to fabricate low-loss optical interconnects and bandgap tuned devices, offering a very promising route toward photonic integration.

We have investigated the influence of SiOx capping layer quality on impurity-free vacancy interdiffusion in GaAs/Al0.54Ga0.46As quantum wells. Dielectric layers were deposited by plasmaenhanced chemical vapor deposition, and properties of layers were changed by varying either the flow rate of silane or deposition temperature. The extent of intermixing in our samples is discussed in terms of the 0 content and incorporation of N in capping layers, and also on their porosity. We also report on the electrically active defects which are introduced in Si02 capped and annealed n-GaAs, and relate them to the intermixing process.

Intersubband transitions in GaAs/AIGaAs multiple quantum wells (MQWs) are studied as a function of 2 MeV electron irradiation doses using the optical absorption technique. The MQW structure was designed with a 5 period Al.4Ga.6As/GaAs superlattice barrier, and two transitions are observed in the spectra. These transitions occur from the ground state to the first excited state and to the miniband formed by the superlattice barrier. The total integrated area from both transition spectra are studied as a function of temperature and electron irradiation dose. For the ground state to first excited state transition the total integrated area decreases exponentially as the irradiation dose increases, which could be explained in terms of the trapping of the 2D-electron gas in the quantum well by the irradiation induced defects. In comparison, the intensity of the ground state to miniband transition was found to increase exponentially as a function of the irradiation dose. Two possible explanations for this behavior are suggested. The temperature dependence of the integrated area of both transitions is also presented.

In this paper we shall discuss techniques for accurate, non-destructive, optical characterisation of structures fabricated using quantum well intermixing (QWI). Spatially resolved photoluminescence and Raman spectroscopy were used to characterise the lateral bandgap profiles produced by impurity free vacancy disordering (IFVD) technology. Different features were used to examine the spatial resolution of the intermixing process. Features include 1:1 gratings as well as isolated stripes. From the measurements, the spatial selectivity of IFVD could be identified, and was found to be ∼4.5 μm, in contrast with the spatial resolution of the process of sputtering induced intermixing, which was found to be ∼2.5 μm. In addition, PL measurements on 1:1 gratings fabricated using IFVD show almost complete suppression of intermixing dielectric cap gratings with periods less than 10 microns. Finally, some insight into the limitations and merits of PL and Raman for the precision characterisation of QWI will be presented.

The dependence of impurity free vacancy disordering (IFVD) of InGaAs/InGaAsP QW structure on the characteristics of dielectric capping layer was studied using SiNx film as capping layers. The characteristics of the SiNx capping layer were varied by changing the NH3 flow rate during SiNx deposition by plasma enhanced chemical vapor deposition (PECVD). The degree of quantum well intermixing (QWI) with SiNX capping layer grown at higher NH3 flow rate was larger than that with SiNx film grown at lower NH3 flow rate. This implies that QWI can be easily controlled by simply changing the reactive gas ratio in the growing process of SiN, capping layer. It was also shown that this method to control QWI is better than the method of using two different capping layers such as SiNx film and SiO2 film in order to get spatially selective QWI on the same substrate.

The effect of disordering on photoluminescence spectra of InGaAs/InGaAsP quantum wells has been investigated experimentally and theoretically taking into account the valence band intermixing, strain, exciton effects, and the non-identical diffusion constants for group III and V materials. The disordering profile of 1.55Q InGaAs/InGaAsP quantum wells lattice matched to InP has been controlled by choice of the cap layer materials as well as the diffusion time and diffusion temperature. By comparing the experimental data and theoretical calculations, the diffusion constant for each material has been extracted.

Interband transitions in n-type InGaAs/AlGaAs multiple quantum wells were studied using a photoluminescence (PL) technique after the samples were irradiated with fast neutrons. It was observed that the PL intensity of the interband transition is reduced as the irradiation dose is increased. In Addition, the peak position energy of the interband transition was increased and then decreased as a function of irradiation dose. The results are explained in terms of electrons trapping, many-body effects, and irradiation-induced damages at the interfaces as well as in the well and barrier regions.