The growth and characterization of device quality InP/ Ga1-xinxasyp1-y double heterostructures by atmospheric-pressure MOVPE using trimethylindium

We report on recent developments of the atmospheric pressure OMVPE of InP and In_xGa_1-xAS_yP_1-y using trimethylindium, trimethylgallium, phosphine and arsine. The use of diffuser organometallic sources significantly increased the accuracy of quaternary composition control. This control was achieved in the whole range of quaternary light emitting wavelengths from 1.20 micrometers up to the ternary GaInAs limit. The influence of the carrier gas was further investigated: device-quality heterostructures were obtained for either of the three carrier gases hydrogen, helium and argon. The experimental conditions for growing quaternaries with a given composition agree well with a simple model. This work has permitted the realization of 1.3 micrometer laser heterostructures with low threshold current density. This work was partially presented at the 1985 Electron Materials Conference, Boulder (Colo. USA), June 1985.     

Studies of the Ga1-xI^As1-ySby quaternary alloy system:-II characterisation by far-infrared reflectance spectroscopy

Reflectivity spectra have been measured on LPE Ga_1-xIn_xAs_1-ySb_y, quaternary alloy layers, lattice-matched to InAs and GaSb substrates. The compositions studied were limited by a miscibility gap to the regionsx = 0,y - 1 (GaSb) tox ~ 0.2,y ~ 0.8 andx = 1,y = 0 (InAs) tox ~ 0.9,y ~ 0.1. The spectra were analysed to give values of carrier density and mobility to investigate Te doping. Fory ~ 0.8 layers werep-type as-grown,n-type conduction being obtained for Te concentrations in the melt above about 10^-6 at.%. Electron mobility for low carrier densities was found to increase sharply with decreasingy. The lattice vibrational properties of the system were also investigated. Three phonon modes were observed in the composition range studied, with GaAs, InSb and mixed InAs/GaSb characteristics. Thus the behaviour of the system may be termed “three-mode” due to the degeneracy of the GaSb and InAs modes. The oscillator strengths of the observed modes are qualitatively as expected from a comparison with appropriate binary systems.     

A composition-dependent model for the complex dielectric function of In1 xGaxAsyP1− y lattice-matched to InP

Accurate and numerically efficient models for the complex dielectric function vs wavelength and material characteristics are essential for the use of nondestructive optical techniques such as spectroscopic ellipsometry or reflectometry. These optical techniques are commonly used for real-time and run-to-run monitoring and control of growth and etch processes to determine a material's composition and thickness. In this work, we discuss an improved composition-dependent model for the complex dielectric function for lattice-matched In_1-xGa_xAs_yP_1-y/InP systems valid over the entire composition range 0 ≤ y ≤ 1. We describe our model, which is an extension of the critical point parabolic band method and is based on the model proposed by Charles Kim et al. for the A_xGa_1-x/GaAs system. We demonstrate the quality of the model in fitting optical data for individual compositions and compare our results to other established models including the harmonic oscillator approximation and the model of Adachi. Using results obtained from the individual fits, we generate a composition-dependent model that is valid for the entire range of lattice-matched compositions. Also, we show how this model can be used to accurately determine the composition (±0.01) of an unknown material whose dielectric response has been obtained using spectroscopic ellipsometry or a similar technique.     

Electrical characterization of high purity InGaAsP alloys

In_xGa_1-xAs_yP_1-y layers grown by liquid phase epitaxy on InP substrates were characterized by Hall effect between 4 and 300K. The thermal activation energy of donor impurities was estimated from the temperature dependence of the free electron concentration ; it was found to increase with phosphorus concentration from less than 1meV in InGaAs to about 2.5meV in InP. Evidence for impurity conduction was also observed in some samples at the lowest temperatures. The mobility analysis led to an estimation of the alloy scattering potential in the whole range of compositions 0≤y≤l. At temperatures below 10K, we observed avalanche effect due to impact ionization of electrons from shallow donor impurities into the conduction band.     

Bandgap and lattice constant of GaInAsP as a function of alloy composition

Published data for the composition dependence of the room-temperature bandgap (E_g) and lattice constant (a_o) in the pseudobinary Ga_yIn_1-yAs, Ga_yIn_1-yP, GaAs_xP_l-x, and InAs_xP_l-x systems have been used to derive the following equations for the quaternary Ga_yIn_l-yAs_x P_l-x, alloys: $$\begin{gathered} a_o ({\AA}) = 5.87 + 0.18x - 0.42y + 0.02xy \hfill \\ E_g (eV) = 1.35 - x + 1.4y - 0.33xy - (0.758 - 0.28x)y(1 - y) \hfill \\ - (0.101 + 0.109y) x(1 - x). \hfill \\ \end{gathered} $$ Available experimental data are in excellent agreement with these equations.     

Measured compositions and laser emission wavelengths of GaXIn1−XAsyP1−y lpe layers lattice-matched TO InP Substrates

The alloy compositions of Ga_XIn_1−XAs_yP_1−y LPE layers lattice-matched to InP substrates have been determined by electron microprobe analysis. The composition data are well repre-sented by x = 0.40y + 0.067y². The emission wavelengths of lattice-matched Ga_XIn_1−XAs_yP_1−y/InP double-heterostructure diode lasers have been measured at 300 and 80 K. The photon energies for laser emission at 300 K are given by hΝ(eV) = 1.307 − 0. 60y + 0.03y². The emission energies at 80 K are 57 meV higher. This work was sponsored by the Department of the Air Force.     

Calculation of energy band gaps in quaternary iii/v alloys

The dielectric theory of electronegativity is applied to the calculation of the compositional dependence of the energy band gap for quaternary III/V alloys of type A_l-xB_xC_1-yD_y and A_1-x-yB_xC_yD. The departure from linearity of E_G versus x and y is taken to be the sum of two terms, the intrinsic or virtual crystal term and the extrinsic term due to effects of aperiodicity which for one type of alloy may occur on both sublattices. Rather than simply treating the quaternary as an average of the bounding ternary systems, as has been common in the past, the intrinsic departure from linearity is calculated by assuming E_h,i,C, and D_av to vary linearly with x and y. The result is a smaller intrinsic deviation from linearity and a much better fit to existing data in the system Ga_1-xIn_xAs_1-y P_y. The calculation is also applied to three systems where no data exist but which are of great interest because of their potential application for the fabrication of lattice matched tandem solar cells: Ga_l-xA1_xAs_l-ySb_y. Ga_1-x-yA1_xIn_yAs, and GaAs_1-x-yP_xSb_y.     

The effect of trimethylaluminum concentration on the incorporation of P In AlxGa1−xPyAs1−y grown by organometallic vapor phase epitaxy

The organometallic vapor phase epitaxial (OM-VPE) growth of Al_xGa_1-xP_yAs_1-y on graded GaP_yAs_1-yGaAs in the compositional range 0 < x < 0.9 and 0 < y < 0.6 is reported. It is found that composition control can be easily achieved, and that the vapor phase ratio of trimethylaluminum to trimethylgallium strongly influences the incorporation of P in the solid. A model is developed which explains this in terms of competing reaction rates. The model gives a good fit to the experimental data.     

Group-V composition control for InGaAsP grown by gas source molecular beam epitaxy

Based on our kinetics models for gas source molecular beam epitaxy of mixed group-V ternary materials, the group-V composition control in In_yGa_1−yAs_1−xP_x epilayers has been studied. The P or As composition in In_yGa_1−yAs_1−xP_x (lattice matched to InP or GaAs) can be obtained from a simple equation for substrate temperatures below 500°C. This has been verified by a series of experimental results.     

Gas-Source molecular beam epitaxy and characterization of inGaAs/lnGaAsP quantum well structures on InP

In this paper, we report the effect of using a group-V residual source evacuation (RSE) time on the interfaces of InGaAs/lnGaAsP quantum wells (QWs) grown by gas-source molecular beam epitaxy. High-resolution x-ray rocking curve and low-temperature photoluminescence (PL) were used to characterize the material quality. By optimizing the RSE time, a PL line width at 15K as narrow as 6.6 meV is observed from a 2 nm wide single QW, which is as good as or better than what has been reported for this material system. Very sharp and distinct satellite peaks as well as Pendellosung fringes are observed in the x-ray rocking curves of In_xGa_1−xAs/InxGa_1−xAS_yP_1−y multiple QWs, indicating good crystalline quality, lateral uniformity, and vertical periodicity. Theoretical considerations of the PL linewidths of In_xGa_1−xAs/InxGa_1−xAS_yP_1−y single QWs show that for QW structures grown with the optimized RSE time, the PL linewidth is mainly due to alloy scattering, whereas the contribution from interface roughness is small, indicating a good interface control.     

Wavelength tuning in strained layer InGaAs-GaAs-AlGaAs quantum well lasers by selective-area MOCVD

Selective-area growth and regrowth using conventional atmospheric pressure metalorganic chemical vapor deposition is investigated for wavelength tuning in strained layer In_xGa_1-xAsGaAs-Al_y Ga_1-yAs quantum well lasers. Growth inhibition from a silicon dioxide mask is the mechanism used for the selective-area growth rate enhancement. By varying the width of the oxide stripe opening, differences in the growth rate yield different quantum well thicknesses, and hence different lasing wavelengths for devices on the same wafer. Both two-and three-step growth processes are utilized for selective-area epitaxy of strained layer In_xGa_1-xAs-GaAs quantum well active regions, with lasers successfully fabricated from the three-step growth. Scanning electron microscopy and transmission electron microscopy indicate that the absence of an oxide mask during Al_yGa_1-yAs growth is essential for successful device operation. A wide wavelength tuning range of over 630Å is achieved for lasers grown on the same substrate.     

Raman scattering study of the immiscible region in InGaAsP grown by LPE on (100) and (111) GaAs

We have studied the asymmetric broadening of the Raman spectra of In_xGa_1-xAs_yP_1-y grown on GaAs substrates by means of the spatial correlation model. The broadening phenomena was found to be enhanced in the region of immiscibility, in agreement with PL observations. In Raman measurements, the broadening is more enhanced in the samples grown on (100) substrates than in the samples grown on (111) substrates. The enhancement is attributed to the immiscibility included in the samples grown on (100) substrate.     

A novel pseudomorphic (GaAs1−xSbx-InyGa1−yAs)/GaAs bilayer-quantum-well structure lattice-matched to GaAs for long-wavelength optoelectronics

Two types of quantum well (QW) structures grown lattice matched on (100) GaAs have been studied. The first type of structure consists of pseudomorphic GaAs_xSb_1-x/GaAs (x≤0.3) SQWs which show emission wavelengths longer than those reported for pseudomorphic In_yGa_1−yAs/GaAs QWs. However, the attractive emission wavelength of 1.3 μm has not been achieved. To reach this goal, a novel type of bilayer QW (BQW) has been grown consisting of a stack of two adjacent pseudomorphic layers of GaAs_xSb_1−x and In Ga_1-y As embedded between GaAs confinement layers. In this BQW, a type-II heterojunction is formed between GaAs_xSb_1−x and In_yGa_1−yAs, resulting in a spatially indirect radiative recombination of electrons and holes at emission wavelengths longer than those achieved in the GaAs_xSb_1−x/GaAs and Ii_yGa_1−yAs/GaAs SQWs. The longest 300K emission wavelength observed so far was 1.332 μm.     

Compositional dependence of the electron mobility in Inl-x Gax Asy P1-y

Hall mobility measurements for the alloy III–V quaternary material In_1-x}Ga_x}As_y}P_1-y} lattice matched to semi-insulating InP substrates are described. For samples spanning the entire compositional range, the carrier concentration varied from 0.4x10¹⁶} to 10¹⁷}cm⁻³ and the room temperature mobilities varied from 3800cm²}/Vsec up to 11,000cm²}/Vsec. Temperature variation of the mobility in the range from 80K to 300K was investigated for selected samples. The results demonstrate that disorder scattering makes a significant contribution to limiting the mobility for material spanning the midrange (y∼0.5). This work was first presented as a paper at the 21^st} Electronic Materials Conference, University of Colorado, Boulder, Colorado, June 27–29, 1979.     

Ga1-xinxas - inp abrupt heterostructures grown by MOVPE at atmospheric pressure

High quality InP and Ga_1-x In_xAs layers have been grown on InP substrates using MOVPE growth at atmospheric pressure. Excellent material quality has been obtained using triethylindium and trimethylgallium sources(n = 1.7 10¹⁴ cm^-3, μ = 106 000 cm²V^-1s^-1 at 77 K for InP andn = 1 ? 3 10¹⁵ cm^-3, μ= 75 000 cm²V^-1 s^-1 at 77 K for Ga_1-xIn_xAs). The InP/Ga_1-xIn_xAs interface width obtained is very small (10 Å). The first PIN diodes grown by the process exhibit excellent characteristics.     

Efficient 2.0–2.6 μm wavelength photoluminescence from narrow bandgap InAsP/InGaAs double heterostructures grown on InP substrates

Photoluminescence spectra and efficiency have been measured for several strained InAs_yP_1−yIn_xGa_1−xAs (0.28 < y ≤ 0.62; 0.66 ≤ x ≤ 0.83) double heterostructures grown by vapor phase epitaxy on InP substrates with graded InAsP buffer layers. Luminescence peak positions between the wavelengths of 1.99 and 2.57 (μm at a temperature of 295K are consistent with bandgap luminescence from the In_xGa_1−xAs active regions. Despite a high density of dislocations in the buffer layers, internal radiative recombination efficiencies of from 25 to 50% for the structures are found at 295K.     

On-line growth monitoring of InP-based device structures by reflectance anisotropy spectroscopy

Reflectance anisotropy spectroscopy (RAS) has been used to study the metalorganic vapor phase epitaxy growth process for Ga_xIn_1−xAs_yP_1−y/InP light emitting diodes. The sensitivity of RAS to morphology changes is demonstrated by InP growth on different InP:Fe substrates. RAS reveals not only development of dull surfaces but also detects initial temporary roughness of mirror-like layers. Based on the RAS results the substrate preparation was optimized. RAS spectra measured on n- and p-type InP and p-type GaInAsP during light emitting diodes production are suitable for finger-printing of the growth process. Spectra from InP:Si and InP:Zn layers show characteristic features near 4.3 eV which allow for assessment of doping level at growth temperature (640°C). Correlation of RAS spectra and transients during growth with the quaternary composition was achieved. A change in composition of only Δx=0.01, Δy=0.03 corresponding to a shift of photoluminescence-peak position by 16 nm was detectable in RAS spectra. The results demonstrate the high sensitivity and thus the suitability of RAS for on-line control during growth of device structures.     

Tertiarybutylarsine and tertiarybutylphosphine for the MOCVD growth of low threshold 1.55 μm InxGa1-xAs/InP quantum-well lasers

Tertiarybutylarsine (TBA) and teriarybutylphosphine (TBP) are liquid organometallic sources that are a safer alternative to arsine and phosphine. In this work, we have grown high-quality In_0.53Ga_0.47As/InP quantum wells at a temperature of 590° with TBA and TBP partial pressures of 0.4 and 2.5 Torr, respectively. A low-temperature photoluminescence study indicated optimized column V growth interruption times of 0.5 s for In_0.53Ga_0.47As wells with InP barriers. Using the optimized growth conditions, we have obtained lattice matched In_0.53Ga_0.47As/In_xGa_1-xAs_yP_1-x single quantum-well lasers emitting at 1.55 μm. Broad-area devices with a length of 3.5 mm exhibit a low threshold current density of 220A/cm². Broad-area lasers containing four quantum wells had a threshold current density of 300A/cm² for a 3.0 mm cavity length and CW powers of 40 mW per facet for an as-cleaved 4 × 750 μm device.     

Growth and characterization of lattice-matched epitaxial films of GaxIn1−xAs/InP by liquid-phase epitaxy

We determined the conditions for successful lattice-matched growth by liquid-phase epitaxy near T = 620‡ C of Ga_XIn_1−XAs on [111B] InP substrates. We have used the results of the growth of both lattice-matched and intentionally lattice-mismatched epitaxial layers, (0.4 ≤ X ≤ 0.7) to calculate a phase diagram which gives the correct liquidus temperature, (T_L ± 1‡ C), and the correct solid composition, (± 5 % of the nominal composition), for the entire range of growth solutions considered for this important ternary semi-conductor system. The parameters appropriate to this calculation are significantly different from those used to describe the growth of Ga_XIn_1−XAs on GaAs. The results of this calculation play an important part in the better understanding of the quaternary alloy Ga_XIn_1−XAs_yP_1−y. Our measurements show that the ternary alloy lattice-matched to InP is Ga_0.47In_0.53As, semiconductor with a direct band gap about 0.75 eV at room temperature. We have grown p-n junction homostructures and double-heterostructures on InP substrates. These wafers have been used to make detectors in the 1.0 – 1.7/um range of the optical spectrum.     

Effect of surface encapsulation and As4 overpressure on Si diffusion and impurity-induced layer disordering in GaAs,AlxGa1-xAs,and AlxGa1-xAs-GaAs quantum well heterostructures

Data are presented demonstrating that the surface encapsulant and the As₄ overpressure strongly affect Si diffusion in GaAs and Al_xGa_1-xAs, and thus are important parameters in impurity-induced layer disordering. Increasing As₄ overpressure results in anincrease in diffusion depth in the case of GaAs, and adecrease in diffusion depth for Al_xGa_1-xAs. In addition, the band-edge exciton is observed in absorption on an Al_xGa_1-xAs-GaAs superlattice that is diffused with Si and is converted to bulk crystal Al_yGa_1-yAs via impurity-induced layer disordering. In contrast, the exciton is not observed in absorption on GaAs diffused with Si in spite of the high degree of compensation. These data indicate that the Si diffusion process, and the properties of the diffused material, are different for GaAs and for Al_xGa_1-xAs-GaAs superlattices converted into uniform Al_yGa_1-yAs (0 ≤y ≤x ≤ 1) via impurity-induced layer disordering with the amphoteric dopant Si.