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At least 235 records · Page 13

Crystal Growth by Physical Vapor Transport: Experiments and Simulation Dynamics

Crystal growth from the vapor phase has various advantages over melt growth. The main advantage is from a lower processing temperature, which makes the process more amenable in instances where the melting temperature of the crystal is high. Other benefits stem from the inherent purification mechanism in the process due to differences in the vapor pressures of the native elements and impurities, and the enhanced interfacial morphological stability during the growth process. Further, the implementation of PVT growth in closed ampoules affords experimental simplicity with minimal needs for complex process control, which makes it an ideal candidate for space investigations in systems where gravity tends to have undesirable effects on the growth process. Bulk growth of wide band gap II-VI semiconductors by PVT has been developed and refined over the past several years at NASA MSFC. A new modeling approach for PVT has also been recently formulated and its validation and testing is the main objective of this work.

Ramachandran, N.↗

Unusual Li 2 O sublimation promotes single-crystal growth and sintering

Li 2 O is rarely used for cathode material synthesis due to its high melting point (1,438 °C). Here we discover that Li 2 O can sublimate at 800-1,000 °C under ambient pressure, opening new possibilities for cathode synthesis. We propose a mechanism that enables synthesis of single crystals-such as LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) or LiNi 0.9 Mn 0.05 Co 0.05 O 2 (NMC90)-without direct contact with Li 2 O salts. We show that Li 2 O vapour successfully converts spent polycrystalline NMC811 into segregated single crystals without milling or post-treatment. The Li 2 O vapour, derived from Li 2 O solids, diffuses rapidly and reacts with precursors, mimicking a molten-salt environment, which facilitates single-crystal growth. The chemical lithiation process continuously drives Li 2 O sublimation, sintering the crystals. Single crystals derived from Li 2 O and fresh precursors or spent polycrystals exhibit outstanding cycling after 1,000 cycles in full cells. The demonstrated Li 2 O sublimation and its universal role in promoting single-crystal growth provides an effective approach for single-crystal synthesis, scale-up and recycling.

25 ENERGY STORAGE↗

Silicon crystal growth in vacuum

The most developed process for silicon crystal growth is the Czochralski (CZ) method which was in production for over two decades. In an effort to reduce cost of single crystal silicon for photovoltaic applications, a directional solidification technique, Heat Exchanger Method (HEM), was adapted. Materials used in HEM and CZ furnaces are quite similar (heaters, crucibles, insulation, etc.). To eliminate the cost of high purity argon, it was intended to use vacuum operation in HEM. Two of the major problems encountered in vacuum processing of silicon are crucible decomposition and silicon carbide formation in the melt.

Khattak, C. P.↗

Tuning the melting point and phase stability of rare-earth oxides to facilitate their crystal growth from the melt

The challenge of growing rare-earth (RE) sesquioxide crystals can be overcome by tailoring their structural stability and melting point via composition engineering. This work contributes to the advancement of the field of crystal growth of high-entropy oxides. A compound with only small REs (Lu,Y,Ho,Yb,Er) 2 O 3 maintains a cubic C-type structure upon cooling from the melt, as observed via in-situ high-temperature neutron diffraction on aerodynamically levitated samples. On the other hand, a compound with a mixture of small and large REs (Lu,Y,Ho,Nd,La) 2 O 3 crystallizes as a mixture of a primary C-type phase with an unstable secondary phase. Crystals of compositions (Lu,Y,Ho,Nd,La) 2 O 3 and (Lu,Y,Gd,Nd,La) 2 O 3 were grown by the micro-pulling-down (mPD) method with a single monoclinic B-type phase, while a powder of (Lu,Y,Ho,Yb,Er) 2 O 3 did not melt at the maximum operating temperature of an iridium-rhenium crucible. The minimization of the melting point of the two grown crystals is attributed to the mismatch in cation sizes. The electron probe microanalysis reveals that the general element segregation behavior in the crystals depends on the composition.

36 MATERIALS SCIENCE↗

Zeolite crystal growth in space - What has been learned

Three zeolite crystal growth experiments developed at WPI have been performed in space in last twelve months. One experiment, GAS-1, illustrated that to grow large, crystallographically uniform crystals in space, the precursor solutions should be mixed in microgravity. Another experiment evaluated the optimum mixing protocol for solutions that chemically interact ('gel') on contact. These results were utilized in setting the protocol for mixing nineteen zeolite solutions that were then processed and yielded zeolites A, X and mordenite. All solutions in which the nucleation event was influenced produced larger, more 'uniform' crystals than did identical solutions processed on earth.

Sacco, A., Jr.↗

Protein crystal growth results from shuttle flight 51-F

The protein crystal growth (PCG) experiments run on 51-F were analyzed. It was found that: (1) sample stability is increased over that observed during the experiments on flight 51-D; (2) the dialysis experiments produced lysozyme crystals that were significantly larger than those obtained in our identical ground-based studies; (3) temperature fluctuations apparently caused problems during the crystallization experiments on 51-F; (4) it is indicated that teflon tape stabilizes droplets on the syringe tips; (5) samples survived during the reentry and landing in glass tips that were not stoppered with plungers; (6) from the ground-based studies, it was expected that equilibration should be complete within 2 to 4 days for all of these vapor-diffusion experiments, thus it appears that the vapor diffusion rates are somewhat slower under microgravity conditions; (7) drop tethering was highly successful, all four of the tethered drops were stable, even though they contained MPD solutions; (8) the PCG experiments on 51-F were done to assess the hardware and experimental procedures that are developed for future flights, when temperature control will be available. Lysozyme crystals obtained by microdialysis are considerably larger than those obtained on the ground, using the identical apparatus and procedures.

Bugg, C. E.↗

Advanced protein crystal growth flight hardware for the Space Station

The operational environment of the Space Station will differ considerably from the previous short term missions such as the Spacelabs. Limited crew availability combined with the near continuous operation of Space Station facilities will require a high degree of facility automation. This paper will discuss current efforts to develop automated flight hardware for advanced protein crystal growth on the Space Station. Particular areas discussed will be the automated monitoring of key growth parameters for vapor diffusion growth and proposed mechanisms for control of these parameters. A history of protein crystal growth efforts will be presented in addition to the rationale and need for improved protein crystals for X-ray diffraction. The facility will be capable of simultaneously processing several hundred protein samples at various temperatures, pH's, concentrations etc., and provide allowances for real time variance of growth parameters.

Herrmann, Frederick T.↗

Skylab experiment performance evaluation manual. Appendix J: Experiment M555 gallium arsenide single crystal growth (MSFC)

Analyses for Experiment M555, Gallium Arsenide Single Crystal Growth (MSFC), to be used for evaluating the performance of the Skylab corollary experiments under preflight, inflight, and post-flight conditions are presented. Experiment contingency plan workaround procedure and malfunction analyses are presented in order to assist in making the experiment operationally successful.

Byers, M. S.↗

Morphological stability and fluid dynamics of vapor crystal growth

Research on morphological stability and fluid dynamics of crystal growth is discussed. Interfacial heat and mass transfer research is discussed. The finding of surface roughening is a precursor to a solid-solid phase transition was further quantified. Progress was obtained with the mass spectroscopic characterization of GeSe-Ge I sub 4.

Rosenberger, F. E.↗

Liquid drop stability for protein crystal growth in microgravity

It is possible to grow protein crystals for biomedical research in microgravity by deploying a protein-rich solution from a syringe, forming a drop in which crystallization can occur with the proper degree of supersaturation. Drop stability is critical to the success of this research, due to the large drop sizes which can be achieved in space. In order to determine the type of syringe tips most suitable to support these large drops, tests were performed during brief periods of weightlessness onboard the NASA KC-135 low-gravity simulation aircraft. The drops were analyzed using three simple models in which the samples were approximated by modified pendulum and spring systems. It was concluded that the higher frequency systems were the most stable, indicating that of the syringes utilized, a disk-shaped configuration provided the most stable environment of low-gravity protein crystal growth.

Owen, Robert B.↗

Opportunity for academic research in a low-gravity environment - Crystal growth

The history of basic and applied research on crystal growth (CG), especially of semiconductor materials, is reviewed, stressing the dominance (at least in the U.S.) of industrial R&D projects over academic programs and the need for more extensive fundamental investigations. The NASA microgravity research program and the recommendations of the University Space Research Association are examined as they affect the availability of space facilities for academic CG research. Also included is a report on ground experiments on the effectiveness of magnetic fields in controlling vertical Bridgman CG and melt stability, using the apparatus employed in the Apollo-Soyuz experiments (Witt et al., 1978); the results are presented in graphs and briefly characterized. The role of NASA's microgravity CG program in stimulating academic work on CG, the importance of convection effects, CG work on materials other than semiconductors, and NSF support of CG research are discussed in a comment by R. F. Sekerka.

Matthiesen, D. H.↗

Device and method for screening crystallization conditions in solution crystal growth

A device and method for detecting optimum protein crystallization conditions and for growing protein crystals in either 1g or microgravity environments comprising a housing, defining at least one pair of chambers for containing crystallization solutions is presented. The housing further defines an orifice therein for providing fluid communication between the chambers. The orifice is adapted to receive a tube which contains a gelling substance for limiting the rate of diffusive mixing of the crystallization solutions. The solutions are diffusively mixed over a period of time defined by the quantity of gelling substance sufficient to achieve equilibration and to substantially reduce density driven convection disturbances therein. The device further includes endcaps to seal the first and second chambers. One of the endcaps includes a dialysis chamber which contains protein solution in which protein crystals are grown. Once the endcaps are in place, the protein solution is exposed to the crystallization solutions wherein the solubility of the protein solution is reduced at a rate responsive to the rate of diffusive mixing of the crystallization solutions. This allows for a controlled approach to supersaturation and allows for screening of crystal growth conditions at preselected intervals.

Carter, Daniel C.↗

The Influence of Reduced Gravity on the Crystal Growth of Electronic Materials

The imperfections in the grown crystals of electronic materials, such as compositional nonuniformity, dopant segregation and crystalline structural defects, are detrimental to the performance of the opto-electronic devices. Some of these imperfections can be attributed to effects caused by Earth gravity during crystal growth process and four areas have been identified as the uniqueness of material processing in reduced gravity environment. The significant results of early flight experiments, i.e. prior to space shuttle era, are briefly reviewed followed by an elaborated review on the recent flight experiments conducted on shuttle missions. The results are presented for two major growth methods of electronic materials: melt and vapor growth. The use of an applied magnetic field in the melt growth of electrically conductive melts on Earth to simulate the conditions of reduced gravity has been investigated and it is believed that the superimposed effect of moderate magnetic fields and the reduced gravity environment of space can result in reduction of convective intensities to the extent unreachable by the exclusive use of magnet on Earth or space processing. In the Discussions section each of the significant results of the flight experiments is attributed to one of the four effects of reduced gravity and the unresolved problems on the measured mass fluxes in some of the vapor transport flight experiments are discussed.

Su, Ching-Hua↗

Device and Method for Screening Crystallization Conditions in Solution Crystal Growth

A device and method for detecting optimum protein crystallization conditions and for growing protein crystals in either 1 g or microgravity environments comprising a housing defining at least one pair of chambers for containing crystallization solutions. The housing further defines an orifice therein for providing fluid communication between the chambers. The orifice is adapted to receive a tube which contains a gelling substance for limiting the rate of diffusive mixing of the crystallization solutions. The solutions are diffusively mixed over a period of time defined by the quantity of gelling substance sufficient to achieve equilibration and to substantially reduce density driven convection disturbances therein. The device further includes endcaps to seal the first and second chambers. One of the endcaps includes a dialysis chamber which contains protein solution in which protein crystals are grown. Once the endcaps are in place. the protein solution is exposed to the crystallization solutions wherein the solubility of the protein solution is reduced at a rate responsive to the rate of diffusive mixing of the crystallization solutions. This allows for a controlled approach to supersaturation and allows for screening of crystal growth conditions at preselected intervals.

Carter, Daniel C.↗

New Directions in NASA's Biological Crystal Growth Program on the International Space Station

NASA's Biological Crystal Growth Program (BCG) on the International Space Station (ISS) is changing direction from the study of crystallization to an emphasis on producing crystals for structure determination in leading problems in structural biology. The program will consist of two phases. The first phase is during assembly of the ISS and will primarily utilize payloads that currently fly in the orbiter middeck but can be adapted for ISS. The second phase begins after assembly of the ISS is complete and BCG payloads will occupy part of the Biotechnology Facility aboard the ISS. Two types of BCG payloads will be flown. One will emphasize the production of crystals for structure determination back on Earth. These types of payloads will allow hundreds of crystallization conditions to be tested. The second type of payload will be designed to study the crystallization process with the primary aim of assisting the structural biology efforts. Access to these facilities will be through the NASA BCG Guest Investigators program, the NASA Research Announcement, and other opportunities currently being formulated. Details of the crystallization hardware, the application procedures, and the operational aspects of the program will be described.

Kundrot, Craig E.↗

New Directions in NASA's Biological Crystal Growth Program on the International Space Station

NASA's Biological Crystal Growth Program (BCG) on the International Space Station (ISS) is changing direction from the study of crystallization to an emphasis on producing crystals for structure determination in leading problems in structural biology. The program will consist of two phases. The first phase is during assembly of the ISS and will primarily utilize payloads that currently fly in the orbiter middeck but can be adapted for ISS. The second phase begins after assembly of the ISS is complete and BCG payloads will occupy part of the Biotechnology Facility aboard the ISS. Two types of BCG payloads will be flown. One will emphasize the production of crystals for structure determination back on Earth. These types of payloads will allow hundreds of crystallization conditions to be tested. The second type of payload will be designed to study the crystallization process with the primary aim of assisting the structural biology efforts. Access to these facilities will be through the NASA BCG Guest Investigators program, the NASA Research Announcement, and other opportunities currently being formulated. Details of the crystallization hardware, the application procedures, and the operational aspects of the program will be described.

Kundrot, Craig E.↗