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At least 253 records · Page 14

Growth rates and interface shapes in germanium and lead tin telluride observed in-situ, real-time in vertical Bridgman furnaces

Using the advanced technology developed to visualize the melt-solid interface in low Prandtl number materials, crystal growth rates and interface shapes have been measured in germanium and lead tin telluride semiconductors grown in vertical Bridgman furnaces. The experimental importance of using in-situ, real time observations to determine interface shapes, to measure crystal growth rates, and to improve furnace and ampoule designs is demonstrated. The interface shapes observed in-situ, in real-time were verified by quenching and mechanically induced interface demarcation, and they were also confirmed using machined models to ascertain the absence of geometric distortions. Interface shapes depended upon the interface position in the furnace insulation zone, varied with the nature of the crystal being grown, and were dependent on the extent of transition zones at the ends of the ampoule. Actual growth rates varied significantly from the constant translation rate in response to the thermophysical properties of the crystal and its melt and the thermal conditions existing in the furnace at the interface. In the elemental semiconductor germanium the observed rates of crystal growth exceeded the imposed translation rate, but in the compound semiconductor lead tin telluride the observed rates of growth were less than the translation rate. Finally, the extent of ampoule thermal loading influenced the interface positions, the shapes, and the growth rates.

Barber, P. G.↗

Growth Angle - a Microscopic View

The growth angle that is formed between the side of the growing crystal and the melt meniscus is an important parameter in the detached Bridgman crystal growth method, where it determines the extent of the crystal-crucible wall gap, and in the Czochralski and float zone methods, where it influences the size and stability of the crystals. The growth angle is a non-equilibrium parameter, defined for the crystal growth process only. For a melt-crystal interface translating towards the crystal (melting), there is no specific angle defined between the melt and the sidewall of the solid. In this case, the corner at the triple line becomes rounded, and the angle between the sidewall and the incipience of meniscus can take a number of values, depending on the position of the triple line. In this work, a microscopic model is developed in which the fluid interacts with the solid surface through long range van der Waals or Casimir dispersive forces. This growth angle model is applied to Si and Ge and compared with the macroscopic approach of Herring. In the limit of a rounded corner with a large radius of curvature, the wetting of the melt on the crystal is defined by the contact angle. The proposed microscopic approach addresses the interesting issue of the transition from a contact angle to a growth angle as the radius of curvature decreases.

Mazurak, K.↗

Crystal Growth Control

We present an innovative design of a vertical transparent multizone furnace which can operate in the temperature range of 25 C to 750 C and deliver thermal gradients of 2 C/cm to 45 C/cm for the commercial applications to crystal growth. The operation of the eight zone furnace is based on a self-tuning temperature control system with a DC power supply for optimal thermal stability. We show that the desired thermal profile over the entire length of the furnace consists of a functional combination of the fundamental thermal profiles for each individual zone obtained by setting the set-point temperature for that zone. The self-tuning system accounts for the zone to zone thermal interactions. The control system operates such that the thermal profile is maintained under thermal load, thus boundary conditions on crystal growth ampoules can be predetermined prior to crystal growth. Temperature profiles for the growth of crystals via directional solidification, vapor transport techniques, and multiple gradient applications are shown to be easily implemented. The unique feature of its transparency and ease of programming thermal profiles make the furnace useful for scientific and commercial applications for the determination of process parameters to optimize crystal growth conditions.

Duval, Walter M. B.↗

The Design of a Transparent Vertical Multizone Furnace: Application to Thermal Field Tuning and Crystal Growth

We present an innovative design of a vertical transparent multizone furnace which can operate in the temperature range of 25 C to 750 C and deliver thermal gradients of 2 C/cm to 45 C/cm for the commercial applications to crystal growth. The operation of the eight zone furnace is based on a self-tuning temperature control system with a DC power supply for optimal thermal stability. We show that the desired thermal profile over the entire length of the furnace consists of a functional combination of the fundamental thermal profiles for each individual zone obtained by setting the set-point temperature for that zone. The self-tuning system accounts for the zone to zone thermal interactions. The control system operates such that the thermal profile is maintained under thermal load, thus boundary conditions on crystal growth ampoules can be predetermined prior to crystal growth. Temperature profiles for the growth of crystals via directional solidification, vapor transport techniques, and multiple gradient applications are shown to be easily implemented. The unique feature of its transparency and ease of programming thermal profiles make the furnace useful in scientific and commercial applications for determining the optimized process parameters for crystal growth.

Duvual, Walter M. B.↗

Material and processing needs for silicon solar cells in space

The technical concerns of NASA in the area of space grade solar cells are summarized. Solar power needs are projected through 1987. The degradation of solar cell performance due to the effects of radiation on impurities and crystal defects and the improved performance of float zone silicon are illustrated. The reduction of oxygen and carbon in float zone silicon allows for much faster low temperature annealing of the defects. The effects of improved crystal purity on cell performance are summarized.

Brandhorst, H. W., Jr.↗

Float zone processing in a weightless environment

Results are given for investigations into: (1) the physical limits which set the maximum practical diameters of Si crystals that can be processed by the float-zone method in a near weightless environment, and (2) the economic impact of large, space-produced Si crystals on the electronics industry. The stability of the melt is evaluated. Heat transfer and fluid flow within the melt as dependent on the crystal size and the degree and type of rotation imparted to the melt are studied. Methods of utilizing the weightless environment for the production of large, stress-free Si crystals of uniform composition are proposed. The economic effect of large size Si crystals, their potential applications, likely utilization and cost advantages in LSI, integrated circuits, and power devices are also evaluated. Foreseeable advantages of larger diameter wafers of good characteristics and the possibilities seen for greater perfection resulting from stress-free growth are discussed.

Fowle, A. A.↗

Chemical abrasion: the mechanics of zircon dissolution

Chemical abrasion is a technique that combines thermal annealing and partial dissolution in hydrofluoric acid (HF) to selectively remove radiation-damaged portions of zircon crystals prior to U–Pb isotopic analysis, and it is applied ubiquitously to zircon prior to U–Pb isotope dilution thermal ionization mass spectrometry (ID-TIMS). The mechanics of zircon dissolution in HF and the impact of different leaching conditions on the zircon structure, however, are poorly resolved. We present a microstructural investigation that integrates microscale X-ray computed tomography (µCT), scanning electron microscopy, and Raman spectroscopy to evaluate zircon dissolution in HF. We show that µCT is an effective tool for imaging metamictization and complex dissolution networks in three dimensions. Acid frequently reaches crystal interiors via fractures spatially associated with radiation damage zoning and inclusions to dissolve soluble high-U zones, some inclusions, and material around fractures, leaving behind a more crystalline zircon residue. Other acid paths to crystal cores include the dissolution of surface-reaching inclusions and the percolation of acid across zones with high defect densities. In highly crystalline samples dissolution is crystallographically controlled with dissolution proceeding almost exclusively along the c axis. Increasing the leaching temperature from 180 to 210 °C results in deeper etching textures, wider acid paths, more complex internal dissolution networks, and greater volume losses. How a grain dissolves strongly depends on its initial radiation damage content and defect distribution as well as the size and position of inclusions. As such, the effectiveness of any chemical abrasion protocol for ID-TIMS U–Pb geochronology is likely sample-dependent. We also briefly discuss the implications of our findings for deep-time (U-Th)/He thermochronology.

58 GEOSCIENCES↗

Method of making single crystal fibers

Single crystal fibers are made from miniature extruded ceramic feed rods. A decomposable binder is mixed with powders to inform a slurry which is extruded into a small rod which may be sintered, either in air or in vacuum, or it may be used in the extruded and dried condition. A pair of laser beams focuses onto the tip of the rod to melt it thereby forming a liquid portion. A single crystal seed fiber of the same material as the feed rod contacts this liquid portion to establish a zone of liquid material between the feed rod and the single crystal seed fiber. The feed rod and the single crystal feed fiber are moved at a predetermined speed to solidify the molten zone onto the seed fiber while simultaneously melting additional feed rod. In this manner a single crystal fiber is formed from the liquid portion.

Westfall, Leonard J.↗

Studies of rotating liquid floating zones on Skylab IV

Liquid zones of water, soap solution and soap foam were deployed between two aligned circular disks which were free to rotate about the zone axis in the microgravity environment of Skylab IV. Such a configuration is of interest in the containerless handling of melts for possible future space processing crystal growth experiments. Three basic types of zone surface deformation and instability were observed for these rotational conditions; axisymmetric shape changes under single disk rotation, nonaxisymmetric, whirling, C-modes for long zones with equal rotation of both disks, and capillary wave phenomena for short zones with equal rotation of both disks. The sources of these instabilities and the conditions promoting them are analyzed in detail from video tape recordings of the Skylab experiments.

Carruthers, J. R.↗

Bulk transport paths through defects in floating zone and Al flux grown SmB 6

We investigate the roles of disorder on low-temperature transport in SmB 6 crystals grown by both the Al flux and floating zone methods. We used the inverted resistance method with Corbino geometry to investigate whether low-temperature variations in the standard resistance plateau arise from a surface or a bulk channel in floating zone samples. The results show significant sample-dependent residual bulk conduction, in contrast to smaller amounts of residual bulk conduction previously observed in Al flux grown samples with Sm vacancies. In this work, we consider hopping in an activated impurity band as a possible source for the observed bulk conduction, but it is unlikely that the large residual bulk conduction seen in floating zone samples is solely due to Sm vacancies. We therefore propose that one-dimensional defects, or dislocations, contribute as well. Using chemical etching, we find evidence for dislocations in both flux and floating zone samples, with higher dislocation density in floating zone samples than in Al flux grown samples. In addition to the possibility of transport through one-dimensional dislocations, we also discuss our results in the context of recent theoretical models of SmB 6 .

36 MATERIALS SCIENCE↗

Analytics of crystal growth in space

Two crystal growth processes considered for spacelab experiments were studied to anticipate and understand phenomena not ordinarily encountered on earth. Computer calculations were performed on transport processes in floating zone melting and on growth of a crystal from solution in a spacecraft environment. Experiments intended to simulate solution growth at micro accelerations were performed.

Wilcox, W. R.↗

Fundamentals of Scalable Nanoparticle Assembly in Engineering Polymres

Systematically improving the properties of polymer nanocomposites is contingent on effectively controlling nanoparticle (NP) dispersion; further, it is necessary to attain this at scale if these methods are to impact practical applications. While most past work has focused on amorphous polymers, ≈ 70% of all polymers sold annually are semicrystalline. Inspired by this apparent disconnect, our work in the current DOE funded grant and this renewal proposal employs a novel handle, polymer crystallization, to organize NPs into the various amorphous zones of the lamellar semicrystalline morphology (interlamellar, interfibrillar and interspherulitic domains) of stereoregular polymers. We hypothesize that the isothermal crystallization rate of a polymer host, G, and NP diffusivity, are the two relevant control parameters in this context. In the case where the NPs are miscible in the melt, they remain spatially well-dispersed when the polymer is crystallized at a rate that is fast relative to NP diffusion. In contrast, monolayer-thick NP sheets with intersheet spacing of ~10-100nm form in slowly crystallized samples. This sheet stacking is remarkably similar to that seen in natural materials, e.g., Nacre. There is also ordering of the NPs at the larger interfibrillar scale. Importantly, the relative fraction of engulfed, interlamellar and interfibrillar NPs is determined by G. Further, the modulus of these materials can increase by a factor of 2-3 due to the organization state of the NPs, while leaving fracture toughness unaffected. We have established the broad applicability of this approach in two polymers, polyethylene (PE) and polyethyleneoxide (PEO). To achieve this goal we developed a method for grafting long PE chains from NPs with controlled graft density and molecular weight, giving us the ability to tailor their dispersion in the PE melt prior to crystallization. In this renewal proposal, we will develop the fundamental, quantitative understanding that will allow us to independently tailor polymer crystallization rate, NP diffusivity and NP agglomeration state in semicrystalline polymers so as to facilely control NP ordering and hence properties. A program that tightly integrates experiment and theory is proposed, and a key outcome of this research will be a three-dimensional design map for different regimes of NP organization (and hence properties) that can be achieved by polymer crystallization. A second independent outcome is the role of directional solidification and how it competes with the rates of polymer crystallization and NP mobility to affect the organization of the NP.

36 MATERIALS SCIENCE↗

Investigation of Three-Dimensional Stress Fields and Slip Systems for FCC Single Crystal Superalloy Notched Specimens

Metals and their alloys, except for a few intermetallics, are inherently ductile, i.e. plastic deformation precedes fracture in these materials. Therefore, resistance to fracture is directly related to the development of the plastic zone at the crack tip. Recent studies indicate that the fracture toughness of single crystals depends on the crystallographic orientation of the notch as well as the loading direction. In general, the dependence of crack propagation resistance on crystallographic orientation arises from the anisotropy of (i) elastic constants, (ii) plastic deformation (or slip), and (iii) the weakest fracture planes (e.g. cleavage planes). Because of the triaxial stress state at the notch tips, many slip systems that otherwise would not be activated during uniaxial testing, become operational. The plastic zone formation in single crystals has been tackled theoretically by Rice and his co-workers and only limited experimental work has been conducted in this area. The study of the stresses and strains in the vicinity of a FCC single crystal notch tip is of relatively recent origin. We present experimental and numerical investigation of 3D stress fields and evolution of slip sector boundaries near notches in FCC single crystal tension test specimens, and demonstrate that a 3D linear elastic finite element model that includes the effect of material anisotropy is shown to predict active slip planes and sectors accurately. The slip sector boundaries are shown to have complex curved shapes with several slip systems active simultaneously near the notch. Results are presented for surface and mid-plane of the specimens. The results demonstrate that accounting for 3D elastic anisotropy is very important for accurate prediction of slip activation near FCC single crystal notches loaded in tension. Results from the study will help establish guidelines for fatigue damage near single crystal notches.

Arakere, Nagaraj K.↗

Two-Zone Bridgman Furnace With Sharp Thermal Gradient

Two-zone vertical directional-solidification furnace designed and built to grow crystals from stoichiometric and nonstoichiometric melts and from solutions. Includes conventional wire heater in lower zone, tubular silicon carbide heating element in upper zone, and thermal baffle between zones. Temperature gradients up to 125 degrees centigrade per centimeter achieved in the crystal-growth region. Sharper gradient enables both faster growth and better separation between solid and liquid. Furnace used in laboratory or industrial setting for growth of crystals from congruently melting materials as well as for growth of compounds formed by peritectic reactions.

Borshchevsky, Alex↗

Crystallization of plagioclase in mare basalts

A detailed study has been made of the morphology, zoning and major- and minor-element chemistry of plagioclase in mare basalt 12021 and for comparison, in several other mare basalts. Two types of plagioclase can be distinguished based on growth rate as expressed by the formation of hollow as opposed to lath-shaped crystals. The liquidus plagioclase is the most sodic part of the hollow crystals and is more sodic than the lath-shaped crystals. Hollow grains show oscillatory zoning, whereas the lath-shaped grains show normal zoning. The ratios FeO/(FeO + MgO) and K2O/(K2O + Na2O) increased in both types of plagioclase as they grew, and these ratios can be used as a guide to the crystallization history of the plagioclase. The FeO/(FeO + MgO) ratios are similar to those of coprecipitating pyroxene. The data presented here suggest the onset of plagioclase nucleation is primarily controlled by magma composition, and the point at which the magma becomes supersaturated with plagioclase.

Crawford, M. L.↗

Single-Heater, Three-Zone Furnace

Temperature profile shaped with help of thermal barriers. Proposed furnace for use in experiments on growth of crystals of highly pure material in ampoule provides three temperature zones, yet contains only one heat-pipe liner and one heater and operates with only one controller. Three temperature zones established as thermal resistances of wicks and noncondensible gas reduces flows of heat into channel containing ampoule. Motion of ampoule along channel causes gradients of temperature to move along specimen in ampoule. Variety of three-zone temperature profiles in furnace created by changing thermal resistances of zones and injecting noncondensible gas at appropriate point. Furnace used for variety of experiments.

Gernert, Nelson J.↗

Computationally-driven discovery of second harmonic generation in EuBa 3 (B 3 O 6 ) 3 through inversion symmetry breaking

Nonlinear optical (NLO) crystals with superior properties are significant for advancing laser technologies and applications. Introducing rare earth metals to borates is a promising and effective way to modify the electronic structure of a crystal to improve its optical properties in the visible and ultraviolet range. In this work, we computationally discover inversion symmetry breaking in EuBa 3 (B 3 O 6 ) 3 , which was previously identified as centric, and demonstrate noncentrosymmetry via synthesizing single crystals for the first time by the floating zone method. We determine the correct space group to be P 6¯. The material has a large direct bandgap of 5.56 eV and is transparent down to 250 nm. The complete anisotropic linear and nonlinear optical properties were also investigated with a d 11 of ∼0.52 pm/V for optical second harmonic generation. Further, it is Type I and Type II phase matchable. This work suggests that rare earth metal borates are an excellent crystal family for exploring future deep ultraviolet (DUV) NLO crystals. It also highlights how first principles computations combined with experiments can be used to identify noncentrosymmetric materials that have been wrongly assigned to be centrosymmetric.

He, Jingyang (ORCID:0000000238863659)↗

Measurements of the aerosol and ice crystal populations in tropical stratospheric cumulonimbus anvils

A pair of particle size spectrometers was flown aboard the NASA U-2 operating from the Canal Zone to make measurements of the aerosol and ice crystal budgets in cirrus produced by thunderstorms in the tropics. Measurements indicate that fairly large crystals up to 1 mm in size are injected into the stratosphere during cumulonimbus activity. Ice water contents range from a few thousandths to a few hundredths of a gram per cubic meter. Because the ambient temperature is typically around -80 C the mass of the larger crystals largely returns to lower altitudes before evaporating. Aerosol size distributions indicate a curious narrow growth mode between 0.15 and 0.2 micron in cirrus anvils which is absent outside these clouds. The presence of this narrow mode is attributed to near water saturation produced at cloud top. Nucleation of new ice crystals as well as aerosol is hypothesized

Knollenberg, R. G.↗