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Reducing and Inducing Convection in Ge-Si Melts with Static Magnetic Field

Results of a study of the effectiveness of using static magnetic fields to reduce convection in Ge-Si melts will be presented. Lenz's law causes a retardation of convection when a static magnetic field is applied to an electrically conducting liquid. However, during the solidification of a solid-solution system such as Ge-Si, the interface is neither isothermal nor isoconcentrational. The variation of temperature and chemical composition along the interface causes thermoelectric currents to be generated within the solidifying material (and the container if it is electrically conductive). These currents, in the presence of a magnetic field, can cause movement (stirring, convection) in the melt which can exceed convection induced by normal thermosolutal mechanisms. Crystals have been grown by both the Bridgman and floating-zone methods. Clear evidence for the existence of this thermoelectromagnetic convection, especially in the case of Si floating-zone growth, will be presented.

Szofran, Frank R.↗

Magnetic Damping of Solid Solution Semiconductor Alloys

The objective of this study is to: (1) experimentally test the validity of the modeling predictions applicable to the magnetic damping of convective flows in electrically conductive melts as this applies to the bulk growth of solid solution semiconducting materials; and (2) assess the effectiveness of steady magnetic fields in reducing the fluid flows occurring in these materials during processing. To achieve the objectives of this investigation, we are carrying out a comprehensive program in the Bridgman and floating-zone configurations using the solid solution alloy system Ge-Si. This alloy system has been studied extensively in environments that have not simultaneously included both low gravity and an applied magnetic field. Also, all compositions have a high electrical conductivity, and the materials parameters permit reasonable growth rates. An important supporting investigation is determining the role, if any, that thermoelectromagnetic convection (TEMC) plays during growth of these materials in a magnetic field. TEMC has significant implications for the deployment of a Magnetic Damping Furnace in space. This effect will be especially important in solid solutions where the growth interface is, in general, neither isothermal nor isoconcentrational. It could be important in single melting point materials, also, if faceting takes place producing a non-isothermal interface. In conclusion, magnetic fields up to 5 Tesla are sufficient to eliminate time-dependent convection in silicon floating zones and possibly Bridgman growth of Ge-Si alloys. In both cases, steady convection appears to be more significant for mass transport than diffusion, even at 5 Tesla in the geometries used here. These results are corroborated in both growth configurations by calculations.

Szofran, Frank R.↗

Uses of Computed Tomography for Characterizing Materials Grown Terrestrially and in Microgravity

Tomography (CT) has proved to be of inestimable use in providing a rapid evaluation of a variety of samples from Mechanics of Granular Materials (MGM) to electronic materials (Ge-Si alloys) to space grown materials such as meteorites. The system at Kennedy Space Center (KSC), because of its convenient geographical location, is ideal for examining samples before launch and immediately after returning to Earth. It also has the advantage of the choice of fluxes, and in particular the use of a radioactive cobalt source, which is basically monochromatic. This permits a reasonable measurement of density to be made from which chemical composition can be determined. Due to the current dearth of long duration space grown materials, the CT instrument has been used: (1) to characterize materials in preparation for flight, (2) to determine thermal expansion values, and (3) to examine long duration space grown materials, i.e. meteorites. This work will first describe the establishment of the protocol for obtaining the optimum density readings for any material. Included will be the effects of the hardware or instrumental parameters that can be controlled, and the techniques used to process the CT data. Examples will be given of the compositional variation along a single crystal of Ge-Si alloy. Density variation with temperature has been measured in preparation for future materials science experiments; this involved the fabrication at MSFC and installation of a single zone furnace at KSC incorporating a heat pipe to ensure high temperature uniformity. At the time of writing the thermal expansion of lead (Pb) has been measured from room temperature to 900 C. Three methods are available. Digital radiography enables length changes to be determined. Prior to melting the sample is smaller than the container and the diameter change can be measured. Most critical, however, is the density change in solid, through the melting region, and in the liquid state. These data are needed for engineering purposes to aid in the design of containment cartridges, and for enabling fluid flow calculations. A second sample, with the Pb alloyed with Sb is ready for scanning. This corresponds to the planned composition of Dr. Poirier s flight experiment. Other materials pertinent to NASA programs such as Al-Cu (Trivedi), CdTe (Banish), HgCdTe (Lehoczky) will be examined below and above the melting point. Finally, three-dimensional results will be shown of the structure of a two-phase metallic meteorite of metal and sulfide, in which the Fe-Ni phase has coarsened during slow cooling over hundreds of millions of years.

Source record↗

Bridgman Growth of Germanium and Germanium-Silicon Crystals under Microgravity

Four different Bridgman growth experiments on Ge:Ga and Ge(sub x)Si(sub 1-x) were performed under microgravity during the FOTON M4 flight in fall 2014 as joint German-Russian experiments. The experiments were also part of the RDGS/ICESAGE project(s) of ESA/NASA on detached growth of Ge and Ge-Si. Three experiments on Ge:Ga investigated different heat and mass transport regimes, i.e. mostly diffusive conditions, flows driven by a rotating magnetic field, and flows driven by vibration. The fourth experiment on Ge(sub 0.98)Si(0.02) investigated detached growth. All four experiments were successful and yielded crystals. Both the Ge-Si experiment and two of the Ge:Ga experiments showed stable detachment from the ampoule wall, although this was not planned for the latter two experiments. The influence of the rotating magnetic field as well as of the vibration was pronounced in the case of the microgram experiments, but dominated by buoyancy convection under 1g.

Croell, A.↗

Oxide-Free Three-Dimensional Germanium/Silicon Core–Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition

Metalattices are crystalline arrays of uniform particles in which the period of the crystal is close to some characteristic physical length scale of the material. In this work, we explore the synthesis and properties of a germanium metalattice in which the similar to 70 nm periodicity of a silica colloidal crystal template is close to the similar to 24 nm Bohr exciton radius of the nanocrystalline Ge replica. The problem of Ge surface oxidation can be significant when exploring quantum confinement effects or designing electronically coupled nanostructures because of the high surface area to volume ratio at the nanoscale. To eliminate surface oxidation, we developed a coreshell synthesis in which the Ge metalattice is protected by an oxide-free Si interfacial layer, and we explore its properties by transmission electron microscopy (TEM), Raman spectroscopy, and electron energy loss spectroscopy (EELS). The interstices of a colloidal crystal film grown from 69 nm diameter spherical silica particles were filled with polycrystalline Ge by high-pressure confined chemical vapor deposition (HPcCVD) from GeH4. After the SiO2 template was etched away with aqueous HF, the Ge replica was uniformly coated with an amorphous Si shell by HPcCVD as confirmed by TEM-EDS (energy-dispersive X-ray spectroscopy) and Raman spectroscopy. Formation of the shell prevents oxidation of the Ge core within the detection limit of XPS. The electronic properties of the core-shell structure were studied by accessing the Ge 3d edge onset using STEM-EELS. A blue shift in the edge onset with decreasing size of Ge sites in the metalattices suggests quantum confinement of the Ge core. The degree of quantum confinement of the Ge core depends on the void sizes in the template, which is tunable by using silica particles of varying size. The edge onset also shows a shift to higher energy near the shell in comparison with the Ge core. This shift along with the observation of Ge-Si vibrational modes in the Raman spectrum indicate interdiffusion of Ge and Si. Both the size of the voids in the template and core-shell interdiffusion of Si and Ge can in principle be tuned to modify the electronic properties of the Ge metalattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduction of Defects in Germanium-Silicon

It is well established that crystals grown without contact with a container have far superior quality to otherwise similar crystals grown in direct contact with a container. In addition to float-zone processing, detached-Bridgman growth is often cited as a promising tool to improve crystal quality, without the limitations of float zoning. Detached growth has been found to occur quite often during microgravity experiments and considerable improvements of crystal quality have been reported for those cases. However, no thorough understanding of the process or quantitative assessment of the quality improvements exists so far. This project will determine the means to reproducibly grow Ge-Si alloys in the detached mode. Specific objectives include: (1) measurement of the relevant material parameters such as contact angle, growth angle, surface tension, and wetting behavior of the GeSi-melt on potential crucible materials; (2) determination of the mechanism of detached growth including the role of convection; (3) quantitative determination of the differences of defects and impurities among normal Bridgman, detached Bridgman, and floating zone (FZ) growth; (4) investigation of the influence of defined azimuthal or meridional flow due to rotating magnetic fields on the characteristics of detached growth; (5) control time-dependent Marangoni convection in the case of FZ-growth by the use of a rotating magnetic field to examine the influence on the curvature of the solid-liquid interface and the heat and mass transport; and (6) grow high quality GeSi-single crystals with Si-concentration up to 10 at% and diameters up to 20 mm.

Szofran, Frank R.↗

Magnetic Damping of Solid Solution Semiconductor Alloys

The objective of this study is to conduct the Earth-based research sufficient to successfully propose a flight experiment (1) to experimentally test the validity of the modeling predictions applicable to the magnetic damping of convective flows in conductive melts as this applies to the bulk growth of solid solution semiconducting materials in the reduced gravitational levels available in low Earth orbit and (2) to assess the effectiveness of steady magnetic fields in reducing the fluid flows occurring in these materials during space processing. To achieve the objectives of this investigation, we are carrying out a comprehensive program in the Bridgman and floating-zone configurations using the solid solution alloy system Ge-Si. This alloy system was chosen because it has been studied extensively in environments that have not simultaneously included both low gravity and an applied magnetic field. Also, all compositions have a high electrical conductivity, and the materials parameters permit high growth rates compared to many other commonly studied alloy semiconductors. An important supporting investigation is determining the role, if any, that thermoelectromagnetic convection (TEMC) plays during growth of these materials in a magnetic field. Some compositional anomalies observed by us in magnetic grown crystals can only be explained by TEMC; this has significant implications for the deployment of a Magnetic Damping Furnace in space. This effect will be especially important in solid solutions where the growth interface is, in general, neither isothermal nor isoconcentrational. It could be important in single melting point materials, also, if faceting takes place producing a non-isothermal interface.

Szofran, Frank R.↗

Reduction of Defects in Germanium-Silicon

It is well established that crystals grown without contact with a container have far superior quality to otherwise similar crystals grown in direct contact with a container. In addition to float- zone processing, detached-Bridgman growth is often cited as a promising tool to improve crystal quality, without the limitations of float zoning. Detached growth has been found to occur quite often during micro-g experiments and considerable improvements of crystal quality have been reported for those cases. However, no thorough understanding of the process or quantitative assessment of the quality improvements exists so far. This project will determine the means to reproducibly grow Ge-Si alloys in the detached mode. Specific objectives include: (1) measurement of the relevant material parameters such as contact angle, growth angle, surface tension, and wetting behavior of the GeSi-melt on potential crucible materials; (2) determination of the mechanism of detached growth including the role of convection; (3) quantitative determination of the differences of defects and impurities among normal Bridgman, detached Bridgman, and Floating Zone (FZ) growth; (4) investigation of the influence of defined azimuthal or meridional flow due to rotating magnetic fields on the characteristics of detached growth; (5) control time-dependent Marangoni convection in the case of FZ-growth by the use of a rotating magnetic field to examine the influence on the curvature of the solid-liquid interface and the heat and mass transport; and (6) grow high quality GeSi-single crystals with Si-concentration up to 10 at% and diameters up to 20 mm.

Szofran, Frank R.↗

Reduction of Defects in Germanium-Silicon

Crystals grown without contact with a container have far superior quality to otherwise similar crystals grown in direct contact with a container. In addition to float-zone processing, detached-Bridgman growth is a promising tool to improve crystal quality, without the limitations of float zoning. Detached growth has been found to occur frequently during microg experiments and considerable improvements of crystal quality have been reported for those cases. However, no thorough understanding of the process or quantitative assessment of the quality improvements exists so far. This project is determining the means to reproducibly grow Ge-Si alloys in the detached mode.

Szofran, F. R.↗

Uses of Computed Tomography in the NASA Materials Science Program

Computed Tomography (CT) has proved to be of inestimable use in providing a rapid evaluation of a variety of samples from Mechanics of Granular Materials (MGM) to electronic materials (Ge-Si alloys) to space grown materials such as meteorites. The system at Kennedy Space Center (KSC), because of its convenient geographical location, is ideal for examining samples immediately after returning to Earth. It also has the advantage of the choice of fluxes, and in particular the use of a radioactive cobalt source, which is basically monochromatic. This permits a reasonable measurement of density to be made from which chemical composition can be determined. Due to the current dearth of long duration space grown materials, the CT instrument has been used to characterize materials in preparation for flight, to determine thermal expansion values, and to examine long duration space grown materials, i.e. meteorites. The work will first describe the establishment of the protocol for obtaining the optimum density readings for any material. This will include both the effects of the hardware or instrumental parameters that can be controlled, and the techniques used to process the CT data. Examples will be given of the compositional variation along single crystals of germanium-silicon alloys. Density variation with temperature has been measured in preparation for future materials science experiments; this involved the fabrication and installation of a single zone furnace incorporating a heat pipe to ensure of high temperature uniformity. At the time of writing the thermal expansion of lead has been measured from room temperature to 900 C. Three methods are available. Digital radiography enable length changes to be determined. Prior to melting the sample is small than the container and the diameter change can be measured. Most critical, however, is the density change in solid, through the melting region, and in the liquid state. These data are needed for engineering purposes to aid in the design of containment cartridges, and for enabling fluid flow calculations. A second sample, with the lead alloyed with antimony is ready for scanning. This corresponds to the planned composition of Dr. Poirier's flight experiment. Finally, three-dimensional results will be shown of the structure of a two-phase metallic meteorite of metal and sulfide, in which the iron-nickel phase has coarsened during slow cooling over hundreds of millions of years.

Engel, H. Peter↗

Semiconductor Crystal Growth in Static and Rotating Magnetic fields

Magnetic fields have been applied during the growth of bulk semiconductor crystals to control the convective flow behavior of the melt. A static magnetic field established Lorentz forces which tend to reduce the convective intensity in the melt. At sufficiently high magnetic field strengths, a boundary layer is established ahead of the solid-liquid interface where mass transport is dominated by diffusion. This can have a significant effect on segregation behavior and can eliminate striations in grown crystals resulting from convective instabilities. Experiments on dilute (Ge:Ga) and solid solution (Ge-Si) semiconductor systems show a transition from a completely mixed convective state to a diffusion-controlled state between 0 and 5 Tesla. In HgCdTe, radial segregation approached the diffusion limited regime and the curvature of the solid-liquid interface was reduced by a factor of 3 during growth in magnetic fields in excess of 0.5 Tesla. Convection can also be controlled during growth at reduced gravitational levels. However, the direction of the residual steady-state acceleration vector can compromise this effect if it cannot be controlled. A magnetic field in reduced gravity can suppress disturbances caused by residual transverse accelerations and by random non-steady accelerations. Indeed, a joint program between NASA and the NHMFL resulted in the construction of a prototype spaceflight magnet for crystal growth applications. An alternative to the suppression of convection by static magnetic fields and reduced gravity is the imposition of controlled steady flow generated by rotating magnetic fields (RMF)'s. The potential benefits of an RMF include homogenization of the melt temperature and concentration distribution, and control of the solid-liquid interface shape. Adjusting the strength and frequency of the applied magnetic field allows tailoring of the resultant flow field. A limitation of RMF's is that they introduce deleterious instabilities above a critical magnetic field value. Growth conditions in which static magnetic fields rotational magnetic fields, and reduced gravitational levels can have a beneficial role will be described.

Volz, Martin↗

Reduction of Defects in Germanium-Silicon

Crystals grown without contact with a container have far superior quality to otherwise similar crystals grown in direct contact with a container. In addition to float-zone processing, detached- Bridgman growth is a promising tool to improve crystal quality, without the limitations of float zoning or the defects introduced by normal Bridgman growth. Goals of this project include the development of the detached Bridgman process to be reproducible and well understood and to quantitatively compare the defect and impurity levels in crystals grown by these three methods. Germanium (Ge) and germanium-silicon (Ge-Si) alloys are being used. At MSFC, we are responsible for the detached Bridgman experiments intended to differentiate among proposed mechanisms of detachment, and to confirm or refine our understanding of detachment. Because the contact angle is critical to determining the conditions for detachment, the sessile drop method was used to measure the contact angles as a function of temperature and composition for a large number of substrates made of potential ampoule materials. Growth experiments have used pyrolytic boron nitride (pBN) and fused silica ampoules with the majority of the detached results occurring predictably in the pBN. Etch pit density (EPD) measurements of normal and detached Bridgman-grown Ge samples show a two order of magnitude improvement in the detached-grown samples. The nature and extent of detachment is determined by using profilometry in conjunction with optical and electron microscopy. The stability of detachment has been analyzed, and an empirical model for the conditions necessary to achieve sufficient stability to maintain detached growth for extended periods has been developed. We have investigated the effects on detachment of ampoule material, pressure difference above and below the melt, and Si concentration; samples that are nearly completely detached can be grown repeatedly in pBN. Current work is concentrated on developing a method to make in situ pressure measurements in the growth ampoules.

Source record↗

Materials Data on Si3Ge by Materials Project

GeSi3 is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ge4+ is bonded in a body-centered cubic geometry to eight equivalent Si+1.33- atoms. All Ge–Si bond lengths are 2.74 Å. There are two inequivalent Si+1.33- sites. In the first Si+1.33- site, Si+1.33- is bonded in a body-centered cubic geometry to four equivalent Ge4+ and four equivalent Si+1.33- atoms. All Si–Si bond lengths are 2.74 Å. In the second Si+1.33- site, Si+1.33- is bonded in a body-centered cubic geometry to eight equivalent Si+1.33- atoms.

36 MATERIALS SCIENCE↗

Materials Data on SiGe3 by Materials Project

Ge3Si crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Ge sites. In the first Ge site, Ge is bonded to eight Ge and four equivalent Si atoms to form a mixture of distorted corner, edge, and face-sharing GeSi4Ge8 cuboctahedra. There are four shorter (2.81 Å) and four longer (3.08 Å) Ge–Ge bond lengths. All Ge–Si bond lengths are 3.08 Å. In the second Ge site, Ge is bonded in a square co-planar geometry to eight equivalent Ge and four equivalent Si atoms. All Ge–Si bond lengths are 2.81 Å. Si is bonded in a square co-planar geometry to twelve Ge atoms.

36 MATERIALS SCIENCE↗

Materials Data on Si7Ge by Materials Project

GeSi7 is Moissanite 9R-like structured and crystallizes in the cubic P-43m space group. The structure is three-dimensional. Ge4+ is bonded to four equivalent Si+0.57- atoms to form GeSi4 tetrahedra that share corners with twelve equivalent SiSi4 tetrahedra. All Ge–Si bond lengths are 2.41 Å. There are two inequivalent Si+0.57- sites. In the first Si+0.57- site, Si+0.57- is bonded to one Ge4+ and three equivalent Si+0.57- atoms to form corner-sharing SiSi3Ge tetrahedra. All Si–Si bond lengths are 2.37 Å. In the second Si+0.57- site, Si+0.57- is bonded to four equivalent Si+0.57- atoms to form SiSi4 tetrahedra that share corners with four equivalent GeSi4 tetrahedra and corners with eight equivalent SiSi4 tetrahedra.

36 MATERIALS SCIENCE↗

Materials Data on SiGe by Materials Project

SiGe is Zincblende, Sphalerite structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. Ge4+ is bonded to four equivalent Si4- atoms to form corner-sharing GeSi4 tetrahedra. All Ge–Si bond lengths are 2.42 Å. Si4- is bonded to four equivalent Ge4+ atoms to form corner-sharing SiGe4 tetrahedra.

36 MATERIALS SCIENCE↗