Octahydriodo diborane (B2H8) and its protonated cations containing five-, six-, and seven-coordinate boron atoms

PubMed Central

Olah, George A.; Surya Prakash, G. K.; Rasul, Golam

2012-01-01

Structures of octahydriodo diborane (B2H8) 1 and its protonated 3, diprotonated 5, triprotonated 6, and tetraprotonated 7 ions were found to be calculationally viable minima at the MP2/cc-pVTZ level of theory. Each structure contains two-electron three-center (2e-3c) bonds. The protonation of 1 to form 3 was found to be strongly exothermic by 176.0 kcal/mol. Subsequent protonation of 3 to form 5 was also found to be exothermic by 28.4 kcal/mol. Further protonation of 5 to form 6 was, however, computed to be endothermic by 122.0 kcal/mol whereas protonation of 6 to form 7 was again highly endothermic by 238.8 kcal/mol. Deprotonation barriers of the ions were also computed. PMID:22511715

Mechanochemistry of the LiBH 4–AlCl 3 System: Structural Characterization of the Products by Solid-State NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kobayashi, T.; Dolotko, O.; Gupta, S.

The double-cation metal borohydride, Li 4Al 3(BH 4) 13, mechanochemically produced from a 13:3 mixture of lithium borohydride (LiBH 4) and aluminum chloride (AlCl 3), has a low hydrogen desorption temperature; however, the material’s decomposition is accompanied by a large emission of toxic diborane (B 2H 6). In this study, we found that a decrease of the LiBH 4:AlCl 3 ratio in the starting mixture yields increased amounts of partially chlorinated products that also dehydrogenate at low temperature, but release negligibly small amounts of diborane. Extensive characterization by solid-state NMR spectroscopy (SSNMR) and powder X-ray diffraction (XRD) found that themore » 11:3 ratio product maintains the Li 4Al 3(BH 4) 13-like structure, with additional Cl – anions substituting for [BH 4] – compared to the 13:3 mixture. Further decrease of relative LiBH 4 concentration in the starting mixture to 9:3 results in a different product composed of tetrahedral [Al(BH 4) 4] - and [Al(BH 4) 2Cl 2] - complexes, in which two hydrogen atoms of each borohydride group are bridged to aluminum sites. Additionally, SSNMR revealed the covalent character of the Al–H bonds, which is not observed in Li 4Al 3(BH 4) 13. In conclusion, these findings suggest that the Al–Cl bonding present in the chlorinated complexes prevents the formation of Al(BH 4) 3, which is a known intermediate leading to the formation of diborane during thermal dehydrogenation of the nearly chlorine-free Li 4Al 3(BH 4) 13.« less

Mechanochemistry of the LiBH 4–AlCl 3 System: Structural Characterization of the Products by Solid-State NMR

DOE PAGES

Kobayashi, T.; Dolotko, O.; Gupta, S.; ...

2017-12-19

The double-cation metal borohydride, Li 4Al 3(BH 4) 13, mechanochemically produced from a 13:3 mixture of lithium borohydride (LiBH 4) and aluminum chloride (AlCl 3), has a low hydrogen desorption temperature; however, the material’s decomposition is accompanied by a large emission of toxic diborane (B 2H 6). In this study, we found that a decrease of the LiBH 4:AlCl 3 ratio in the starting mixture yields increased amounts of partially chlorinated products that also dehydrogenate at low temperature, but release negligibly small amounts of diborane. Extensive characterization by solid-state NMR spectroscopy (SSNMR) and powder X-ray diffraction (XRD) found that themore » 11:3 ratio product maintains the Li 4Al 3(BH 4) 13-like structure, with additional Cl – anions substituting for [BH 4] – compared to the 13:3 mixture. Further decrease of relative LiBH 4 concentration in the starting mixture to 9:3 results in a different product composed of tetrahedral [Al(BH 4) 4] - and [Al(BH 4) 2Cl 2] - complexes, in which two hydrogen atoms of each borohydride group are bridged to aluminum sites. Additionally, SSNMR revealed the covalent character of the Al–H bonds, which is not observed in Li 4Al 3(BH 4) 13. In conclusion, these findings suggest that the Al–Cl bonding present in the chlorinated complexes prevents the formation of Al(BH 4) 3, which is a known intermediate leading to the formation of diborane during thermal dehydrogenation of the nearly chlorine-free Li 4Al 3(BH 4) 13.« less

Preparation of Zn(BH4)2 and diborane and hydrogen release properties of Zn(BH4)2+xMgH2 (x=1, 5, 10, and 15)

NASA Astrophysics Data System (ADS)

Kwak, Young Jun; Kwon, Sung Nam; Song, Myoung Youp

2015-09-01

Zn(BH4)2 was prepared by milling ZnCl2 and NaBH4 in a planetary ball mill under Ar atmosphere, and Zn(BH4)2+xMgH2 (x=1, 5, 10, and 15) samples were prepared. Diborane (B2H6) and hydrogen release characteristics of the Zn(BH4)2 and Zn(BH4)2+xMgH2 samples were studied. The samples synthesized by milling ZnCl2 and NaBH4 contained Zn(BH4)2 and NaCl, together with small amounts of ZnCl2 and NaBH4. We designated these samples as Zn(BH4)2(+NaCl). The weight loss up to 400 °C of the Zn(BH4)2(+NaCl) sample synthesized by milling 4 h was 11.2 wt%. FT-IR analysis showed that Zn(BH4)2 was formed in the Zn(BH4)2(+NaCl) samples. MgH2 was also milled in a planetary ball mill, and mixed with the Zn(BH4)2(+NaCl) synthesized by milling for 4 h in a mortar and pestle. The weight loss up to 400 °C of Zn(BH4)2(+NaCl)+MgH2 was 8.2 wt%, corresponding to the weight % of diborane and hydrogen released from the Zn(BH4)2(+NaCl)+MgH2 sample, with respect to the sample weight. DTA results of Zn(BH4)2(+NaCl)+xMgH2 showed that the decomposition peak of Zn(BH4)2 was at about 61 °C, and that of MgH2 was at about 370-389 °C.

Facile scission of isonitrile carbon–nitrogen triple bond using a diborane(4) reagent

PubMed Central

Asakawa, Hiroki; Lee, Ka-Ho; Lin, Zhenyang; Yamashita, Makoto

2014-01-01

Transition metal reagents and catalysts are generally effective to cleave all three bonds (one σ and two π) in a triple bond despite its high bonding energy. Recently, chemistry of single-bond cleavage by using main-group element compounds is rapidly being developed in the absence of transition metals. However, the cleavage of a triple bond using non-transition-metal compounds is less explored. Here we report that an unsymmetrical diborane(4) compound could react with carbon monoxide and tert-butyl isonitrile at room temperature. In the latter case, the carbon–nitrogen triple bond was completely cleaved in the absence of transition metal as confirmed by X-ray crystallographic analysis, 13C NMR spectroscopy with 13C labelling and DFT calculations. The DFT calculations also revealed the detailed reaction mechanism and indicated that the key for the carbon–nitrogen triple-bond cleavage could be attributed to the presence of nucleophilic nitrogen atom in one of the intermediates. PMID:24967910

Coulombic Models in Chemical Bonding.

ERIC Educational Resources Information Center

Sacks, Lawrence J.

1986-01-01

Describes a bonding theory which provides a framework for the description of a wide range of substances and provides quantitative information of remarkable accuracy with far less computational effort than that required of other approaches. Includes applications, such as calculation of bond energies of two binary hydrides (methane and diborane).…

A Military Guide to Terrorism in the Twenty-First Century. U.S. Army DCSINT Handbook No. 1 (Version 3.0)

DTIC Science & Technology

2005-08-15

or varnished brown Length: 102mm Width: 61mm Weight: 773g Filler: Amatol Characteristics Color: Black and unmarked Length: 131mm Width: 55mm...isocyanate Diborane Boron tribromide Nitrogen dioxide Ethylene oxide Carbon monoxide Phosphine Fluorine Carbonyl sulfide Phosphorus oxychloride

Deprotonation of a Seemingly Hydridic Diborane(6) To Build a B-B Bond.

PubMed

Kaese, Thomas; Budy, Hendrik; Bolte, Michael; Lerner, Hans-Wolfram; Wagner, Matthias

2017-06-19

Deprotonation of the doubly arylene-bridged diborane(6) derivative 1H 2 with (Me 3 Si) 3 CLi or (Me 3 Si) 2 NK gives the B-B σ-bonded species M[1H] in essentially quantitative yields (THF, room temperature; M=Li, K, arylene=4,4'-di-tert-butyl-2,2'-biphenylylene). With nBuLi as the base, the yield of Li[1H] drops to 20 % and the 1,1-bis(9-borafluorenyl)butane Li[2H] is formed as a side product (30 %). In addition to the 1,1-butanediyl fragment, the two boron atoms of Li[2H] are linked by a μ-H bridge. In the closely related molecule Li[3H], the corresponding μ-H atom can be abstracted with (Me 3 Si) 3 CLi to afford the B-B-bonded conjugated base Li 2 [3] (THF, 150 °C; 15 %). Li[1H] and Li[2H] were characterized by NMR spectroscopy and X-ray crystallography. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical Combustion Performance of Several High-Energy Fuels for Ramjet Engines

NASA Technical Reports Server (NTRS)

Tower, Leonard K; Breitwieser, Roland; Gammon, Benson E

1958-01-01

An analytical evaluation of the air and fuel specific-impulse characteristics of magnesium, magnesium octene-1 slurries, aluminum, aluminum octene-1 slurries, boron, boron octene-1 slurries, carbon, hydrogen, alpha-methylnaphthalene, diborane, pentaborane, and octene-1 is presented. While chemical equilibrium was assumed in the combustion process, the expansion was assumed to occur at fixed composition.

Formation of amorphous metal alloys by chemical vapor deposition

DOEpatents

Mullendore, Arthur W.

1990-01-01

Amorphous alloys are deposited by a process of thermal dissociation of mixtures or organometallic compounds and metalloid hydrides, e.g., transition metal carbonyl such as nickel carbonyl, and diborane. Various sizes and shapes of deposits can be achieved, including near-net-shape free standing articles, multilayer deposits, and the like. Manipulation or absence of a magnetic field affects the nature and the structure of the deposit.

Formation of amorphous metal alloys by chemical vapor deposition

DOEpatents

Mullendore, A.W.

1988-03-18

Amorphous alloys are deposited by a process of thermal dissociation of mixtures of organometallic compounds and metalloid hydrides,e.g., transition metal carbonyl, such as nickel carbonyl and diborane. Various sizes and shapes of deposits can be achieved, including near-net-shape free standing articles, multilayer deposits, and the like. Manipulation or absence of a magnetic field affects the nature and the structure of the deposit. 1 fig.

Reclassification of Materials Listed as Transportation Health Hazards

DTIC Science & Technology

1972-08-01

f. Hyg., 7:233, 1887. 152.3 Prentiss, A. M., Chemicals in War, McGrall-Hill, N. Y., 1937. A-183 TOXICITY DATA SHEET COMPOUND: CHLORINE TRIFLUORIDE ...l%3 Chlorine Trifluoride to # 161 Diborane Highly Toxic Extrenmely Toxic 169 Fluorine 171 Hlydrazine. anhydrous Toxic- Highly Toxic. 1I 172...were run on mice and rats exposed to chlorine , anhy lrous ammonia and hydrogen sulfide. Results have been included and reflected in the

Calculating Toxic Corridors. Revision

DTIC Science & Technology

1989-04-01

16 Table 9 Chlorine Pentafluoride 1CL ........... ................... .. 17 Table 10 Chlorine Trifluoride TCL...60-min EEL: 3.0 ppm 31 Chlorine Pentafluoride 130.445 0.3 4.64 1.5 1(T) 2.03 Mone - (T) - Tentative Chlorine Trifluoride 92.448 0.63 3.88 3.01 1.70...CIF 5 770.4 Chlorine Trifluoride 26.6 1,B33.410 54.141 80 92.448 CIF.3 247.2 Diborane 16.859 B2 H Ethylene- Oxide 27.0 f 1,860.98 54.96 80 44.054 C

Nanotechnology and the Environment: Report of a National Nanotechnology Initiative Workshop Held in Arlington, Virginia on 8-9 May 2003

DTIC Science & Technology

2007-01-01

cover: Image shows an artist’s rendition of the core-shell structure of metal- oxide -coated palladium- doped zero-valent iron nanoparticles for catalytic...demonstrated the creation of functionalized gold nanoparticles (see figure c) without the need for many of the toxic solvents (e.g., diborane...Size-selected nanoparticle chemistry: Kinetics of soot oxidation , J. Phys. Chem. A 106, 96–103 (2002). 6. H. J. Tobias, D. E. Beving, P. J. Ziemann, H

Study of advanced techniques for determining the long-term performance of components

NASA Technical Reports Server (NTRS)

1972-01-01

A study was conducted of techniques having the capability of determining the performance and reliability of components for spacecraft liquid propulsion applications for long term missions. The study utilized two major approaches; improvement in the existing technology, and the evolution of new technology. The criteria established and methods evolved are applicable to valve components. Primary emphasis was placed on the propellants oxygen difluoride and diborane combination. The investigation included analysis, fabrication, and tests of experimental equipment to provide data and performance criteria.

Boundary cooled rocket engines for space storable propellants

NASA Technical Reports Server (NTRS)

Kesselring, R. C.; Mcfarland, B. L.; Knight, R. M.; Gurnitz, R. N.

1972-01-01

An evaluation of an existing analytical heat transfer model was made to develop the technology of boundary film/conduction cooled rocket thrust chambers to the space storable propellant combination oxygen difluoride/diborane. Critical design parameters were identified and their importance determined. Test reduction methods were developed to enable data obtained from short duration hot firings with a thin walled (calorimeter) chamber to be used quantitatively evaluate the heat absorbing capability of the vapor film. The modification of the existing like-doublet injector was based on the results obtained from the calorimeter firings.

Low-Temperature Synthesis of Superconducting Nanocrystalline MgB 2

DOE PAGES

Lu, Jun; Xiao, Zhili; Lin, Qiyin; ...

2010-01-01

Magnesium diboride (MgB 2 ) is considered a promising material for practical application in superconducting devices, with a transition temperature near 40 K. In the present paper, nanocrystalline MgB 2 with an average particle size of approximately 70 nm is synthesized by reacting LiBH 4 with MgH 2 at temperatures as low as 450 ° C. This synthesis approach successfully bypasses the usage of either elemental boron or toxic diborane gas. The superconductivity of the nanostructures is confirmed by magnetization measurements, showing a superconducting critical temperature of 38.7 K.

Design of a Facility to Implement a Low Cost Process for Production of NHC

DTIC Science & Technology

1979-05-15

CO4PANY V. i In brief, crude NHC is produced by sequential batch- wise solution processing, initially converting BIO to the sulfide ligand with subsequent...L 1.03 50 214 R-3 (Dibutyl Sulfide ) L 0.84 -112 360 R-4 (Pyridine) L 0.98 - 44 240 1-Octyne L 0.75 -110 260 Acetone L 0.79 -138 134 Methanol L 0.79...R3 -- 25-Octyne- 300 C5 30 TOL 4 NHC -AREA 40 LEGEND: 82 - Diborane R2 - Dioxane B10 - Decaborane R3 - Butyl Sulfide C5 - Pentane MEOH - Methanol C6

Analytical evaluation of effect of equivalence ratio inlet-air temperature and combustion pressure on performance of several possible ram-jet fuels

NASA Technical Reports Server (NTRS)

Tower, Leonard K; Gammon, Benson E

1953-01-01

The results of an analytical investigation of the theoretical air specific impulse performance and adiabatic combustion temperatures of several possible ram-jet fuels over a range of equivalence ratios, inlet-air temperatures, and combustion pressures, is presented herein. The fuels include octane-1, 50-percent-magnesium slurry, boron, pentaborane, diborane, hydrogen, carbon, and aluminum. Thermal effects from high combustion temperatures were found to effect considerably the combustion performance of all the fuels. An increase in combustion pressure was beneficial to air specific impulse at high combustion temperatures. The use of these theoretical data in engine operation and in the evaluation of experimental data is described.

Highly conducting and preferred <220> oriented boron doped nc–Si films for window layers in nc–Si solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mondal, Praloy; Das, Debajyoti, E-mail: erdd@iacs.res.in

2016-05-23

Growth and optimization of the boron dopednanocrystalline silicon (nc-Si) films have been studied by varyingthe gaspressure applied to the hydrogendiluted silane plasma in RF (13.56 MHz) plasma-enhanced chemical vapor deposition (PECVD) system, using diborane (B{sub 2}H{sub 6}) as the dopant gas. High magnitudeof electrical conductivity (~10{sup 2} S cm{sup −1}) and<220>orientedcrystallographic lattice planes have been obtained with high crystalline volume fraction (~86 %) at an optimum pressure of 2.5 Torr. XRD and Raman studies reveal good crystallinity with preferred orientation, suitable for applications in stacked layer devices, particularly in nc–Si solar cells.

Thermally grown oxide and diffusions for automatic processing of integrated circuits

NASA Technical Reports Server (NTRS)

Kennedy, B. W.

1979-01-01

A totally automated facility for semiconductor oxidation and diffusion was developed using a state-of-the-art diffusion furnace and high temperature grown oxides. Major innovations include: (1) a process controller specifically for semiconductor processing; (2) an automatic loading system to accept wafers from an air track, insert them into a quartz carrier and then place the carrier on a paddle for insertion into the furnace; (3) automatic unloading of the wafers back onto the air track, and (4) boron diffusion using diborane with plus or minus 5 percent uniformity. Processes demonstrated include Wet and dry oxidation for general use and for gate oxide, boron diffusion, phosphorous diffusion, and sintering.

Nuclear diagnostic for fast alpha particles

DOEpatents

Grisham, Larry R.; Post Jr., Douglass E.; Dawson, John M.

1986-06-03

Measurement of the velocity distribution of confined energetic alpha particles resulting from deuterium-tritium fusion reactions in a magnetically contained plasma is provided. The fusion plasma is seeded with energetic boron neutrals for producing, by means of the reaction .sup.10 B (.alpha.,n) .sup.13 N reaction, radioactive nitrogen nuclei which are then collected by a probe. The radioactivity of the probe is then measured by conventional techniques in determining the energy distribution of the alpha particles in the plasma. In a preferred embodiment, diborane gas (B.sub.2 H.sub.6) is the source of the boron neutrals to produce .sup.13 N which decays almost exclusively by positron emission with a convenient half-life of 10 minutes.

Nuclear diagnostic for fast alpha particles

DOEpatents

Grisham, Larry R.; Post, Jr., Douglass E.; Dawson, John M.

1986-01-01

Measurement of the velocity distribution of confined energetic alpha particles resulting from deuterium-tritium fusion reactions in a magnetically contained plasma is provided. The fusion plasma is seeded with energetic boron neutrals for producing, by means of the reaction .sup.10 B (.alpha.,n) .sup.13 N reaction, radioactive nitrogen nuclei which are then collected by a probe. The radioactivity of the probe is then measured by conventional techniques in determining the energy distribution of the alpha particles in the plasma. In a preferred embodiment, diborane gas (B.sub.2 H.sub.6) is the source of the boron neutrals to produce .sup.13 N which decays almost exclusively by positron emission with a convenient half-life of 10 minutes.

Electronic Transitions of Palladium Monoboride and Platinum Monoboride

NASA Astrophysics Data System (ADS)

Ng, Y. W.; Pang, H. F.; Wong, Y. S.; Qian, Yue; Cheung, A. S.-C.

2012-06-01

Electronic transition spectrum of palladium monoboride (PdB) and platinum (PtB) monoboride have been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. The metal monoborides were produced by reacting laser ablated metal atoms and diborane ((B_2H_6) seeded in argon. Five and six vibrational bands were observed respectively for the PdB and PtB molecules. Preliminary analysis of the rotationally resolved structure showed that both molecules have X2 Σ+ ground state. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. Molecular and electronic structures of PdB and PtB are discussed using a molecular orbital energy level diagram. Financial support from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. HKU 701008P) is gratefully acknowledged.

Lateral gas phase diffusion length of boron atoms over Si/B surfaces during CVD of pure boron layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohammadi, V., E-mail: V.Mohammadi@tudelft.nl; Nihtianov, S.

The lateral gas phase diffusion length of boron atoms, L{sub B}, along silicon and boron surfaces during chemical vapor deposition (CVD) using diborane (B{sub 2}H{sub 6}) is reported. The value of L{sub B} is critical for reliable and uniform boron layer coverage. The presented information was obtained experimentally and confirmed analytically in the boron deposition temperature range from 700 °C down to 400 °C. For this temperature range the local loading effect of the boron deposition is investigated on the micro scale. A L{sub B} = 2.2 mm was determined for boron deposition at 700 °C, while a L{sub B}more » of less than 1 mm was observed at temperatures lower than 500 °C.« less

Improved synthesis of 3 alpha, 7 alpha, 12 alpha, 24 = xi-tetrahydroxy-5 beta-cholestan-26-oic acid.

PubMed

Batta, A K; Tint, G S; Dayal, B; Shefer, S; Salen, G

1982-06-01

This paper describes three simple and short methods for the conversion of cholic acid into cholylaldehyde with protected hydroxyl groups. The first method involves lithium aluminum hydride reduction of the tetrahydropyranyl ether of methyl cholate and oxidation of the resulting primary alcohol with pyridinium chlorochromate. The second method employs diborane for the reduction of the -COOH group to the -CH2OH group, while the third method involves the reduction of 3 alpha, 7 alpha, 12 alpha-triformyloxy-5 beta-cholan-24-oic acid (as the acid chloride) directly into 3 alpha, 7 alpha, 12 alpha-triformyloxy-5 beta-cholan-24-al with TMA-ferride (tetramethylammonium hydridoirontetracarbonyl). The aldehyde obtained by any of the above methods underwent smooth Reformatsky reaction with ethyl alpha-bromopropionate to yield 3 alpha, 7 alpha, 12 alpha, 24 xi-tetrahydroxy-5 beta-cholestan-26-oic acid.

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

Effect of nitrogen on the growth of boron doped single crystal diamond

DOE PAGES

Karna, Sunil; Vohra, Yogesh

2013-11-18

Boron-doped single crystal diamond films were grown homoepitaxially on synthetic (100) Type Ib diamond substrates using microwave plasma assisted chemical vapor deposition. A modification in surface morphology of the film with increasing boron concentration in the plasma has been observed using atomic force microscopy. Use of nitrogen during boron doping has been found to improve the surface morphology and the growth rate of films but it lowers the electrical conductivity of the film. The Raman spectra indicated a zone center optical phonon mode along with a few additional bands at the lower wavenumber regions. The change in the peak profilemore » of the zone center optical phonon mode and its downshift were observed with the increasing boron content in the film. Furthermore, sharpening and upshift of Raman line was observed in the film that was grown in presence of nitrogen along with diborane in process gas.« less

Vapor phase diamond growth technology

NASA Technical Reports Server (NTRS)

Angus, J. C.

1981-01-01

Ion beam deposition chambers used for carbon film generation were designed and constructed. Features of the developed equipment include: (1) carbon ion energies down to approx. 50 eV; (2) in suit surface monitoring with HEED; (3) provision for flooding the surface with ultraviolet radiation; (4) infrared laser heating of substrate; (5) residual gas monitoring; (6) provision for several source gases, including diborane for doping studies; and (7) growth from either hydrocarbon source gases or from carbon/argon arc sources. Various analytical techniques for characterization of from carbon/argon arc sources. Various analytical techniques for characterization of the ion deposited carbon films used to establish the nature of the chemical bonding and crystallographic structure of the films are discussed. These include: H2204/HN03 etch; resistance measurements; hardness tests; Fourier transform infrared spectroscopy; scanning auger microscopy; electron spectroscopy for chemical analysis; electron diffraction and energy dispersive X-ray analysis; electron energy loss spectroscopy; density measurements; secondary ion mass spectroscopy; high energy electron diffraction; and electron spin resonance. Results of the tests are summarized.

Structural and electrical properties of trimethylboron-doped silicon nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lew, K.-K.; Pan Ling; Bogart, Timothy E.

2004-10-11

Trimethylboron (TMB) was investigated as a p-type dopant source for the vapor-liquid-solid growth of boron-doped silicon nanowires (SiNWs). The boron concentration in the nanowires was measured using secondary ion mass spectrometry and results were compared for boron-doping using TMB and diborane (B{sub 2}H{sub 6}) sources. Boron concentrations ranging from 1x10{sup 18} to 4x10{sup 19} cm{sup -3} were obtained by varying the inlet dopant/SiH{sub 4} gas ratio. TEM characterization revealed that the B{sub 2}H{sub 6}-doped SiNWs consisted of a crystalline core with a thick amorphous Si coating, while the TMB-doped SiNWs were predominantly single crystal even at high boron concentrations. Themore » difference in structural properties was attributed to the higher thermal stability and reduced reactivity of TMB compared to B{sub 2}H{sub 6}. Four-point resistivity and gate-dependent conductance measurements were used to confirm p-type conductivity in the TMB-doped nanowires and to investigate the effect of dopant concentration on nanowire resistivity.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alnajjar, Mikhail S.; Quigley, David; Kuntamukkula, Murty

Due to the inherent nature of pyrophoric substances to ignite spontaneously upon exposure to air, special precautions must be taken to ensure their safe handling and use. Pyrophoric gases (such as diborane, dichloroborane, phosphine, etc.) are typically the easiest class of pyrophoric substances to handle since the gas can be plumbed directly to the application and used remotely. Pyrophoric solids and liquids, however, require the user to physically manipulate them when transferring them from one container to another. Failure to follow proper safety precautions could result in serious injury or unintended consequences to laboratory personnel.12 Because of this danger, pyrophoricsmore » should be handled only by experienced personnel. Users with limited experience must be trained on how to handle pyrophoric reagents and consult with a knowledgeable staff member prior to performing the experimental task. The purpose of this article is three fold: 1) to provide guidelines and general safety precautions to avoid accidents, 2) describe proper techniques on how to successfully handle, store, and dispose of pyrophoric liquids and solids, and 3) illustrate best practices for working with this class of reactants in a laboratory environment.« less

X Ray Mask Of Gold-Carbon Mixture Absorber On BCN Compound Substrate Fabricated By Plasma Processes

NASA Astrophysics Data System (ADS)

Aiyer, Chandrasekhar R.; Itoh, Satoshi; Yamada, Hitomi; Morita, Shinzo; Hattori, Shuzo

1988-06-01

X-ray mask fabrication based on BCN compound membrane and gold containing polymeric carbon ( Au-C ) absorber by totally dry processes is proposed. The Au-C films were depo-sited by plasma polymerization of propylene or styrene monomers and co-evaporation of gold. These films have 2 to 5 times higher etching rate than that of pure gold for 09 RIE, depending on the Au content. The stress in the films could be reduced to 1.9 E 7 N/m2 by annealing. The BCN films were deposited on silicon wafers by rf (13.56 MHz) plasma CVD with diborane, methane and nitrogen as source gases at typical deposition rate of 30 nm/min. The optical (633nm) and X ray (Pd L~) transparencies were nearly 80% for film thickness of 6 um. Patterning of Au-C was achieved by using tungsten as intermediate layer and PMMA electron beam resist. CF4 RIE was used to etch the tungsten layer which in turn acted as mask for the gold carbide 02 RIE. The process parameters and the characteristics of the Au-C and BCN films are presented.

Atomic-level spatial distributions of dopants on silicon surfaces: toward a microscopic understanding of surface chemical reactivity

NASA Astrophysics Data System (ADS)

Hamers, Robert J.; Wang, Yajun; Shan, Jun

1996-11-01

We have investigated the interaction of phosphine (PH 3) and diborane (B 2H 6) with the Si(001) surface using scanning tunneling microscopy, infrared spectroscopy, and ab initio molecular orbital calculations. Experiment and theory show that the formation of PSi heterodimers is energetically favorable compared with formation of PP dimers. The stability of the heterodimers arises from a large strain energy associated with formation of PP dimers. At moderate P coverages, the formation of PSi heterodimers leaves the surface with few locations where there are two adjacent reactive sites. This in turn modifies the chemical reactivity toward species such as PH 3, which require only one site to adsorb but require two adjacent sites to dissociate. Boron on Si(001) strongly segregates into localized regions of high boron concentration, separated by large regions of clean Si. This leads to a spatially-modulated chemical reactivity which during subsequent growth by chemical vapor deposition (CVD) leads to formation of a rough surface. The implications of the atomic-level spatial distribution of dopants on the rates and mechanisms of CVD growth processes are discussed.

Solid Aluminum Borohydrides for Prospective Hydrogen Storage.

PubMed

Dovgaliuk, Iurii; Safin, Damir A; Tumanov, Nikolay A; Morelle, Fabrice; Moulai, Adel; Černý, Radovan; Łodziana, Zbigniew; Devillers, Michel; Filinchuk, Yaroslav

2017-12-08

Metal borohydrides are intensively researched as high-capacity hydrogen storage materials. Aluminum is a cheap, light, and abundant element and Al 3+ can serve as a template for reversible dehydrogenation. However, Al(BH 4 ) 3 , containing 16.9 wt % of hydrogen, has a low boiling point, is explosive on air and has poor storage stability. A new family of mixed-cation borohydrides M[Al(BH 4 ) 4 ], which are all solid under ambient conditions, show diverse thermal decomposition behaviors: Al(BH 4 ) 3 is released for M=Li + or Na + , whereas heavier derivatives evolve hydrogen and diborane. NH 4 [Al(BH 4 ) 4 ], containing both protic and hydridic hydrogen, has the lowest decomposition temperature of 35 °C and yields Al(BH 4 ) 3 ⋅NHBH and hydrogen. The decomposition temperatures, correlated with the cations' ionic potential, show that M[Al(BH 4 ) 4 ] species are in the most practical stability window. This family of solids, with convenient and versatile properties, puts aluminum borohydride chemistry in the mainstream of hydrogen storage research, for example, for the development of reactive hydride composites with increased hydrogen content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Research on High-Bandgap Materials and Amorphous Silicon-Based Solar Cells, Final Technical Report, 15 May 1994-15 January 1998

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schiff, E. A.; Gu, Q.; Jiang, L.

1998-12-28

This report describes work performed by Syracuse University under this subcontract. Researchers developed a technique based on electroabsorption measurements for obtaining quantitative estimates of the built-in potential Vbi in a-Si:H-based heterostructure solar cells incorporating microcrystalline or a-SiC:H p layers. Using this new electroabsorption technique, researchers confirmed previous estimates of Vbi {yields} 1.0 V in a-Si:H solar cells with ''conventional'' intrinsic layers and either microcrystalline or a-SiC:H p layers. Researchers also explored the recent claim that light-soaking of a-Si:H substantially changes the polarized electroabsorption associated with interband optical transitions (and hence, not defect transitions). Researchers confirmed measurements of improved (5') holemore » drift mobilities in some specially prepared a-Si:H samples. Disturbingly, solar cells made with such materials did not show improved efficiencies. Researchers significantly clarified the relationship of ambipolar diffusion-length measurements to hole drift mobilities in a-Si:H, and have shown that the photocapacitance measurements can be interpreted in terms of hole drift mobilities in amorphous silicon. They also completed a survey of thin BP:H and BPC:H films prepared by plasma deposition using phosphine, diborane, trimethylboron, and hydrogen as precursor gases.« less

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

NASA Astrophysics Data System (ADS)

Wu, Hui; Zhou, Xiuquan; Rodriguez, Efrain E.; Zhou, Wei; Udovic, Terrence J.; Yildirim, Taner; Rush, John J.

2016-10-01

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH4·nCN3H5, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH4)2·6CN3H5 is composed of large complex Mg[CN3H5]62+ cations and surrounding BH4- ions, while Ca(BH4)2·2CN3H5 possesses layers of corner-sharing Ca[BH4]4(CN3H5)2 octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be released from MBH4·nCN3H5 (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH4)2·nCN3H5 can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release.

Improved method for mutagenicity testing of gaseous compounds by using a gas sampling bag.

PubMed

Araki, A; Noguchi, T; Kato, F; Matsushima, T

1994-05-01

A simple and safety gas exposure method was developed using a gas sampling bag as an exposure vessel and a preparation vessel of diluted gas. The gas exposure conditions such as amount of S9 in the plate, volume of gas for the plate, amount of top agar, exposure period and exposure temperature were examined by mutagenicity testing of 1,3-butadiene using the gas sampling bag. Mutagenicity tests of 14 compounds and 1,3-butadiene on S. typhimurium TA98, TA100, TA1535 and TA1537, and E. coli WP2 uvrA were also examined by the developed gas exposure method. 1,3-Butadiene, propyne (methyl acetylene), monochlorodifluoromethane, ethylchloride, diborane and silane were mutagenic. 1-Butene, 2-butene, 2-methylpropene, methyl vinyl ether, trichlorofluoromethane, dichlorodifluoromethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-difluoroethane and phosphine were not mutagenic on S. typhimurium TA98, TA100, TA1535 and TA1537, and E. coli WP2 uvrA with or without metabolic activation. These results were compatible with a previous report, and this developed method has the advantage that it can be tested easily and safely for combustible and self-combustible substances such as 1,3-butadiene and silane.

Sticking and recombination of the SiH 3 radical on hydrogenated amorphous silicon: The catalytic effect of diborane

NASA Astrophysics Data System (ADS)

Perrin, Jérôme; Takeda, Yoshihiko; Hirano, Naoto; Takeuchi, Yoshiaki; Matsuda, Akihisa

1989-03-01

The deposition rate of hydrogenated amorphous silicon films in SiH 4 glow-discharge is drastically enhanced upon addition of B 2H 6 when the gas-phase concentration exceeds 10 -4. This cannot be attributed to gas-phase reactions and must be interpreted as an increase of the sticking probability of the dominant SiH 3 radical. However, the total surface loss probability ( β) of SiH 3 which includes both sticking ( s) and recombination ( γ) increases only above 10 -2 B 2H 6 concentration, which reveals that between 10 -4 and 10 -2 the ratio {s}/{β} increases. A precursor-state model is proposed in which SiH 3 first physisorbs on the H-covered surface and migrates until it recombines, or chemisorbs on a free dangling bond site. At a typical deposition temperature of 200° C, the only mechanism of creation of dangling bonds in the absence of B 2H 6 is precisely the recombination of SiH 3 as SiH 4 by H abstraction, which limits the sticking probability to a fraction of β. This restriction is overcome with the help of hydroboron radicals, presumably BH 3, which catalyze H 2 desorption.

Final Technical Report: Effects of Impurities on Fuel Cell Performance and Durability

DOE Office of Scientific and Technical Information (OSTI.GOV)

James G. Goodwin, Jr.; Hector Colon-Mercado; Kitiya Hongsirikarn

2011-11-11

The main objectives of this project were to investigate the effect of a series of potential impurities on fuel cell operation and on the particular components of the fuel cell MEA, to propose (where possible) mechanism(s) by which these impurities affected fuel cell performance, and to suggest strategies for minimizing these impurity effects. The negative effect on Pt/C was to decrease hydrogen surface coverage and hydrogen activation at fuel cell conditions. The negative effect on Nafion components was to decrease proton conductivity, primarily by replacing/reacting with the protons on the Bronsted acid sites of the Nafion. Even though already wellmore » known as fuel cell poisons, the effects of CO and NH3 were studied in great detail early on in the project in order to develop methodology for evaluating poisoning effects in general, to help establish reproducibility of results among a number of laboratories in the U.S. investigating impurity effects, and to help establish lower limit standards for impurities during hydrogen production for fuel cell utilization. New methodologies developed included (1) a means to measure hydrogen surface concentration on the Pt catalyst (HDSAP) before and after exposure to impurities, (2) a way to predict conductivity of a Nafion membranes exposed to impurities using a characteristic acid catalyzed reaction (methanol esterification of acetic acid), and, more importantly, (3) application of the latter technique to predict conductivity on Nafion in the catalyst layer of the MEA. H2-D2 exchange was found to be suitable for predicting hydrogen activation of Pt catalysts. The Nafion (ca. 30 wt%) on the Pt/C catalyst resides primarily on the external surface of the C support where it blocks significant numbers of micropores, but only partially blocks the pore openings of the meso- and macro-pores wherein lie the small Pt particles (crystallites). For this reason, even with 30 wt% Nafion on the Pt/C, few Pt sites are blocked and, hence, are accessible for hydrogen activation. Of the impurities studied, CO, NH3, perchloroethylene (also known as tetrachloroethylene), tetrahydrofuran, diborane, and metal cations had significant negative effects on the components in a fuel cell. While CO has no effect on the Nafion, it significantly poisons the Pt catalyst by adsorbing and blocking hydrogen activation. The effect can be reversed with time once the flow of CO is stopped. NH3 has no effect on the Pt catalyst at fuel cell conditions; it poisons the proton sites on Nafion (by forming NH4+ cations), decreasing drastically the proton conductivity of Nafion. This poisoning can slowly be reversed once the flow of NH3 is stopped. Perchloroethylene has a major effect on fuel cell performance. Since it has little/no effect on Nafion conductivity, its poisoning effect is on the Pt catalyst. However, this effect takes place primarily for the Pt catalyst at the cathode, since the presence of oxygen is very important for this poisoning effect. Tetrahydrofuran was shown not to impact Nafion conductivity; however, it does affect fuel cell performance. Therefore, its primary effect is on the Pt catalyst. The effect of THF on fuel cell performance is reversible. Diborane also can significant affect fuel cell performance. This effect is reversible once diborane is removed from the inlet streams. H2O2 is not an impurity usually present in the hydrogen or oxygen streams to a fuel cell. However, it is generated during fuel cell operation. The presence of Fe cations in the Nafion due to system corrosion and/or arising from MEA production act to catalyze the severe degradation of the Nafion by H2O2. Finally, the presence of metal cation impurities (Na+, Ca 2+, Fe3+) in Nafion from MEA preparation or from corrosion significantly impacts its proton conductivity due to replacement of proton sites. This effect is not reversible. Hydrocarbons, such as ethylene, might be expected to affect Pt or Nafion but do not at a typical fuel cell temperature of 80oC. In the presence of large quantities of hydrogen on the anode side, ethylene is converted to ethane which is very nonreactive. More surprisingly, even more reactive hydrocarbons such as formic acid and acetaldehyde do not appear to react enough with the strong Bronsted acid sites on Nafion at such low temperatures to affect Nafion conductivity properties. These results clearly identify a number of impurities which can have a detrimental impact on fuel cell performance, although some are reversible. Obviously, fuel cells exposed to impurities/poisons which are reversible can recover their original performance capabilities once the impurity flow is stopped. Impurities with irreversible effects should be either minimized in the feed streams, if possible, or new catalytic materials or ion conductors will need to be used to minimize their impact.« less

Plasma boriding of a cobalt-chromium alloy as an interlayer for nanostructured diamond growth

NASA Astrophysics Data System (ADS)

Johnston, Jamin M.; Jubinsky, Matthew; Catledge, Shane A.

2015-02-01

Chemical vapor deposited (CVD) diamond coatings can potentially improve the wear resistance of cobalt-chromium medical implant surfaces, but the high cobalt content in these alloys acts as a catalyst to form graphitic carbon. Boriding by high temperature liquid baths and powder packing has been shown to improve CVD diamond compatibility with cobalt alloys. We use the microwave plasma-enhanced (PE) CVD process to deposit interlayers composed primarily of the borides of cobalt and chromium. The use of diborane (B2H6) in the plasma feedgas allows for the formation of a robust boride interlayer for suppressing graphitic carbon during subsequent CVD of nano-structured diamond (NSD). This metal-boride interlayer is shown to be an effective diffusion barrier against elemental cobalt for improving nucleation and adhesion of NSD coatings on a CoCrMo alloy. Migration of elemental cobalt to the surface of the interlayer is significantly reduced and undetectable on the surface of the subsequently-grown NSD coating. The effects of PECVD boriding are compared for a range of substrate temperatures and deposition times and are evaluated using glancing-angle X-ray diffraction (XRD), cross-sectional scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and micro-Raman spectroscopy. Boriding of CoCrMo results in adhered nanostructured diamond coatings with low surface roughness.

Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.

2012-04-19

Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 releasemore » properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.« less

Ultrathin Single‐Crystalline Boron Nanosheets for Enhanced Electro‐Optical Performances

PubMed Central

Xu, Junqi; Chang, Yangyang; Gan, Lin; Ma, Ying

2015-01-01

Large‐scale single‐crystalline ultrathin boron nanosheets (UBNSs, ≈10 nm) are fabricated through an effective vapor–solid process via thermal decomposition of diborane. The UBNSs have obvious advantages over thicker boron nanomaterials in many aspects. Specifically, the UBNSs demonstrate excellent field emission performances with a low turn‐on field, E to, of 3.60 V μm−1 and a good stability. Further, the dependence of (turn‐on field) E to/(threshold field) E thr and effective work function, Φ e, on temperature is investigated and the possible mechanism of temperature‐dependent field emission phenomenon has been discussed. Moreover, electronic transport in a single UBNS reveals it to be an intrinsic p‐type semiconductor behavior with carrier mobility about 1.26 × 10−1 cm2 V−1 s−1, which is the best data in reported works. Interestingly, a multiconductive mechanism coexisting phenomenon has been explored based on the study of temperature‐dependent conductivity behavior of the UBNSs. Besides, the photodetector device fabricated from single‐crystalline UBNS demonstrates good sensitivity, reliable stability, and fast response, obviously superior to other reported boron nanomaterials. Such superior electronic‐optical performances are originated from the high quality of single crystal and large specific surface area of the UBNSs, suggesting the potential applications of the UBNSs in field‐emitters, interconnects, integrated circuits, and optoelectronic devices. PMID:27980947

High-Energy Propellant Rocket Firing at the Rocket Lab

NASA Image and Video Library

1955-01-21

A rocket using high-energy propellant is fired from the Rocket Laboratory at the National Advisory Committee for Aeronautics (NACA) Lewis Flight Propulsion Laboratory. The Rocket Lab was a collection of ten one-story cinderblock test cells located behind earthen barriers at the western edge of the campus. The rocket engines tested there were comparatively small, but the Lewis researchers were able to study different configurations, combustion performance, and injectors and nozzle design. The rockets were generally mounted horizontally and fired, as seen in this photograph of Test Cell No. 22. A group of fuels researchers at Lewis refocused their efforts after World War II in order to explore high energy propellants, combustion, and cooling. Research in these three areas began in 1945 and continued through the 1960s. The group of rocket researches was not elevated to a division branch until 1952. The early NACA Lewis work led to the development of liquid hydrogen as a viable propellant in the late 1950s. Following the 1949 reorganization of the research divisions, the rocket group began working with high-energy propellants such as diborane, pentaborane, and hydrogen. The lightweight fuels offered high levels of energy but were difficult to handle and required large tanks. In late 1954, Lewis researchers studied the combustion characteristics of gaseous hydrogen in a turbojet combustor. Despite poor mixing of the fuel and air, it was found that the hydrogen yielded more than a 90-percent efficiency. Liquid hydrogen became the focus of Lewis researchers for the next 15 years.

Boron Doped Nanocrystalline Film with Improved Work Function as a Buffer Layer in Thin Film Silicon Solar Cells.

PubMed

Park, Jinjoo; Shin, Chonghoon; Park, Hyeongsik; Jung, Junhee; Lee, Youn-Jung; Bong, Sungjae; Dao, Vinh Ai; Balaji, Nagarajan; Yi, Junsin

2015-03-01

We investigated thin film silicon solar cells with boron doped hydrogenated nanocrystalline silicon/ hydrogenated amorphous silicon oxide [p-type nc-Si:H/a-SiOx:H] layer. First, we researched the bandgap engineering of diborane (B2H6) doped wide bandgap hydrogenated nanocryslline silicon (p-type nc-Si:H) films, which have excellent electrical properties of high dark conductivity, and low activation energy. The films prepared with lower doping ratio and higher hydrogen dilution ratio had higher optical gap (Eg), with higher dark conductivity (σ(d)), and lower activation energy (Ea). We controlled Eg from 2.10 eV to 1.75 eV, with σ(d) from 1.1 S/cm to 7.59 x 10(-3) S/cm, and Ea from 0.040 eV to 0.128 eV. Next, we focused on the fabrication of thin film silicon solar cells. By inserting p-type nc-Si:H film into the thin film silicon solar cells, we achieved a remarkable increase in the built-in potential from 0.803 eV to 0.901 eV. By forming p-type nc-Si:H film between SnO2:F/ZnO:Al (30 nm) and p-type a-SiOx:H layer, the solar cell properties of open circuit voltage (Voc), short circuit current density (Jsc), and efficiency (η) were improved by 3.7%, 9.2%, and 9.8%, respectively.

Diverse roles of hydrogen in rhenium carbonyl chemistry: hydrides, dihydrogen complexes, and a formyl derivative.

PubMed

Li, Nan; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

2010-11-04

Rhenium carbonyl hydride chemistry dates back to the 1959 synthesis of HRe(CO)₅ by Hieber and Braun. The binuclear H₂Re₂(CO)₈ was subsequently synthesized as a stable compound with a central Re₂(μ-H)₂ unit analogous to the B₂(μ-H)₂ unit in diborane. The complete series of HRe(CO)(n) (n = 5, 4, 3) and H₂Re₂(CO)(n) (n = 9, 8, 7, 6) derivatives have now been investigated by density functional theory. In contrast to the corresponding manganese derivatives, all of the triplet rhenium structures are found to lie at relatively high energies compared with the corresponding singlet structures consistent with the higher ligand field splitting of rhenium relative to manganese. The lowest energy HRe(CO)₅ structure is the expected octahedral structure. Low-energy structures for HRe(CO)(n) (n = 4, 3) are singlet structures derived from the octahedral HRe(CO)₅ structure by removal of one or two carbonyl groups. For H₂Re₂(CO)₉ a structure HRe₂(CO)₉(μ-H), with one terminal and one bridging hydrogen atom, lies within 3 kcal/mol of the structure Re₂(CO)₉(η²-H₂), similar to that of Re₂(CO)₁₀. For H₂Re₂(CO)(n) (n = 8, 7, 6) the only low-energy structures are doubly bridged singlet Re₂(μ-H)₂(CO)(n) structures. Higher energy dihydrogen complex structures are also found.

Cat-doping: Novel method for phosphorus and boron shallow doping in crystalline silicon at 80 °C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsumura, Hideki; Hayakawa, Taro; Ohta, Tatsunori

Phosphorus (P) or boron (B) atoms can be doped at temperatures as low as 80 to 350 °C, when crystalline silicon (c-Si) is exposed only for a few minutes to species generated by catalytic cracking reaction of phosphine (PH₃) or diborane (B₂H₆) with heated tungsten (W) catalyzer. This paper is to investigate systematically this novel doping method, “Cat-doping”, in detail. The electrical properties of P or B doped layers are studied by the Van der Pauw method based on the Hall effects measurement. The profiles of P or B atoms in c-Si are observed by secondary ion mass spectrometry mainlymore » from back side of samples to eliminate knock-on effects. It is confirmed that the surface of p-type c-Si is converted to n-type by P Cat-doping at 80 °C, and similarly, that of n-type c-Si is to p-type by B Cat-doping. The doping depth is as shallow as 5 nm or less and the electrically activated doping concentration is 10¹⁸ to 10¹⁹cm⁻³ for both P and B doping. It is also found that the surface potential of c-Si is controlled by the shallow Cat-doping and that the surface recombination velocity of minority carriers in c-Si can be enormously lowered by this potential control.« less

Description and hydrogeologic evaluation of nine hazardous-waste sites in Kansas, 1984-86

USGS Publications Warehouse

Hart, R.J.; Spruill, T.B.

1988-01-01

Wastes generated at nine hazardous-waste sites in Kansas were disposed in open pits, 55-gal drums, or large storage tanks. These disposal methods have the potential to contaminate groundwater beneath the sites, the soil on the sites, and nearby surface water bodies. Various activities on the nine sites included production of diborane, transformer oil waste, production of soda ash, use of solvents for the manufacture of farm implements, reclamation of solvents and paints, oil-refinery wastes, meat packaging, and the manufacture and cleaning of tanker-truck tanks. Monitoring wells were installed upgradient and downgradient from the potential contamination source on each site. Strict decontamination procedures were followed to prevent cross contamination between well installations. Air-quality surveys were made on each site before other investigative procedures started. Hydrogeologic investigative techniques, such as terrain geophysical surveys, gamma-ray logs, and laboratory permeameter tests, were used. Groundwater level measurements provide data to determine the direction of flow. Groundwater contamination detected under the sites posed the greatest threat to the environment because of possible migration of contaminants by groundwater flow. Concentrations of volatile organic compounds, polynuclear aromatic hydrocarbons, and trace metals were detected in the groundwater at several of the sites. Many of the same compounds detected in the groundwater also were detected in soil and bed-material samples collected onsite or adjacent to the sites. Several contaminants were detected in background samples of groundwater and soil. (USGS)

Ultrathin, wafer-scale hexagonal boron nitride on dielectric surfaces by diffusion and segregation mechanism

NASA Astrophysics Data System (ADS)

Sonde, Sushant; Dolocan, Andrei; Lu, Ning; Corbet, Chris; Kim, Moon J.; Tutuc, Emanuel; Banerjee, Sanjay K.; Colombo, Luigi

2017-06-01

Chemical vapor deposition (CVD) of two-dimensional (2D) hexagonal boron nitride (h-BN) is at the center of numerous studies for its applications in novel electronic devices. However, a clear understanding of the growth mechanism is lacking for its wider industrial adoption on technologically relevant substrates such as SiO2. Here, we demonstrate a controllable growth method of thin, wafer scale h-BN films on arbitrary substrates. We also clarify the growth mechanism to be diffusion and surface segregation (D-SS) of boron (B) and nitrogen (N) in Ni and Co thin films on SiO2/Si substrates after exposure to diborane and ammonia precursors at high temperature. The segregation was found to be independent of the cooling rates employed in this report, and to our knowledge has not been found nor reported for 2D h-BN growth so far, and thus provides an important direction for controlled growth of h-BN. This unique segregation behavior is a result of a combined effect of high diffusivity, small film thickness and the inability to achieve extremely high cooling rates in CVD systems. The resulting D-SS h-BN films exhibit excellent electrical insulating behavior with an optical bandgap of about 5.8 eV. Moreover, graphene-on-h-BN field effect transistors using the as-grown D-SS h-BN films show a mobility of about 6000 cm2 V-1 s-1 at room temperature.

Synthesis and Characterization of Methylammonium Borohydride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graham, Kathryn R.; Bowden, Mark E.; Kemmitt, Tim

2011-01-06

A new borohydride, [CH3NH3]+[BH4]-, has been synthesised by the metathesis of CH3NH3X and MBH4 in methylamine in order to determine its behaviour in comparison to ammonium borohydride [NH4]+[BH4]-. The introduction of methyl groups is expected to disrupt the hydrogen bonding network of [NH4]+[BH4]- and in turn alter the hydrogen release properties. Room temperature X-ray diffraction studies have shown that [CH3NH3]+[BH4]- adopts a tetragonal unit cell with lattice parameters of a = 4.9486 Å and b = 8.9083 Å. The room temperature structure shows considerable hydrogen mobility similar to that observed in NH3BH3. The kinetics and thermodynamics of these reactions havemore » been investigated and show hydrogen release follows a similar pathway to that of [NH4]+[BH4]-. Both compounds decompose slowly at room temperature and rapidly at ca. 40 °C to form the diammoniate of diborane or the methylated analogue [BH2(CH3NH2)2]+BH4-. The first stage of decomposition has been further investigated by means on in-situ X-ray diffraction and solid state 11B NMR spectroscopy, and appears to occur in the absence of any detectable intermediates to form crystalline [BH2(CH3NH2)2]+BH4-. [(CH3)2NH2]+[BH4]- and [BH2{(CH3)2NH}2]+BH4- have also been synthesised by analogous routes, indicating a more general applicability of the synthetic method.« less

Metal-Borohydride-Modified Zr(BH4 )4 ⋅8 NH3 : Low-Temperature Dehydrogenation Yielding Highly Pure Hydrogen.

PubMed

Huang, Jianmei; Ouyang, Liuzhang; Gu, Qinfen; Yu, Xuebin; Zhu, Min

2015-10-12

Due to its high hydrogen density (14.8 wt %) and low dehydrogenation peak temperature (130 °C), Zr(BH4 )4 ⋅8 NH3 is considered to be one of the most promising hydrogen-storage materials. To further decrease its dehydrogenation temperature and suppress its ammonia release, a strategy of introducing LiBH4 and Mg(BH4 )2 was applied to this system. Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 composites showed main dehydrogenation peaks centered at 81 and 106 °C as well as high hydrogen purities of 99.3 and 99.8 mol % H2 , respectively. Isothermal measurements showed that 6.6 wt % (within 60 min) and 5.5 wt % (within 360 min) of hydrogen were released at 100 °C from Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , respectively. The lower dehydrogenation temperatures and improved hydrogen purities could be attributed to the formation of the diammoniate of diborane for Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 , and the partial transfer of NH3 groups from Zr(BH4 )4 ⋅8 NH3 to Mg(BH4 )2 for Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , which result in balanced numbers of BH4 and NH3 groups and a more active H(δ+) ⋅⋅⋅(-δ) H interaction. These advanced dehydrogenation properties make these two composites promising candidates as hydrogen-storage materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Research on ZnO/Si heterojunction solar cells

NASA Astrophysics Data System (ADS)

Chen, Li; Chen, Xinliang; Liu, Yiming; Zhao, Ying; Zhang, Xiaodan

2017-06-01

We put forward an n-ZnO/p-Si heterojunction solar cell model based on AFORS-HET simulations and provide experimental support in this article. ZnO:B (B-doped ZnO) thin films deposited by metal-organic chemical vapor deposition (MOCVD) are planned to act as electrical emitter layer on p-type c-Si substrate for photovoltaic applications. We investigate the effects of thickness, buffer layer, ZnO:B affinity and work function of electrodes on performances of solar cells through computer simulations using AFORS-HET software package. The energy conversion efficiency of the ZnO:B(n)/ZnO/c-Si(p) solar cell can achieve 17.16% ({V}{oc}: 675.8 mV, {J}{sc}: 30.24 mA/cm2, FF: 83.96%) via simulation. On a basis of optimized conditions in simulation, we carry out some experiments, which testify that the ZnO buffer layer of 20 nm contributes to improving performances of solar cells. The influences of growth temperature, thickness and diborane (B2H6) flow rates are also discussed. We achieve an appropriate condition for the fabrication of the solar cells using the MOCVD technique. The obtained conversion efficiency reaches 2.82% ({V}{oc}: 294.4 mV, {J}{sc}: 26.108 mA/cm2, FF: 36.66%). Project supported by the State Key Development Program for Basic Research of China (Nos. 2011CBA00706, 2011CBA00707), the Tianjin Applied Basic Research Project and Cutting-Edge Technology Research Plan (No. 13JCZDJC26900), the Tianjin Major Science and Technology Support Project (No. 11TXSYGX22100), the National High Technology Research and Development Program of China (No. 2013AA050302), and the Fundamental Research Funds for the Central Universities (No. 65010341).

Analysis of gas membrane ultra-high purification of small quantities of mono-isotopic silane

DOE PAGES

de Almeida, Valmor F.; Hart, Kevin J.

2017-01-03

A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. In addition, analytic solutions are invaluable to verify numerical solutions obtained from computer-aided methods. Hence, in this paper wemore » provide new analytic solutions for the purification loops proposed. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similar to silane. Other potential problematic compounds are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. And finally, future extension of this work to the non-dilute limit may apply to the recovery of silane from rejected streams of natural silicon semi-conductor processes.« less

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Hui, E-mail: huiwu@nist.gov; Zhou, Xiuquan; Rodriguez, Efrain E.

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH{sub 4}·nCN{sub 3}H{sub 5}, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH{sub 4}){sub 2}·6CN{sub 3}H{sub 5} is composed of large complex Mg[CN{sub 3}H{sub 5}]{sub 6}{sup 2+} cations and surrounding BH{sub 4}{sup -} ions, while Ca(BH{sub 4}){sub 2}·2CN{sub 3}H{sub 5} possesses layers of corner-sharing Ca[BH{sub 4}]{sub 4}(CN{sub 3}H{sub 5}){sub 2} octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be releasedmore » from MBH{sub 4}·nCN{sub 3}H{sub 5} (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH{sub 4}){sub 2}·nCN{sub 3}H{sub 5} can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release. - Graphical abstract: A new family of complex hydrides: borohydride guanidinates, was developed with diverse crystal structures and remarkable hydrogen storage properties. - Highlights: • A new family of complex hydrides, borohydride guanidinate complexes, are synthesized. • Their diverse crystal structures are determined using combined characterizations. • These compounds can release ~10 wt% pure H{sub 2} at moderate temperatures. • Dehydrogenation thermodynamics and H{sub 2} purity can be tuned by varying cation species.« less

Very low temperature (450 °C) selective epitaxial growth of heavily in situ boron-doped SiGe layers

NASA Astrophysics Data System (ADS)

Aubin, J.; Hartmann, J. M.; Veillerot, M.; Essa, Z.; Sermage, B.

2015-11-01

We have investigated the feasibility of selectively growing SiGe:B layers at 450 °C, 20 Torr in a 300 mm industrial reduced pressure chemical vapor deposition tool. A reduced H2 carrier gas mass-flow has been used in order to have acceptable growth rates at such a temperature, which is very low indeed. We have first of all studied on blanket Si wafers the in situ boron doping of SiGe with Si2H6, GeH4 and B2H6. A growth rate increase by a factor close to 7 together with a Ge concentration decrease from 53% down to 32% occurred as the diborane mass-flow increased. Very high B+ ion concentrations were obtained in layers that were single crystalline and smooth. Their concentration increased almost linearly with the B2H6 mass-flow, from 1.8 up to 8.3 × 1020 cm-3. The associated resistivity dropped from 0.43 down to 0.26 mΩ cm. We have then tested whether or not selectivity versus SiO2 could be achieved by adding various amounts of HCl to Si2H6 + GeH4 +B2H6. Single crystalline growth rates of intrinsic SiGe(:B) on Si were very similar to poly-crystalline growth rates on SiO2-covered substrates irrespective of the HCl flow. Straightforward selectivity was thus not feasible with a co-flow approach. As a consequence, a 450 °C deposition/etch (DE) process was evaluated. Growth occurred at 20 Torr with the above-mentioned chemistry, while the selective etch of poly-SiGe:B versus c-SiGe:B was conducted at 740 Torr with a medium HCl mass-flow (F(HCl)/F(H2) = 0.2) and a high H2 flow. A 2.2 etch selectivity was achieved while retaining single crystalline if slightly rough SiGe:B layers.

The preparation of in situ doped hydrogenated amorphous silicon by homogeneous chemical vapor deposition

NASA Astrophysics Data System (ADS)

Meyerson, B. S.; Scott, B. A.; Wolford, D. J.

1983-03-01

Raman scattering, infrared absorption, conductivity measurements, electron microprobe, and secondary ion mass spectrometry (SIMS) were used to characterize boron and phosphorus doped hydrogenated amorphous silicon (a-Si:H) films prepared by Homogeneous Chemical Vapor Deposition (HOMOCVD). HOMOCVD is a thermal process which relies upon the gas phase pyrolysis of a source (silane containing up to 1.0% diborane or phosphine) to generate activated species for deposition upon a cooled substrate. Doped films prepared at 275 °C by this process were found to contain ˜12-at. % hydrogen as determined by infrared absorption. We examined dopant incorporation from the gas phase, obtaining values for a distribution coefficient CD (film dopant content/gas phase dopant concentration, atomic basis) of 0.33≤CD ≤0.63 for boron, while 0.4≤CD ≤10.75 in the limits 3.3×10-5≤PH3/SiH4≤0.004. We interpret the data as indicative of the formation of an unstable phosphorus/silicon intermediate in the gas phase, leading to the observed enhancements in CD at high gas phase phosphine content. HOMOCVD films doped at least as efficiently as their prepared counterparts, but tended to achieve higher conductivities [σ≥0.1 (Ω cm)-1 for 4.0% incorporated phosphorus] in the limit of heavy doping. Raman spectra showed no evidence of crystallinity in the doped films. Film properties (conductivity, activation energy of of conduction) have not saturated at the doping levels investigated here, making the attainment of higher ``active'' dopant levels a possibility. We attribute the observation that HOMOCVD appears more amenable to high ``active'' dopant levels than plasma techniques to the low (˜0.1 eV) thermal energy at which HOMOCVD proceeds, versus ˜10-100 eV for plasma techniques. Low substrate temperature (75 °C) doped films were prepared with initial results showing these films to dope as readily as those prepared at high temperature (T˜275 °C).

Analysis of gas membrane ultra-high purification of small quantities of mono-isotopic silane

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Almeida, Valmor F.; Hart, Kevin J.

A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. In addition, analytic solutions are invaluable to verify numerical solutions obtained from computer-aided methods. Hence, in this paper wemore » provide new analytic solutions for the purification loops proposed. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similar to silane. Other potential problematic compounds are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. And finally, future extension of this work to the non-dilute limit may apply to the recovery of silane from rejected streams of natural silicon semi-conductor processes.« less

Analysis of Gas Membrane Ultra-High Purification of Small Quantities of Mono-Isotopic Silane

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Almeida, Valmor F.; Hart, Kevin J.

A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similarmore » to silane. Other potential problematic surprises are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. To improve the separation selectivity, it is advantageous to use a permeate chamber under vacuum, however this also requires greater control of in-leakage of impurities in the system. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. Last but not least, future extension of this work to the non-dilute limit may apply to the recovery of silane from rejected streams of natural silicon semi-conductor processes.« less

Growth of boron doped hydrogenated nanocrystalline cubic silicon carbide (3C-SiC) films by Hot Wire-CVD

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pawbake, Amit; Tata Institute of Fundamental Research, Colaba, Mumbai 400 005; Mayabadi, Azam

Highlights: • Boron doped nc-3C-SiC films prepared by HW-CVD using SiH{sub 4}/CH{sub 4}/B{sub 2}H{sub 6}. • 3C-Si-C films have preferred orientation in (1 1 1) direction. • Introduction of boron into SiC matrix retard the crystallanity in the film structure. • Film large number of SiC nanocrystallites embedded in the a-Si matrix. • Band gap values, E{sub Tauc} and E{sub 04} (E{sub 04} > E{sub Tauc}) decreases with increase in B{sub 2}H{sub 6} flow rate. - Abstract: Boron doped nanocrystalline cubic silicon carbide (3C-SiC) films have been prepared by HW-CVD using silane (SiH{sub 4})/methane (CH{sub 4})/diborane (B{sub 2}H{sub 6}) gasmore » mixture. The influence of boron doping on structural, optical, morphological and electrical properties have been investigated. The formation of 3C-SiC films have been confirmed by low angle XRD, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) spectroscopy and high resolution-transmission electron microscopy (HR-TEM) analysis whereas effective boron doping in nc-3C-SiC have been confirmed by conductivity, charge carrier activation energy, and Hall measurements. Raman spectroscopy and HR-TEM analysis revealed that introduction of boron into the SiC matrix retards the crystallanity in the film structure. The field emission scanning electron microscopy (FE-SEM) and non contact atomic force microscopy (NC-AFM) results signify that 3C-SiC film contain well resolved, large number of silicon carbide (SiC) nanocrystallites embedded in the a-Si matrix having rms surface roughness ∼1.64 nm. Hydrogen content in doped films are found smaller than that of un-doped films. Optical band gap values, E{sub Tauc} and E{sub 04} decreases with increase in B{sub 2}H{sub 6} flow rate.« less

Understanding the synthesis, performance, and passivation of metal oxide photocathodes

NASA Astrophysics Data System (ADS)

Flynn, Cory James

Metal oxides are ubiquitous in semiconductor technologies for their ease of synthesis, chemical stability, and tunable optical/electronic properties. These properties are especially important to fabricating efficient photoelectrodes for solar-energy applications. To counter inherent problems in these materials, new strategies were developed and successfully implemented on the widely-utilized p-type semiconductor, NiO. As the size of semiconductor materials shrink, the surface-to-volume ratio increases and surface defects dominate the performance of the materials. Surface defects can alter the optical and electronic characteristics of materials by changing the Fermi level, charge-carrier mobility, and surface reactivity. We first present a strategy to increase the electrical mobility of mesoporous metal oxide electrode materials by optimizing shape morphology. Transitioning from nanospheres to hexagonal nanoplatelets increased the charge-carrier mobility by one order of magnitude. We then employed this improved material with a new vapor-phase deposition method termed targeted atomic deposition (TAD) to selectively passivate defect sites in semiconductor nanomaterials. We demonstrated the capabilities of this passivation method by applying a TAD of aluminum onto NiO. By exploiting a temperature-dependent deposition process, we selectively passivated the highly reactive sites in NiO: oxygen dangling bonds associated with Ni vacancies. The TAD treatment completely passivated all measurable surface defects, optically bleached the material, and significantly improved all photovoltaic performance metrics in dye-sensitized solar cells. The technique was proven to be generic to numerous forms of NiO. While the implementation of TAD of Al was successful, the process involved pulsing two precursors to passivate the material. Ideally, the TAD process should require only a single precursor and continuous exposure. We utilized a continuous flow of diborane to perform a TAD of B onto NiO. The TAD process was successfully implemented in a simplified manner. The treatment moderately increased DSSC performance and proved viability with a different vapor-phase precursor.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simmons, F.; Kuntamukkula, M.; Alnajjar, M.

Pyrophoric reagents represent an important class of reactants because they can participate in many different types of reactions. They are very useful in organic synthesis and in industrial applications. The Occupational Safety and Health Administration (OSHA) and the National Fire Protection Association (NFPA) define Pyrophorics as substances that will self-ignite in air at temperatures of 130 F (54.4 C) or less. However, the U.S. Department of Transportation (DOT) uses criteria different from the auto-ignition temperature criterion. The DOT defines a pyrophoric material as a liquid or solid that, even in small quantities and without an external ignition source, can ignitemore » within five minutes after coming in contact with air when tested according to the United Nations Manual of Tests and Criteria. The Environmental Protection Agency has adopted the DOT definition. Regardless of which definition is used, oxidation of the pyrophoric reagents by oxygen or exothermic reactions with moisture in the air (resulting in the generation of a flammable gas such as hydrogen) is so rapid that ignition occurs spontaneously. Due to the inherent nature of pyrophoric substances to ignite spontaneously upon exposure to air, special precautions must be taken to ensure their safe handling and use. Pyrophoric gases (such as diborane, dichloroborane, phosphine, etc.) are typically the easiest class of pyrophoric substances to handle since the gas can be plumbed directly to the application and used remotely. Pyrophoric solids and liquids, however, require the user to physically manipulate them when transferring them from one container to another. Failure to follow proper safety precautions could result in serious injury or unintended consequences to laboratory personnel. Because of this danger, pyrophorics should be handled only by experienced personnel. Users with limited experience must be trained on how to handle pyrophoric reagents and consult with a knowledgeable staff member prior to performing the experimental task. The purpose of this article is three fold: (1) to provide guidelines and general safety precautions to avoid accidents, (2) describe proper techniques on how to successfully handle, store, and dispose of pyrophoric liquids and solids, and (3) illustrate best practices for working with this class of reactants in a laboratory environment.« less

Synthesis and characterization of group IV semiconductor nanowires by vapor-liquid-solid growth

NASA Astrophysics Data System (ADS)

Lew, Kok-Keong

There is currently intense interest in one-dimensional nanostructures, such as nanotubes and nanowires, due to their potential to test fundamental concepts of dimensionality and to serve as building blocks for nanoscale devices. Vapor-liquid-solid (VLS) growth, which is one of the most common fabrication methods, has been used to produce single crystal semiconductor nanowires such as silicon (Si), germanium (Ge), and gallium arsenide (GaAs). In the VLS growth of Group IV semiconductor nanowires, a metal, such as gold (Au) is used as a catalyst agent to nucleate whisker growth from a Si-containing (silane (SIH4)) or Ge-containing vapor (germane (GeH 4)). Au and Si/Ge form a liquid alloy that has a eutectic temperature of around 360°C, which, upon supersaturation, nucleates the growth of a Si or Ge wire. The goal of this work is to develop a more fundamental understanding of VLS growth kinetics and intentional doping of Group IV semiconductor nanowires in order to better control the properties of the nanowires. The fabrication of p-type and n-type Si nanowires will be studied via the addition of dopant gases such as diborane (B2H 6), trimethylboron (TMB), and phosphine (PH3) during growth. The use of gaseous dopant sources provides more flexibility in growth, particularly for the fabrication of p-n junctions and structures with axial dopant variations (e.g. p+-p- p+). The study is then extended to fabricate SiGe alloy nanowires by mixing SiH4 and GeH4. Bandgap engineering in Si/SiGe heterostructures can lead to novel devices with improved performance compared to those made entirely of Si. The scientific findings will lead to a better understanding of the fabrication of Si/SiGe axial and radial heterostructure nanowires for functional nanowire device structures, such as heterojunction bipolar transistors (HBTs) and high electron mobility transistors (HEMTs). Eventually, the central theme of this research is to provide a scientific knowledge base and foundation for the design of Si, Ge, and SiGe nanostructures that will be of importance in nanoscale device applications.

trans-[Pt(BCat')Me(PCy3)2]: an experimental case study of reductive elimination processes in Pt-Boryls through associative mechanisms.

PubMed

Braunschweig, Holger; Bertermann, Rüdiger; Brenner, Peter; Burzler, Michael; Dewhurst, Rian D; Radacki, Krzysztof; Seeler, Fabian

2011-10-10

A stable trans-(alkyl)(boryl) platinum complex trans-[Pt(BCat')Me(PCy(3))(2)] (Cat'=Cat-4-tBu; Cy=cyclohexyl=C(6)H(11)) was synthesised by salt metathesis reaction of trans-[Pt(BCat')Br(PCy(3))(2)] with LiMe and was fully characterised. Investigation of the reactivity of the title compound showed complete reductive elimination of Cat'BMe at 80 °C within four weeks. This process may be accelerated by the addition of a variety of alkynes, thereby leading to the formation of the corresponding η(2) -alkyne platinum complexes, of which [Pt(η(2)-MeCCMe)(PCy(3))(2)] was characterised by X-ray crystallography. Conversion of the trans-configured title compound to a cis derivative remained unsuccessful due to an instantaneous reductive elimination process during the reaction with chelating phosphines. Treatment of trans-[Pt(BCat')Me(PCy(3))(2)] with Cat(2)B(2) led to the formation of CatBMe and Cat'BMe. In the course of further investigations into this reaction, indications for two indistinguishable reaction mechanisms were found: 1) associative formation of a six-coordinate platinum centre prior to reductive elimination and 2) σ-bond metathesis of B-B and C-Pt bonds. Mechanism 1 provides a straightforward explanation for the formation of both methylboranes. Scrambling of diboranes(4) Cat(2)B(2) and Cat'(2)B(2) in the presence of [Pt(PCy(3))(2)], fully reductive elimination of CatBMe or Cat'BMe from trans-[Pt(BCat')Me(PCy(3))(2)] in the presence of sub-stoichiometric amounts of Cat(2)B(2), and evidence for the reversibility of the oxidative addition of Cat(2)B(2) to [Pt(PCy(3))(2)] all support mechanism 2, which consists of sequential equilibria reactions. Furthermore, the solid-state molecular structure of cis-[Pt(BCat)(2)(PCy(3))(2)] and cis-[Pt(BCat')(2)(PCy(3))(2)] were investigated. The remarkably short B-B separations in both bis(boryl) complexes suggest that the two boryl ligands in each case are more loosely bound to the Pt(II) centre than in related bis(boryl) species. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasma enhanced chemical vapor deposition of metalboride interfacial layers as diffusion barriers for nanostructured diamond growth on cobalt containing alloys CoCrMo and WC-Co

NASA Astrophysics Data System (ADS)

Johnston, Jamin M.

This work is a compilation of theory, finite element modeling and experimental research related to the use of microwave plasma enhanced chemical vapor deposition (MPECVD) of diborane to create metal-boride surface coatings on CoCrMo and WC-Co, including the subsequent growth of nanostructured diamond (NSD). Motivation for this research stems from the need for wear resistant coatings on industrial materials, which require improved wear resistance and product lifetime to remain competitive and satisfy growing demand. Nanostructured diamond coatings are a promising solution to material wear but cannot be directly applied to cobalt containing substrates due to graphite nucleation. Unfortunately, conventional pre-treatment methods, such as acid etching, render the substrate too brittle. Thus, the use of boron in a MPECVD process is explored to create robust interlayers which inhibit carbon-cobalt interaction. Furthermore, modeling of the MPECVD process, through the COMSOL MultiphysicsRTM platform, is performed to provide insight into plasma-surface interactions using the simulation of a real-world apparatus. Experimental investigation of MPECVD boriding and NSD deposition was conducted at surface temperatures from 700 to 1100 °C. Several well-adhered metal-boride surface layers were formed: consisting of CoB, CrB, WCoB, CoB and/or W2CoB2. Many of the interlayers were shown to be effective diffusion barriers against elemental cobalt for improving nucleation and adhesion of NSD coatings; diamond on W2CoB2 was well adhered. However, predominantly WCoB and CoB phase interlayers suffered from diamond film delamination. Metal-boride and NSD surfaces were evaluated using glancing-angle x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), cross-sectional scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), micro-Raman spectroscopy, nanoindentation, scratch testing and epoxy pull testing. COMSOL MultiphysicsRTM was used to construct a representation of the MPECVD chamber. Relevant material properties, boundary conditions and adjustable parameters were applied to match the actual experimental set-up. Despite approximations, simulations for the surface temperature and surface accumulation matched well with experimental data. The combination of data from CoCrMo, WC-Co and modeling of the MPECVD process confirms that the use of boron to create metal-boride interlayers is applicable for subsequent nanostructured diamond coatings and that the surface temperature and deposition thickness can be predicted using finite element modeling.

Molecular approaches to p- and n-nanoscale doping of Ge 1-ySn y semiconductors: Structural, electrical and transport properties

NASA Astrophysics Data System (ADS)

Xie, Junqi; Tolle, J.; D'Costa, V. R.; Weng, C.; Chizmeshya, A. V. G.; Menendez, J.; Kouvetakis, J.

2009-08-01

We report the development of practical doping protocols via designer molecular sources to create n- and p-type doped Ge 1-ySn y layers grown directly upon Si(1 0 0). These materials will have applications in the fabrication of advanced PIN devices that are intended to extend the infrared optical response beyond that of Ge by utilizing the Sn composition as an additional design parameter. Highly controlled and efficient n-doping of single-layer structures is achieved using custom built P(GeH 3) 3 and As(GeH 3) 3, precursors containing preformed Ge-As and Ge-P near-tetrahedral bonding arrangements compatible with the structure of the host Ge-Sn lattice. Facile substitution and complete activation of the P and As atoms at levels ˜10 17-10 19 cm -3 is obtained via in situ depositions at low temperatures (350 °C). Acceptor doping is readily achieved using conventional diborane yielding carrier concentrations between 10 17-10 19 cm -3 under similar growth conditions. Full activation of the as-grown dopant concentrations is demonstrated by combined SIMS and Hall experiments, and corroborated using a contactless spectroscopic ellipsometry approach. RTA processing of the samples leads to a significant increase in carrier mobility comparable to that of bulk Ge containing similar doping levels. The alloy scattering contribution appears to be negligible for electron carrier concentrations beyond 10 19 cm -3 in n-type samples and hole concentrations beyond 10 18 cm -3 in p-type samples. A comparative study using the classical lower-order hydrides PH 3 and AsH 3 produced n-doped films with carrier densities (up to 9 × 10 19 cm -3) similar to those afforded by P(GeH 3) 3 and As(GeH 3) 3. However, early results indicate that the simpler PH 3 and AsH 3 sources yield materials with inferior morphology and microstructure. Calculations of surface energetics using bond enthalpies suggest that the latter massive compounds bind to the surface via strong Ge-Ge bonds and likely act as "retardants" that moderate surface diffusion of the reactions species, thereby promoting layer-by-layer growth leading to thick, atomically smooth films, particularly in the case of P(GeH 3) 3. Furthermore, the intact incorporation of the Ge 3P and Ge 3As molecular cores results in highly uniform compositional, strain and doping profiles at the atomic level.

Interface properties of the amorphous silicon/crystalline silicon heterojunction photovoltaic cell

NASA Astrophysics Data System (ADS)

Halliop, Basia

Amorphous-crystalline silicon (a-Si:H/c-Si) heterojunctions have the potential of being a very high efficiency silicon photovoltaic platform technology with accompanying cost and energy budget reductions. In this research a heterojunction cell structure based on a-Si:H deposited using a DC saddle field plasma enhanced vapour deposition (DCSF PECVD) technique is studied, and the a-Si:H/c-Si and indium tin oxide/a-Si:H interfaces are examined using several characterization methods. Photocarrier radiometry (PCR) is used for the first time to probe the a-Si:H/c-Si junction. PCR is demonstrated as a carrier lifetime measurement technique -- specifically, confirming carrier lifetimes above 1 ms for 1-5 Ocm phosphorous-doped c-Si wafers passivated on both sides with 30 nm of i-a-Si:H. PCR is also used to determine surface recombination velocity and mobility, and to probe recombination at the a-Si:H/c-Si interface, distinguishing interface recombination from recombination within the a-Si:H layer or at the a-Si:H surface. A complementary technique, lateral conductivity is applied over a temperature range of 140 K to 430 K to construct energy band diagrams of a-Si:H/c-Si junctions. Boron doped a-Si:H films on glass are shown to have activation energies of 0.3 to 0.35 eV, tuneable by adjusting the diborane to silane gas ratio during deposition. Heterojunction samples show evidence of a strong hole inversion layer and a valence band offset of approximately 0.4 eV; carrier concentration in the inversion layer is reduced in p-a-Si:H/i-a-Si:H/ c-Si structures as intrinsic layer thickness increases, while carrier lifetime is increased. The indium tin oxide/amorphous silicon interface is also examined. Optimal ITO films were prepared with a sheet resistance of 17.3 O/[special character omitted] and AM1.5 averaged transmittance of 92.1%., for a film thickness of approximately 85 nm, using temperatures below 200°C. Two different heat treatments are found to cause crystallization of ITO and to change the properties of the underlying a-Si:H film. Finally, an open circuit voltage of 699 mV was achieved using DCSF PECVD in the tetrode configuration to fabricate a metal/ITO/p-a-Si:H/ i-a-Si:H/n-c-Si/i-a-Si:H/ n+-a-Si:H/metal photovoltaic cell on a texturized wafer. The 4 cm2 cell had an efficiency of 16.5%, a short circuit current of 36.4 mA/cm2 and a fill factor of 64.7%.

Boron carbide nanowires: Synthesis and characterization

NASA Astrophysics Data System (ADS)

Guan, Zhe

Bulk boron carbide has been widely used in ballistic armored vest and the property characterization has been heavily focused on mechanical properties. Even though boron carbides have also been projected as a promising class of high temperature thermoelectric materials for energy harvesting, the research has been limited in this field. Since the thermal conductivity of bulk boron carbide is still relatively high, there is a great opportunity to take advantage of the nano effect to further reduce it for better thermoelectric performance. This dissertation work aims to explore whether improved thermoelectric performance can be found in boron carbide nanowires compared with their bulk counterparts. This dissertation work consists of four main parts. (1) Synthesis of boron carbide nanowires. Boron carbide nanowires were synthesized by co-pyrolysis of diborane and methane at low temperatures (with 879 °C as the lowest) in a home-built low pressure chemical vapor deposition (LPCVD) system. The CVD-based method is energy efficient and cost effective. The as-synthesized nanowires were characterized by electron microscopy extensively. The transmission electron microscopy (TEM) results show the nanowires are single crystalline with planar defects. Depending on the geometrical relationship between the preferred growth direction of the nanowire and the orientation of the defects, the as-synthesized nanowires could be further divided into two categories: transverse fault (TF) nanowires grow normal to the defect plane, while axial fault (AF) ones grow within the defect plane. (2) Understanding the growth mechanism of as-synthesized boron carbide nanowires. The growth mechanism can be generally considered as the famous vapor-liquid-solid (VLS) mechanism. TF and AF nanowires were found to be guided by Ni-B catalysts of two phases. A TF nanowire is lead by a hexagonal phase catalyst, which was proved to be in a liquid state during reaction. While an AF nanowires is catalyzed by a solid orthorhombic phase catalyst. The status of a catalyst depends mainly on temperature. (3) Observation of "invisible" defects in boron carbide nanowires. The planar defects can only be seen under a transmission electron microscope when the electron beam is within the defect plane. Furthermore, there are only two directions within that plane, along which the orientation of defect can be told and clear TEM results can be taken. The challenge is that the TEM sample holder is limited to tilt +/-30° in each direction. A theory was developed based on lattice calculation and simulation to tell the orientation of defect even not from those unique directions. Furthermore, it was tested by experimental data and proved to be successful. (4) Preliminary exploration of structure-transport property of as-synthesized boron carbide nanowires. In collaboration with experts in the field of thermal science, thermal transport properties of a few boron carbide nanowires were studied. All measured nanowires were either pre-characterized or post-characterized by TEM to reveal their structural information such as diameter, fault orientations and chemical composition. The obtained structural information was then analyzed together with measured thermal conductivity to establish a structure-transport property relation. Current data indicate that TF ones have a lower thermal conductivity, which is also diameter-dependent.

Design and fabrication of a novel self-powered solid-state neutron detector

NASA Astrophysics Data System (ADS)

LiCausi, Nicholas

There is a strong interest in intercepting special nuclear materials (SNM) at national and international borders and ports for homeland security applications. Detection of SNM such as U and Pu is often accomplished by sensing their natural or induced neutron emission. Such detector systems typically use thermal neutron detectors inside a plastic moderator. In order to achieve high detection efficiency gas filled detectors are often used; these detectors require high voltage bias for operation, which complicates the system when tens or hundreds of detectors are deployed. A better type of detector would be an inexpensive solid-state detector that can be mass-produced like any other computer chip. Research surrounding solid-state detectors has been underway since the late 1990's. A simple solid-state detector employs a planar solar-cell type p-n junction and a thin conversion material that converts incident thermal neutrons into detectable alpha-particles and 7Li ions. Existing work has typically used 6LiF or 10B as this conversion layer. Although a simple planar detector can act as a highly portable, low cost detector, it is limited to relatively low detection efficiency (˜10%). To increase the efficiency, 3D perforated p-i-n silicon devices were proposed. To get high efficiency, these detectors need to be biased, resulting in increased leakage current and hence detector noise. In this research, a new type of detector structure was proposed, designed and fabricated. Among several detector structures evaluated, a honeycomb-like silicon p-n structure was selected, which is filled with natural boron as the neutron converter. A silicon p+-n diode formed on the thin silicon wall of the honeycomb structure detects the energetic alpha-particles emitted from the boron conversion layer. The silicon detection layer is fabricated to be fully depleted with an integral step during the boron filling process. This novel feature results in a simplified fabrication process. Three key advantages of the novel devices are theoretical neutron detection efficiency of ˜48%, a self-passivating structure that reduces leakage current and detector operation with no bias resulting in extremely low device noise. Processes required to fabricate the 3D type detector were explored and developed in this thesis. The detector capacitance and processing steps have been simulated with MEDICI and TSuprem-4, respectively. Lithography masks were then designed using Cadence. The fabrication process development was conducted in line with standard CMOS grade integrated circuit processing to allow for simple integration with existing fabrication facilities. A number of new processes were developed including the low pressure chemical vapor deposition of conformal boron films using diborane on very high aspect-ratio trenches and holes. Development also included methods for "wet" chemical etching and "dry" reactive ion etching of the deposited boron films. Fabricated detectors were characterized with the transmission line method, 4-point probe, I-V measurements and C-V measurements. Finally the detector response to thermal neutrons was studied. Characterization has shown significant reduction in reverse leakage current density to ˜8x10-8 A/cm2 (nearly 4 orders of magnitude over the previously published data). Results show that the fabrication process developed is capable of producing efficient (˜22.5%) solid-state thermal neutron detectors.

Interlayer utilization (including metal borides) for subsequent deposition of NSD films via microwave plasma CVD on 316 and 440C stainless steels

NASA Astrophysics Data System (ADS)

Ballinger, Jared

Diamond thin films have promising applications in numerous fields due to the extreme properties of diamonds in conjunction with the surface enhancement of thin films. Biomedical applications are numerous including temporary implants and various dental and surgical instruments. The unique combination of properties offered by nanostructured diamond films that make it such an attractive surface coating include extreme hardness, low obtainable surface roughness, excellent thermal conductivity, and chemical inertness. Regrettably, numerous problems exist when attempting to coat stainless steel with diamond generating a readily delaminated film: outward diffusion of iron to the surface, inward diffusion of carbon limiting necessary surface carbon precursor, and the mismatch between the coefficients of thermal expansion yielding substantial residual stress. While some exotic methods have been attempted to overcome these hindrances, the most common approach is the use of an intermediate layer between the stainless steel substrate and the diamond thin film. In this research, both 316 stainless steel disks and 440C stainless steel ball bearings were tested with interlayers including discrete coatings and graded, diffusion-based surface enhancements. Titanium nitride and thermochemical diffusion boride interlayers were both examined for their effectiveness at allowing for the growth of continuous and adherent diamond films. Titanium nitride interlayers were deposited by cathodic arc vacuum deposition on 440C bearings. Lower temperature diamond processing resulted in improved surface coverage after cooling, but ultimately, both continuity and adhesion of the nanostructured diamond films were unacceptable. The ability to grow quality diamond films on TiN interlayers is in agreement with previous work on iron and low alloy steel substrates, and the similarly seen inadequate adhesion strength is partially a consequence of the lacking establishment of an interfacial carbide phase. Surface boriding was implemented using the novel method of microwave plasma CVD with a mixture of hydrogen and diborane gases. On 440C bearings, dual phase boride layers of Fe2B and FeB were formed which supported adhered nanostructured diamond films. Continuity of the films was not seamless with limited regions remaining uncoated potentially corresponding to delamination of the film as evidenced by the presence of tubular structures presumably composed of sp2 bonded carbon. Surface boriding of 316 stainless steel discs was conducted at various powers and pressures to achieve temperatures ranging from 550-800 °C. The substrate boriding temperature was found to substantially influence the resultant interlayer by altering the metal boride(s) present. The lowest temperatures produced an interlayer where CrB was the single detected phase, higher temperatures yielded the presence of only Fe2B, and a combination of the two phases resulted from an intermediate boriding temperature. Compared with the more common, commercialized boriding methods, this a profound result given the problems posed by the FeB phase in addition to other advantages offered by CVD processes and microwave generated plasmas in general. Indentation testing of the boride layers revealed excellent adhesion strength for all borided interlayers, and above all, no evidence of cracking was observed for a sole Fe2B phase. As with boriding of 440C bearings, subsequent diamond deposition was achieved on these interlayers with substantially improved adhesion strength relative to diamond coated TiN interlayers. Both XRD and Raman spectroscopy confirmed a nanostructured diamond film with interfacial chromium carbides responsible for enhanced adhesion strength. Interlayers consisting solely of Fe2B have displayed an ability to support fully continuous nanostructured diamond films, yet additional study is required for consistent reproduction. This is in good agreement with initial work on pack borided high alloy steels to promote diamond film surface modification. The future direction for continued research of nanostructured diamond coatings on microwave plasma CVD borided stainless steel should further investigate the adhesion of both borided interlayers and subsequent NSD films in addition to short, interrupted diamond depositions to study the interlayer/diamond film interface.

Synthesis of thin films in boron-carbon-nitrogen ternary system by microwave plasma enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Kukreja, Ratandeep Singh

The Boron Carbon Nitorgen (B-C-N) ternary system includes materials with exceptional properties such as wide band gap, excellent thermal conductivity, high bulk modulus, extreme hardness and transparency in the optical and UV range that find application in most fields ranging from micro-electronics, bio-sensors, and cutting tools to materials for space age technology. Interesting materials that belong to the B-C-N ternary system include Carbon nano-tubes, Boron Carbide, Boron Carbon Nitride (B-CN), hexagonal Boron Nitride ( h-BN), cubic Boron Nitride (c-BN), Diamond and beta Carbon Nitride (beta-C3N4). Synthesis of these materials requires precisely controlled and energetically favorable conditions. Chemical vapor deposition is widely used technique for deposition of thin films of ceramics, metals and metal-organic compounds. Microwave plasma enhanced chemical vapor deposition (MPECVD) is especially interesting because of its ability to deposit materials that are meta-stable under the deposition conditions, for e.g. diamond. In the present study, attempt has been made to synthesize beta-carbon nitride (beta-C3N4) and cubic-Boron Nitride (c-BN) thin films by MPECVD. Also included is the investigation of dependence of residual stress and thermal conductivity of the diamond thin films, deposited by MPECVD, on substrate pre-treatment and deposition temperature. Si incorporated CNx thin films are synthesized and characterized while attempting to deposit beta-C3N4 thin films on Si substrates using Methane (CH4), Nitrogen (N2), and Hydrogen (H2). It is shown that the composition and morphology of Si incorporated CNx thin film can be tailored by controlling the sequence of introduction of the precursor gases in the plasma chamber. Greater than 100mum size hexagonal crystals of N-Si-C are deposited when Nitrogen precursor is introduced first while agglomerates of nano-meter range graphitic needles of C-Si-N are deposited when Carbon precursor is introduced first in the deposition chamber. Hexagonal -- BN thin films are successfully deposited using Diborane (B2H6) (5% in H2), Ammonia (NH3) and H2 as precursor gases in the conventional MPECVD mode with and without the negative DC bias. The quality of h-BN in the films improved with pressure and when NH3 used as the first precursor gas in the deposition chamber. c-BN thin films are successfully deposited using Boron-Trifluoride (BF3) (10% in Argon (Ar)), N2, H2, Ar and Helium (He) gases in the electron cyclotron resonance (ECR) mode of the MPECVD system with negative DC bias. Up-to 66% c-BN in the films is achieved under deposition conditions of lower gas flow rates and higher deposition pressures than that reported in the literature for film deposited by ECR-MPECVD. It is shown that the percentage c-BN in the films correlates with the deposition pressure, BF3/H2 ratio and, negative DC bias during nucleation and growth. Diamond thin films are deposited using 60%Ar, 39% H2 and, 1%CH4 at 600°C, 700°C and 800°C substrate temperatures, measured by an IR pyrometer, on Si substrates pre-treated with 3-6nm diamond sol and 20-40mum diamond slurry. Raman spectroscopy, FTIR, X-Ray diffraction (XRD) and, photo-thermal reflectivity methods are used to characterize the thin films. Residual stresses observed for the diamond thin films deposited in this study are tensile in nature and increased with deposition temperature. Better quality diamond films with lower residual stresses are obtained for films deposited on Si substrate pre-treated with 3-6nm diamond sol. Preliminary results on thermal conductivity, k, suggest that k is directly dependent on the deposition temperature and independent of substrate pre-treatment signifying that the nano-seeding technique can be used to replace conventional surface activation technique for diamond seeding where needed.

Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lesch, David A; Adriaan Sachtler, J.W. J.; Low, John J

UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. Themore » assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 LiAlH4Mg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the alanate from alkali hydride, Al and hydrogen, was hampering reversibility. The reverse reaction was then studied for the same phase diagram, starting with LiH, NaH, and MgH2, and Al. The study was extended to phase diagrams including KH and CaH2 as well. The observed hydrogen storage capacity in the Al hexahydrides was less than 4 wt. %, well short of DOE targets. The HT assay came on line and after certification with studies on NaAlH4, was first applied to the LiNH2 - LiBH4 - MgH2 phase diagram. The 60-point study elucidated trends within the system locating an optimum material of 0.6 LiNH2 0.3 MgH2 0.1 LiBH4 that stored about 4 wt. % H2 reversibly and operated below 220 °C. Also present was the phase Li4(NH2)3BH4, which had been discovered in the LiNH2 -LiBH4 system. This new ternary formulation performed much better than the well-known 2 LiNH2MgH2 system by 50 °C in the HT assay. The Li4(NH2)3BH4 is a low melting ionic liquid under our test conditions and facilitates the phase transformations required in the hydrogen storage reaction, which no longer relies on a higher energy solid state reaction pathway. Further study showed that the 0.6 LiNH2 0.3 MgH2 0.1 LiBH4 formulation was very stable with respect to ammonia and diborane desorption, the observed desorption was from hydrogen. This result could not have been anticipated and was made possible by the efficiency of HT combinatorial methods. Investigation of the analogous LiNH2 LiBH4 CaH2 phase diagram revealed new reversible hydrogen storage materials 0.625 LiBH4 + 0.375 CaH2 and 0.375 LiNH2 + 0.25 LiBH4 + 0.375 CaH2 operating at 1 wt. % reversible hydrogen below 175 °C. Powder x-ray diffraction revealed a new structure for the spent materials which had not been previously observed. While the storage capacity was not impressive, an important aspect is that it boron appears to participate in a low temperature reversible reaction. The last major area of study also focused on activating boron-based materials in order to exploit the tremendous gravimetric capacity of LiBH4. A number of LiNH2 LiBH4 transition metal (TM) systems were investigated for the following reasons. No additional leads were discovered in this system. Another major project activity was the assembly of a high throughput synthesis system. The automated synthesizer was set up in a glovebox and was capable of handling liquids and powders and carrying out sealed block syntheses up to 250 °C. Unfortunately, the synthesizer could not handle the delivery of the fine powders required fro hydrogen storage applications. Although the powder delivery system was overhauled and redesigned several times, this problem was never remedied.« less