Isolation and control of voids and void-hillocks during molecular beam epitaxial growth of HgCdTe

Formation of small voids and defect complexes involving small voids during the molecular beam epitaxial growth of mercury cadmium telluride on cadmium zinc telluride was investigated. Some of these defects were demonstrated to form away from the substrate-epi interface. Other defects were demonstrated to close before reaching the top surface without leaving any perturbations on the surface, thus remaining completely hidden. The voids, which formed away from the substrate-epifilm fixed interface, nucleated on defects introduced into the film already grown, leading to the formation of defect complexes, unlike the voids which nucleated at the substrate-epifilm fixed interface. These defect complexes are decorated with high density dislocation nests. The voids which closed before reaching the film surface usually also nucleated slightly away from the film-substrate interface, continued to replicate for a while as the growth progressed, but then relatively rapidly closed off at a significant depth from the film surface. These voids also appeared to form defect complexes with other kinds of defects. Correlations between these materials defects and performance of individual vertically integrated photodiode (VIP) devices were demonstrated, where the relative location of these defects with respect to the junction boundary appears to be particularly important. Elimination or reduction of fluctuations in relative flux magnitudes or substrate temperature, more likely during multi-composition layer growth, yielded films with significantly lower defect concentrations.     

Electromigration-Induced Void Formation at the Cu<Subscript>5</Subscript>Zn<Subscript>8</Subscript>/Solder Interface in a Cu/Sn-9Zn/Cu Sandwich

The electromigration that occurs in a Cu/Sn-9Zn/Cu sandwich was investigated for void formation at room temperature with 10³ A/cm². A focused ion beam revealed that voids nucleated at the intermetallic compound (IMC)/solder interface regardless of the electron flow direction. The needle-like voids initiated at the cathode Cu₅Zn₈/solder interface due to the outward diffusion of Zn atoms in the Zn-rich phase and expanded as a result of the surface diffusion of Sn atoms upon current stressing.     

Fast vapor growth of cadmium telluride single crystals

Cadmium telluride single crystals were grown at growth rates of 35 mm per day by the physical vapor transport (PVT) method under high temperature gradient conditions. This is believed to be the highest PVT growth rate of CdTe reported to date. Lamellar twins are the only ones present in the CdTe crystals grown under optimal conditions in this work. At growth rates up to 15 mm per day, the crystals have a dislocation density of ∼10⁴ cm⁻². The etch pit density increases to ∼10⁵ cm⁻² with an increase of the growth rate up to 35 mm per day. Based on a uniform thermal field and high interface stability, which are established by large temperature gradients up to 40°C/cm at the growth interface, spurious nucleation and lateral twins were effectively eliminated, and the density of the lamellar twins remained low at crystal growth rates up to 35 mm per day. The major contributions of the high temperature gradients to the single crystalline growth and the apparent origin of polycrystalline grains are also discussed in this paper.     

Molecular beam epitaxy HgCdTe growth-induced void defects and their effect on infrared photodiodes

We have carried out a study and identified that MBE HgCdTe growth-induced void defects are detrimental to long wavelength infrared photodiode performance. These defects were induced during nucleation by having surface growth conditions deficient in Hg. Precise control and reproducibility of the CdZnTe surface temperature and beam fluxes are required to minimize such defects. Device quality material with void defect concentration values in the low 10² cm² range were demonstrated.     

Realization of very long wavelength infrared photovoltaic detector arrays on mercury cadmium telluride epitaxial layers grown on Si substrates

This paper proposes a development of n-on-p structures for realizing very long wavelength infrared (VLWIR) detector arrays on mercury cadmium telluride (HgCdTe) epitaxial layers grown on Si substrates. It is shown from a comparative study of zero-bias resistance-area product (R₀A) of diodes in n-on-p and p-on-n configurations that the n-on-p structure has promising potential to control contribution of dislocations, without actually reducing dislocation density below the current level (mid-10⁶ cm⁻²) of HgCdTe/Si material technology. The resulting gain will be in terms of both higher numerical magnitudes of R₀A and its reduced scatter.     

Analysis of Dislocation Density in Pb<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se Grown on ZnTe/Si by MBE

The growth of (211) Pb_(1−x)Sn _x Se on Si is achieved with a thick ZnTe buffer layer. The obtained films are specular, but contain widely dispersed void defects. Because the lattice misfit between Pb_(1−x)Sn _x Se and ZnTe is small, dislocation density values on the order of 10⁶/cm² in the Pb_(1−x)Sn _x Se are obtained. The variation of the dislocation density as a function of Pb_(1−x)Sn _x Se thickness, h, is analyzed in terms of dislocation annihilation. The analysis predicts an inverse quadratic dependence of dislocation density on h, and quantitative agreement with experimental measurements of the dislocation density is obtained.     

Wurtzite CdS on CdTe grown by molecular beam epitaxy

Growth of single crystal wurtzite cadmium sulfide on CdTe(111)B substrates has been achieved using molecular beam epitaxy. Reflection high-energy electron diffraction (RHEED) indicates smooth surface morphology for several hundreds of nanometers after nucleation. X-ray diffraction measurements confirm the crystalline orientation to be [0001] in the growth direction. X-ray photoelectron spectroscopy (XPS) indicates mostly stoichiometric CdS layers and the existence of a reaction at the interface. Sulfur incorporation into CdTe for various S fluxes has been investigated by Auger electron spectroscopy (AES). High-resolution TEM images of the interface between such epilayers were recorded. During the growth In was used as an in-situ dopant. The concentration and uniformity of In was determined by secondary ion mass spectrometry. Indium profiles were obtained for concentrations ranging from 5 × 10¹⁷ to 1.4 × 10²¹ cm⁻³. The experimental concentration agrees well with the variation expected from the In flux.     

Reduction of dislocation densities in InP single crystals by the LEC method using thermal baffles

We have developed a modified liquid encapsulated Czochralski (LEC) method with thermal baffles, by which low dislocation density InP crystals can be grown. In this method, thermal baffles are set on top of the crucible in order to suppress the gas convection and thus to improve the temperature gradient in the LEC furnace. However, the dislocation densities depend not only on the temperature gradient but also on other growth conditions, such as crystal/crucible rotation rates, cooling rates, and the thickness of the pBN crucible. Since the rotation rate affects the solid/liquid interface shape, it is an important factor for the reduction of dislocation densities. By optimizing these conditions, for Sn and Fe doped InP crystals, average dislocation densities less than 5 x 10³ cm⁻² can be achieved. Dislocation free (DF) S and Zn doped InP crystals can also be grown if the carrier concentration is more than 3 x 1018 cm⁻³. The DF crystals become rectangular in shape.     

Flexibility of p–n Junction Formation from SWIR to LWIR Using MBE-Grown Hg(1–x)CdxTe on Si Substrates

In this paper, we show the versatility of using molecular-beam epitaxy (MBE) for the growth of the mercury cadmium telluride (HgCdTe) system. Abrupt composition profiles, changes in doping levels or switching doping types are easily performed. It is shown that high-quality material is achieved with Hg_(1–x)Cd _x Te grown by MBE from a cadmium mole fraction of x = 0.15 to x = 0.72. Doping elements incorporation as low as 10¹⁵ cm⁻³ for both n-type and p-type material as well as high incorporation levels >10¹⁸ cm⁻³ for both carrier types were achieved. X-ray curves, secondary-ion mass spectrometry (SIMS) data, Hall data, the influence of doping incorporation with cadmium content and growth rate, etch pit density (EPD), composition uniformity determined from Fourier-transform infrared (FTIR) transmission spectro- scopy, and surface defect maps from low to high x values are presented to illustrate the versatility and quality of HgCdTe material grown by MBE. All data presented in this work are from layers grown on silicon (112) substrate.     

Studies on solder bump electromigration in Cu/Sn–3Ag–0.5Cu/Cu system

This paper aims to understand the solder bump electromigration phenomenon in the Cu/Sn–3Ag–0.5Cu/Cu system. A temperature of 453 K with a current density of 10 kA/cm² was applied. A void nucleated at the highest current density point at the cathode. As the void grew along the cathode side, a solder depletion occurred on the opposite side of the electron entry point, resulting in an open failure. A unique purposely-designed 3D model simulation methodology provides a good understanding of the void nucleation and growth behavior. The temperature of the solder joint during the electromigration test was measured successfully by the resistance change in the junction line between the two joints.     

Threading and misfit-dislocation motion in molecular-beam epitaxy-grown HgCdTe epilayers

Lattice mismatch between the substrate and the absorber layer in single-color HgCdTe infrared (IR) detectors and between band 1 and band 2 in two-color detectors results in the formation of crosshatch lines on the surface and an array of misfit dislocations at the epi-interfaces. Threading dislocations originating in the substrate can also bend into the interface plane and result in misfit dislocations because of the lattice mismatch. The existence of dislocations threading through the junction region of HgCdTe IR-photovoltaic detectors can greatly affect device performance. High-quality CdZnTe substrates and controlled molecular-beam epitaxy (MBE) growth of HgCdTe can result in very low threading-dislocation densities as measured by the etch-pit density (EPD ∼ 10⁴cm⁻²). However, dislocation gettering to regions of high stress (such as etched holes, voids, and implanted-junction regions) at elevated-processing temperatures can result in a high density of dislocations in the junction region that can greatly reduce detector performance. We have performed experiments to determine if the dislocations that getter to these regions of high stress are misfit dislocations at the substrate/absorber interface that have a threading component extending to the upper surface of the epilayer, or if the dislocations originate at the cap/absorber interface as misfit dislocations. The preceding mechanisms for dislocation motion are discussed in detail, and the possible diode-performance consequences are explored.     

<Emphasis Type="Italic">Ex Situ</Emphasis> Thermal Cycle Annealing of Molecular Beam Epitaxy Grown HgCdTe/Si Layers

We present the results of ex situ thermal cycle annealing (TCA) of molecular beam epitaxy grown mercury cadmium telluride (HgCdTe) on Cd(Se)Te/Si(211) composite substrates. We examined the variation in the etch pit density (EPD) and overall crystalline quality with respect to annealing temperature, number of annealing cycles, total annealing time, pre-annealed EPD/crystal quality, buffer layer quality, and buffer layer lattice constant. Using TCA we observed an order of magnitude reduction in the dislocation density of the HgCdTe layers and a corresponding decrease in x-ray full width at half maximum, when the as-grown layer EPD was on the order of 1 × 10⁷ cm⁻². Among all the parameters studied, the one with the greatest influence on reducing EPD was the number of annealing cycles. We also noticed a saturation point where the HgCdTe/Si EPD did not decrease below ∼1 × 10⁶ cm⁻², regardless of further TCA treatment or the as-grown EPD value.     

LPE HgCdTe on sapphire status and advancements

With the evolution of infrared arrays to over four million pixels, larger formats have demanded higher quality mercury cadmium telluride (MCT) wafers. Since single defects can easily degrade multiple diodes, high operability requires very homogeneous and nearly flawless epitaxial surfaces. Subsequent photolithography and hybridization also demand unprecedented levels of substrate flatness and low imperfections. To consistently and reliably produce large area arrays, Insaco Inc., The Boeing Company, and Rockwell International Corporation have developed major quality improvement procedures which address all three components of the infrared material wafer architecture. Centered on the producible alternative to cadmium telluride for epitaxy (PACE) process, technological advancements encompassed sapphire substrates, organometallic vapor phase epitaxy (OMVPE), cadmium telluride (CdTe) buffer layer growth, and liquid phase epitaxial (LPE) mercury cadmium telluride growth. Processed material from these runs mated to Conexant^™ fabricated multiplexers have successfully produced 1024 1024 and the first 2048 2048 IR short-wave (2.5 m at 80 K) hybrid focal plane arrays. Operabilities in these implanted n-on-p junction devices reach 99.98% with near 70% quantum efficiency in the astronomy ‘K’ band (2.2–2.4 microns).     

Influence of annealing porous templates in an ammonia atmosphere on gallium nitride growth behaviors in hydride vapor phase epitaxy

Porous templates were fabricated by hydrogen-etching metal organic chemical vapor deposited gallium nitride (GaN); these templates were used as substrates for the growth of GaN via hydride vapor phase epitaxy. The influence of annealing porous templates on GaN growth behavior was investigated. GaN epitaxied on the unannealing porous template followed the Volmer–Weber mode with the void preserved at the growth plane, whereas the GaN film on the annealed porous templates exhibited a layer-by-layer growth and filled the porous material. The GaN crystal quality was characterized by high-resolution XRD and CL, the results indicated that GaN grown with pores preserved at the template interface had a lower dislocation density than that grown with pores filled, and the best GaN film had a TD density of 10⁴ cm⁻².     

X-ray rocking curve analysis of ion implanted mercury cadmium telluride

Junction formation by ion implantation is a critical step in producing high quality infrared focal plane arrays in mercury cadmium telluride (MCT). We have analyzed the structural properties of MCT implanted with B at doses of 10¹⁴ and 10¹⁵ cm⁻² using double and triple crystal x-ray diffraction (DCD and TCD) to monitor the disorder and strain of the implanted region as a function of processing conditions. TCD (333) reflections show that a distinct tensile peak is produced by the high dose implant while the low dose implant shows only a low angle shoulder on the substrate peak. A preliminary association of the low angle shoulder with point defects has been made since no extended defects have been observed in the low dose range. For the high dose implant, extended defect formation has been reported and may be responsible for the tensile peak. After annealing, the low angle shoulder on the low dose implant has disappeared, while the high dose implant exhibits an increase in the tensile strain from 6.5 × 10⁻⁴ to 9.3 × 10⁻⁴ after 24 h of annealing and then decreases in tensile strain to 7.3 × 10⁻⁴ after 48 h of annealing. It is believed the changes in strain are associated with the Oswald ripening and dissolution of extended defects, which has been observed during annealing of ion implanted Si.     

The growth of low dislocation density Sr1−x,Bax Nb2O6 crystals

The dislocation structures of both pure and Nd doped strontium barium niobate crystals, grown by the Czochralski method, were studied using an etch pit technique. It was determined that dislocations in the boule were being propagated from the seed and were confined to the center of the crystal. Typical dislocation density was 5x10⁴ cm⁻². Through the careful control of growth parameters and use of seed material cut from the dislocation free outer portion of a crystal, it was possible to grow crystals with very low dislocation densities, 1x10² cm⁻², and on occasion dislocation free crystals.     

Growth and characterization of indium arsenide thin films

The growth and characterization of indium arsenide films grown on indium phosphide substrates by the metal organic chemical vapor deposition (MOCVD) process is reported. Either ethyl dimethyl indium or trimethyl indium were found to be suitable in combination with arsine as source compounds. The highest electron mobilities were observed in films nucleated at reduced growth temperature. Scanning electron microscopy studies show that film nucleation at low temperature prevents thermal etch pits from forming on the InP surface before growth proceeds at an elevated temperature. Electron mobilities as high as 21,000 cm²V⁻¹ sec⁻¹ at 300 K were thus obtained for a film only 3.4 μm thick. This mobility is significantly higher than was previously observed in InAs films grown by MOCVD. From the depth dependence of transport properties, we find that in our films electrons are accumulated near the air interface of the film, presumably by positive ions in the native oxide. The mobility is limited by electrons scattering predominantly from ionized impurities at low temperature and from lattice vibrations and dislocations at high temperature. However, scattering from dislocations is greatly reduced in the surface accumulation layer due to screening by a high density of electrons. These dislocations arise from lattice mismatch and interface disorder at the film-substrate interface, preventing these films from obtaining mobility values of bulk indium arsenide.     

Liquid phase epitaxial growth and assessment of Pb1−xSn x Te alloys

The liquid-phase epitaxial growth of Pb_1−xSn_x Te on PbTe (100) substrates has been investigated over a range of growth temperatures from 600-400°C, and has been found to produce material with good uniformity and reproducibility of carrier concen-tration and alloy composition. The assessment of the epitaxial layers by such techniques as x-ray diffraction, dislocation etching and thermo-electric power measurements is described. Various features of the epitaxial layers such as interface irregularity, dislocation and diffusion effects are discussed, and likely mechanisms for their existence are proposed. The hole concentrations of the epitaxial layers, obtained by thermoelectric power measurements, are shown to have a similar dependence on preparation temperature as for bulk annealed material, suggesting that native defects are the dominant source of carriers above~ 2×10* cm^-3.     

The thermal stability of lattice mismatched InGaAs grown on patterned GaAs

Patterning and etching substrates into mesas separated by trenches before the growth of mismatched (by about 1% or less) epitaxial layers considerably reduces the interface misfit dislocation density when the layer thickness exceeds the critical thickness. Such films are in a metastable state, since misfit dislocations allow the epitaxial layers to relax to an in-plane lattice parameter closer to its strain-free value. Thermal annealing (from 600 to 850° C) has been used to study the stability of these structures to explore the properties of the misfit dislocations and their formation. The misfit dislocation density was determined by counting the dark line defects at the InGaAs/GaAs interface, imaged by scanning cathodoluminescence. InGaAs epitaxial layers grown on patterned GaAs substrates by organometallic chemical vapor deposition possess a very small as-grown misfit dislocation density, and even after severe annealing for up to 300 sec at 800° C the defect density is less than 1500 cm⁻¹ for a In_0.04Ga_0.96As, 300 nm thick layer (about 25% of the dislocation density found in unpatterned material that has not been annealed). The misfit dislocation nucleation properties of the material are found to depend on the trench depth; samples made with deeper (greater than 0.5 μm) trenches are more stable. Molecular beam epitaxially grown layers are much less stable than the above material; misfit dislocations nucleate in much greater numbers than in comparable organo-metallic chemical vapor deposited material at all of the temperatures studied.     

Electrically active defects in shallow pre-amorphisedp + n junctions in silicon

An examination of shallow pre-amorphisedp ⁺ n junctions in silicon has revealed three distinct defect related phenomena determined largely by the annealing temperature and relative location of the junction and the amorphous-crystalline (α-c) boundary. For temperatures below 800‡ C all samples displayed leakage currents of ∼10⁻³ A/cm² irrespective of the amorphising atom (Si⁺, Ge⁺ or Sn⁺). The generation centres responsible were identified to be near mid-gap deep level donors lying beyond the α-c interface. For samples annealed above 800‡ C, the leakage current was determined by the interstitial dislocation loops at the α-c boundary. If these were deeper than the junction, a leakage current density of ∼10⁻⁵ A/cm² resulted. From the growth of these loops during furnace annealing it was concluded that the growth was supported by the influx of recoil implanted silicon interstitials initially positioned beyond the α-c boundary. In the case where the as-implanted junction was deeper than the α-c boundary, annealing above 800° C resulted in a transient enhancement in the boron diffusion coefficient. As with the dislocation loop growth, this was attributed to the presence of the recoil implanted silicon interstitials.