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The control of stoichiometry in Epitaxial semiconductor structures. Interfacial Chemistry: Property relations. A workshop review

A workshop on the control of stoichiometry in epitaxial semiconductor structures was held on August 21-26, 1995 in the hotel Stutenhaus at Vesser in Germany. The secluded location of the workshop in the forest of Thuringia and its informal style stimulated extensive private discussions among the participants and promoted new contacts between young scientists from Eastern and Western Europe and the USA. Topics addressed by the presentations were interactions of precursors to heteroepitaxy and doping with the substrate surface, the control of interfacial properties under the conditions of heteroepitaxy for selected materials systems, methods of characterization of interfaces and native point defects in semiconductor heterostructures and an in depth evaluation of the present status of the control and characterization of the point defect chemistry for one specific semiconductor (ZnGeP2), including studies of both heterostructures and bulk single crystals. The selected examples of presentations and comments given here represent individual choices - made by the author to highlight major points of the discussions.

Bachmann, Klaus J.↗

Growth and Properties of Lattice Matched GaAsSbN Epilayer on GaAs for Solar Cell Applications

The growth and properties of GaAsSbN single quantum wells (SQWs) are investigated in this work. The heterostructures were grown on GaAs substrates in an elemental solid source molecular beam epitaxy (MBE) system assisted with a RF plasma nitrogen source. A systematic study has been carried out to determine the influence of various growth conditions, such as the growth temperature and the source shutter-opening sequence, on the quality of the grown layers and the incorporation of N and Sb. The effects of ex situ and in situ annealing under As overpressure on the optical properties of the layers have also been investigated. Substrate temperature in the range of 450-470 C was found to be optimum. Simultaneous opening of the source shutters was found to yield sharper QW interfaces. N and Sb incorporations were found to depend strongly upon substrate temperatures and source shutter opening sequences. A significant increase in PL intensity with a narrowing of PL line shape and blue shift in emission energy were observed on annealing the GaAsSbN/GaAs SQW, with in situ annealing under As overpressure providing better results, compared to ex situ annealing.

Bharatan, Sudhakar↗

LPE growth of 1.3 micron InGaAsP CW lasers on /110/ InP substrates

A description is presented of the liquid-phase epitaxial (LPE) growth of high-quality InGaAsP/InP continuous-wave (CW) laser structures on (110) InP substrates using conventional LPE without the need for special growth procedures. Double heterojunction laser structures were grown using the LPE supercooling method with a horizontal sliding boat. Low broad-area current densities (970 A/sq cm) and CW operation achieved at room temperature indicate that results comparable to up-to-date devices may be achieved. The inherent tendency for surface planarity maintenance due to the perfect surface stoichiometry of the (110) surface is a feature that may lend itself to the generation of improved interface growth in quaternary III-V and related semiconductor alloy systems. The similar cross-sectional appearance of structures grown on (110) and (100) orientations show that conventional LPE can be used with (110) surface planes without introducing special growth procedures.

Hawrylo, F. Z.↗

Transient-mode liquid phase epitaxial growth of GaAs on GaAs-coated Si substrates prepared by migration-enhanced molecular beam epitaxy

Planar oxide-maskless growth of GaAs was demonstrated by transient-mode liquid phase epitaxy (TMLPE) on GaAs-coated Si substrates that were prepared by migration-enhanced molecular beam epitaxy (MEMBE). In TMLPE, the cool substrate was brought into contact with hot melts for a short time. A GaAs layer as thick as 30 microns was grown in 10 sec. The etch pits observed in TMLPE-grown layers became longer in one direction and decreased in density with increasing the TMLPE epilayer thickness. The density of etch pits in a 20 micron-thick layer was approximately 5 x 10 the 6th/sq cm. Strong bandgap emission elliptically polarized with a major axis perpendicular to the surface was observed at about 910 nm, while deep-level emission from the TMLPE/MEMBE GaAs interface was detected at 980 nm. The photoluminescence intensity divided by the carrier concentration of the TMLPE-grown layer was about 270 times larger than that of the MEMBE-grown layer used as a substrate.

Nakamura, Shuji↗

GaAs Photovoltaics on Polycrystalline Ge Substrates

High efficiency III-V multijunction solar cells deposited on metal foil or even polymer substrates can provide tremendous advantages in mass and stowage, particularly for planetary missions. As a first step towards that goal, poly-crystalline p/i/n GaAs solar cells are under development on polycrystalline Ge substrates. Organo Metallic Vapor Phase Epitaxy (OMVPE) parameters for pre-growth bake, nucleation and deposition have been examined. Single junction p/i/n GaAs photovoltaic devices, incorporating InGaP front and back window layers, have been grown and processed. Device performance has shown a dependence upon the thickness of a GaAs buffer layer deposited between the Ge substrate and the active device structure. A thick (2 m) GaAs buffer provides for both increased average device performance as well as reduced sensitivity to variations in grain size and orientation. Illumination under IR light (lambda > 1 micron), the cells showed a Voc, demonstrating the presence of an unintended photoactive junction at the GaAs/Ge interface. The presence of this junction limited the efficiency to approx.13% (estimated with an anti-refection coating) due to the current mismatch and lack of tunnel junction interconnect.

Wilt, David M.↗

Effects of substrate misorientation and background impurities on electron transport in molecular-beam-epitaxial grown GaAs/AlGaAs modulation-doped quantum-well structures

The effects of substrate misorientation off the (001) plane and of background impurities on electron transport in MBE-grown GaAs/AlGaAs modulation-doped superlattice-buffered quantum-well structures were investigated. Low-field transport data were obtained on GaAs/AlGaAs structures grown on substrates oriented 0, 2, 4, and 6.5 deg off the (001) plane towards either (111)A or (111)B. It is shown that the low-field two-dimensional electron gas (2DEG) mobility is a function of the angle and direction of the substrate orientation, and that the 2DEG mobility is a function of the direction of the applied electric field in the GaAs quantum well. The anisotropy in the 2DEG mobility is also a function of the tilt angle and tilt azimuth direction of the substrate from the (001) plane. In addition, it is shown that the amount of interface scattering from the inverted interface is a sensitive function of the amount of background impurities in the MBE machine.

Radulescu, D. C.↗

A Chemical and Structural Study of the AlN-Si Interface

The growth of low defect density heteroepitaxial AlN has great implications for optoelectronic and high power devices since the AlN can be used either as device material or as a buffer layer for the overgrowth of other group-III nitrides. In this work, the results of transmission electron microscopy (TEM) involving both high resolution imaging and electron energy loss spectroscopy (EELS) of AlN/Si layers is reported and the relationship between Si-Al-N interactions and the misorientation of AlN nuclei is elucidated.

epitaxial optoelectronic silicon gallium nitride↗

Self-assembled InAsSb quantum dots on (001) InP substrates

Self-assembled InAsSb quantum dots (QD) on (001) InP substrates have been grown using metalorganic vapor phase epitaxy. The dot density and size are found to be strongly dependent on the presence of arsine. Direct deposition of InSb on InP and GaSb substrates formed large islands of InSb with low density of less than 53109/cm², however, InAsSb QDs of density as high as 4 X10¹º/cm² could be self-assembled by alternating group III and group V precursors, and high density almost pure InSb QDs were achieved on In0.53Ga0.47As/InP. The formation of high density InAsSb QDs is a result of a local nonequilibrium process and a reduction in mobility of In adatoms on the growth surface due to the presence of arsenic atoms, and in the case of high density almost pure InSb QDs on InGaAs/InP, the InAs interface layer is believed to be responsible. Photoluminescence shows that InSb QDs emit light at room temperature in the range of 1.7–2.2µm.

Uhl, David↗

Recent Results from Epitaxial Growth on Step Free 4H-SiC Mesas

This paper updates recent progress made in growth, characterization, and understanding of high quality homoepitaxial and heteroepitaxial films grown on step-free 4H-SiC mesas. First, we report initial achievement of step-free 4H-SiC surfaces with carbon-face surface polarity. Next, we will describe further observations of how step-free 4H-SiC thin lateral cantilever evolution is significantly impacted by crystal faceting behavior that imposes non-uniform film thickness on cantilever undersides. Finally, recent investigations of in-plane lattice constant mismatch strain relief mechanisms observed for heteroepitaxial growth of 3C-SiC as well as 2H-AlN/GaN heterofilms on step-free 4H-SiC mesas will be reviewed. In both cases, the complete elimination of atomic heterointerface steps on the mesa structure enables uniquely well-ordered misfit dislocation arrays to form near the heterointerfaces with remarkable lack of dislocations threading vertically into the heteroepilayers. In the case of 3C-SiC heterofilms, it has been proposed that dislocation half-loops nucleate at mesa edges and glide laterally along the step-free 3C/4H interfaces. In contrast, 3C-SiC and 2H-AlN/GaN heterofilms grown on 4H-SiC mesas with steps exhibit highly disordered interface misfit dislocation structure coupled with 100X greater density of dislocations threading through the thickness of the heteroepilayers. These results indicate that the presence of steps at the heteroepitaxial interface (i.e., on the initial heteroepitaxial nucleation surface) plays a highly important role in the defect structure, quality, and relaxation mechanisms of single-crystal heteroepitaxial films.

Neudeck, Philip G.↗

Gallium Arsenide welded panel technology for advanced spaceflight applications

A significant impediment to the widespread use of GaAs solar cells in space is the cost and weight of the GaAs substrate. In order to overcome these problems, Spectrolab is pursuing thin cell technologies encompassing both liquid phase epitaxy (LPE) GaAs on GaAs and MOCVD GaAs on Ge cells. Spectrolab's experience in the manufacture of 4 to 6 mil 2 cm x 4 cm GaAs cells on a LPE production line is discussed. By thinning the cells at a late state of processing, production yields comparable to 12 mil cells have been achieved. Data are presented showing that GaAs cells can be welded without degradation and have achieved minimum average efficiencies of 18 percent AM0, 28 C with efficiencies up to 20 percent. Spectrolab, in conjunction with Spire Corporation has also been pursuing GaAs on Ge cell technology in support of larger area lighter weight power systems. Data are presented showing that individual 2 cm x 2 cm, 8 mil cell efficiencies up to 21.7 percent have been achieved. Efficiencies up to 24 percent AM0 will be possible by optimizing the GaAs/Ge interface. Cells have been welded without degradation using silver interconnects and have been laid down on an aluminum honeycomb/graphite facesheet substrate to produce a small coupon. The efficiency was 18.1 percent at AM0, 28 C.

Lillington, D. R.↗

Extremely low nonalloyed and alloyed contact resistance using an InAs cap layer on InGaAs by molecular-beam epitaxy

Extremely low alloyed and nonalloyed ohmic contact resistances have been formed on n-type InAs/In(0.53)Ga(0.47)As/In(0.52)Al(0.48)As structures grown on InP(Fe) by molecular-beam epitaxy. To insure the accuracy of the small contact resistances measured, an extended transmission line model was used to extrapolate contact resistances from test patterns with multiple gap spacings varying from 1 to 20 microns. For a 150-A-thick InAs layer doped to 2 x 10 to the 18th/cu cm and a 0.1-micron-thick InGaAs layer doped to 1 x 10 to the 18th/cu cm, a specific contact resistance of 2.6 x 10 to the -8th ohm-asterisk sq cm was measured for the nonalloyed contact, while a resistance less than 1.7 x 10 to the -8th ohm-asterisk sq cm is reported for the alloyed contact. Conventional Au-Ge/Ni/Au was used for the ohmic metal contact and alloying was performed at 500 C for 50 s in flowing H2. Using a thermionic field emission model, the barrier height at the InAs/InGaAs interface was calculated to be 20 meV.

Peng, C. K.↗

Homoepitaxial and Heteroepitaxial Growth on Step-Free SiC Mesas

This article describes the initial discovery and development of new approaches to SiC homoepitaxial and heteroepitaxial growth. These approaches are based upon the previously unanticipated ability to effectively supress two-dimensional nucleation of 3C-SiC on large basal plane terraces that form between growth steps when epitaxy is carried out on 4H- and 6H-SiC nearly on-axis substrates. After subdividing the growth surface into mesa regions, pure stepflow homoeptixay with no terrace nucleation was then used to grow all existing surface steps off the edges of screw-dislocation-free mesas, leaving behind perfectly on-axis (0001) basal plane mesa surfaces completely free of atomic-scale steps. Step-free mesa surfaces as large as 0.4 mm x 0.4 mm were experimentally realized, with the yield and size of step-free mesas being initally limited by substrate screw dislocations. Continued epitaxial growth following step-free surface formation leads to the formation of thin lateral cantilevers that extend the step-free surface area from the top edge of the mesa sidewalls. By selecting a proper pre-growth mesa shape and crystallographic orientation, the rate of cantilever growth can be greatly enhanced in a web growth process that has been used to (1) enlarge step-free surface areas and (2) overgrow and laterally relocate micropipes and screw dislocations. A new growth process, named step-free surface heteroepitaxy, has been developed to achieve 3C-SiC films on 4H- and 6H-SiC substrate mesas completely free of double positioning boundary and stacking fault defects. The process is based upon the controlled terrace nucleation and lateral expansion of a single island of 3C-SiC across a step-free mesa surface. Experimental results indicate that substrateepilayer lattice mismatch is at least partially relieved parallel to the interface without dislocations that undesirably thread through the thickness of the epilayer. These results should enable realization of improved SiC homojunction and heterojunction devices. In addition, these experiments offer important insights into the nature of polytypism during SiC crystal growth.

Neudeck, Philip G.↗

Nucleation, growth, and strain relaxation of lattice-mismatched 3-5 semiconductor epitaxial layers

We have investigated the early stages of evolution of highly strained 2-D InAs layers and 3-D InAs islands grown by metal-organic chemical vapor deposition (MOCVD) on (100) and (111)B GaAs substrates. The InAs epilayer/GaAs substrate combination has been chosen because the lattice-mismatch is severe (approximately 7.2 percent), yet these materials are otherwise very similar. By examining InAs-on-GaAs composites instead of the more common In(x)Ga(1-x)As alloy we remove an additional degree of freedom (x) and thereby simplify data interpretation. A matrix of experiments is described in which the MOCVD growth parameters - susceptor temperature, Thin flux, and AsH3 flux - have been varied over a wide range. Scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and electron microprobe analysis have been employed to observe the thin film surface morphology. In the case of 3-D growth, we have extracted activation energies and power-dependent exponents that characterize the nucleation process. As a consequence, optimized growth conditions have been identified for depositing approximately 250 A thick (100) and (111)B oriented InAs layers with relatively smooth surfaces. Together with preliminary data on the strain relaxation of these layers, the above results on the evolution of thin InAs films indicate that the (111)B orientation is particularly promising for yielding lattice-mismatched films that are fully relaxed with only misfit dislocations at the epilayer/substrate interface.

Welser, R. E.↗

Nucleation, Growth, and Strain Relaxation of Lattice-Mismatched III-V Semiconductor Epitaxial Layers

We have investigated the early stages of evolution of highly strained 2-D InAs layers and 3-D InAs islands grown by metal-organic chemical vapor deposition (MOCVD) on (100) and (111) B GaAs substrates. The InAs epilayer / GaAs substrate combination has been chosen because the lattice-mismatch is severe (approx. 7.20%), yet these materials are otherwise very similar. By examining InAs-on-GaAs composites Instead of the more common In(x)Ga(1-x)As alloy, we remove an additional degree of freedom (x) and thereby simplify data interpretation. A matrix of experiments is described in which the MOCVD growth parameters -- susceptor temperature, TMIn flux, and AsH3 flux -- have been varied over a wide range. Scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and electron microprobe analysis have been employed to observe the thin film surface morphology. In the case of 3-D growth, we have extracted activation energies and power-dependent exponents that characterize the nucleation process. As a consequence, optimized growth conditions have been identified for depositing approx. 250 A thick (100) and (111)B oriented InAs layers with relatively smooth surfaces. Together with preliminary data on the strain relaxation of these layers, the above results on the evolution of thin InAs films indicate that the (111)B orientation is particularly promising for yielding lattice-mismatched films that are fully relaxed with only misfit dislocations at the epilayer / substrate interface.

Welser, R. E.↗

High Quality GaAs Growth by MBE on Si Using GeSi Buffers and Prospects for Space Photovoltaics

III-V solar cells on Si substrates are of interest for space photovoltaics since this would combine high performance space cells with a strong, lightweight and inexpensive substrate. However, the primary obstacles blocking III-V/Si cells from achieving high performance to date have been fundamental materials incompatabilities, namely the 4% lattice mismatch between GaAs and Si, and the large mismatch in thermal expansion coefficient. In this paper, we report on the molecular beam epitaxial (MBE) growth and properties of GaAs layers and single junction GaAs cells on Si wafers which utilize compositionally graded GeSi Intermediate buffers grown by ultra-high vacuum chemical vapor deposition (UHVCVD) to mitigate the large lattice mismatch between GaAs and Si. Ga As cell structures were found to incorporate a threading dislocation density of 0.9-1.5 x 10 (exp 6) per square centimeter, identical to the underlying relaxed Ge cap of the graded buffer, via a combination of transmission electron microscopy, electron beam induced current, and etch pit density measurements. AlGaAs/GaAs double heterostructures wre grown on the GeSi/Si substrates for time-resolved photoluminescence measurements, which revealed a bulk GaAs minority carrier lifetime in excess of 10 ns, the highest lifetime ever reported for GaAs on Si. A series of growth were performed to ass3ss the impact of a GaAs buffer to a thickness of only 0.1 micrometer. Secondary ion mass spectroscopy studies revealed that there is negligible cross diffusion of Ga, As and Ge at he III-V/Ge interface, identical to our earlier findings for GaAs grown on Ge wafers using MBE. This indicates that there is no need for a buffer to "bury" regions of high autodopjing,a nd that either pn or np configuration cells are easily accomodated by these substrates. Preliminary diodes and single junction Al Ga As heteroface cells were grown and fabricated on the Ge/GeSi/Si substrates for the first time. Diodes fabricated on GaAs, Ge and Ge/GeSi/Si substrate show nearly identical I-V characteristics in both forward and reverse bias regions. External quantum efficiencies of AlGaAs/GaAs cell structures grown on Ge/GeSi/Si and Ge substrates demonstrated nearly identical photoresponse, which indicates that high lifetimes, diffusion lengths and efficient minority carrier collection is maintained after complete cell processing.

Carlin, J. A.↗

Transmission Electron Microscopy (TEM) Sample Preparation of Si(1-x)Gex in c-Plane Sapphire Substrate

The National Aeronautics and Space Administration-invented X-ray diffraction (XRD) methods, including the total defect density measurement method and the spatial wafer mapping method, have confirmed super hetero epitaxy growth for rhombohedral single crystalline silicon germanium (Si1-xGex) on a c-plane sapphire substrate. However, the XRD method cannot observe the surface morphology or roughness because of the method s limited resolution. Therefore the authors used transmission electron microscopy (TEM) with samples prepared in two ways, the focused ion beam (FIB) method and the tripod method to study the structure between Si1-xGex and sapphire substrate and Si1?xGex itself. The sample preparation for TEM should be as fast as possible so that the sample should contain few or no artifacts induced by the preparation. The standard sample preparation method of mechanical polishing often requires a relatively long ion milling time (several hours), which increases the probability of inducing defects into the sample. The TEM sampling of the Si1-xGex on sapphire is also difficult because of the sapphire s high hardness and mechanical instability. The FIB method and the tripod method eliminate both problems when performing a cross-section TEM sampling of Si1-xGex on c-plane sapphire, which shows the surface morphology, the interface between film and substrate, and the crystal structure of the film. This paper explains the FIB sampling method and the tripod sampling method, and why sampling Si1-xGex, on a sapphire substrate with TEM, is necessary.

Kim, Hyun Jung↗

Glennan Microsystems Initiative

During the 2001-2002 award period, we performed research on Pt/Ti/bare 6H-SiC and bare 4H-SiC interfaces in order to identify their electronic properties as a function of surface preparation. The overall aim of this work is to optimize the electronic properties of metal contacts to SiC as well as the active SiC material itself as a function of surface preparation and subsequent processing. Initially, this work has involved identifying bare surface, subsurface, and metal induced gap states at the metal-SiC contact and correlating energies and densities of deep levels with Schottky barrier heights. We used low energy electron-excited nanoluminescence (LEEN) spectroscopy, X-ray photoemission spectroscopy (XPS), and Secondary Ion Mass Spectrometry (SIMS) in order to correlate electronic states and energy bands with chemical composition, bonding, and crystal structure. A major development has been the discovery of polytype transformations that occur in 4H-SiC under standard microelectronic process conditions used to fabricate SiC devices. Our results are consistent with the stacking fault generation, defect formation, and consequent degradation of SiC recently reported for state-of-the-art ABB commercial diodes under localized electrical stress. Our results highlight the importance of -optimizing process conditions and material properties - anneal times, temperatures and doping to control such structural changes within epitaxial SiC layers. Thus far, we have established threshold times and temperatures beyond which 4H-SiC exhibits 3C-SiC transformation bands for a subset of dopant concentrations and process conditions. On the basis of this temperature time behavior, we have been able to establish an activation energy of approximately 2.5 eV for polytype transformation and dislocation motion. Work continues to establish the fundamental mechanisms underlying the polytype changes and its dependence on material parameters.

Brillson, Leonard J.↗

Non-Geiger-Mode Single-Photon Avalanche Detector with Low Excess Noise

This design constitutes a self-resetting (gain quenching), room-temperature operational semiconductor single-photon-sensitive detector that is sensitive to telecommunications optical wavelengths and is scalable to large areas (millimeter diameter) with high bandwidth and efficiencies. The device can detect single photons at a 1,550-nm wavelength at a gain of 1 x 10(exp 6). Unlike conventional single photon avalanche detectors (SPADs), where gain is an extremely sensitive function to the bias voltage, the multiplication gain of this device is stable at 1 x 10(exp 6) over a wide range of bias from 30.2 to 30.9 V. Here, the multiplication gain is defined as the total number of charge carriers contained in one output pulse that is triggered by the absorption of a single photon. The statistics of magnitude of output signals also shows that the device has a very narrow pulse height distribution, which demonstrates a greatly suppressed gain fluctuation. From the histograms of both pulse height and pulse charge, the equivalent gain variance (excess noise) is between 1.001 and 1.007 at a gain of 1 x 10(exp 6). With these advantages, the device holds promise to function as a PMT-like photon counter at a 1,550- nm wavelength. The epitaxial layer structure of the device allows photons to be absorbed in the InGaAs layer, generating electron/hole (e-h) pairs. Driven by an electrical field in InGaAs, electrons are collected at the anode while holes reach the multiplication region (InAlAs p-i-n structure) and trigger the avalanche process. As a result, a large number of e-h pairs are created, and the holes move toward the cathode. Holes created by the avalanche process gain large kinetic energy through the electric field, and are considered hot. These hot holes are cooled as they travel across a p -InAlAs low field region, and are eventually blocked by energy barriers formed by the InGaAsP/ InAlAs heterojunctions. The composition of the InGaAsP alloy was chosen to have an 80 meV valance band offset with InAlAs, which is high enough to hinder the transport of the already cooled holes. Being stopped by the energy barrier, holes are accumulated at the junctions to shield the electric field, resulting in a decrease of the electric field in the multiplication region. Because the impact ionization rate is extremely sensitive to the magnitude of the electric field, the field-screening effect drastically reduces the impact ionization rate and quenches the output signals. After the avalanche pulse signal is self-quenched, the accumulated holes at the InGaAsP/ InAlAs interface escape the energy barrier through thermal excitation and tunneling and finally leave the device. The device is thus reset and ready for subsequent photon detection. This recovery time is controlled by the height of the energy barrier and the hole-cooling rate.

Zhao, Kai↗