DOCSLIB.ORG

(12) United States Patent (10) Patent No.: US 9,174,853 B2 Arkles Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) United States Patent (10) Patent No.: US 9,174,853 B2 Arkles Et Al US009 174853B2 (12) United States Patent (10) Patent No.: US 9,174,853 B2 Arkles et al. (45) Date of Patent: Nov. 3, 2015 (54) METHOD FOR PRODUCING HIGH PURITY B01D 2257/304; B01D 2257/406; B01D GERMANE BY A CONTINUOUS OR 53/52; B01D 53/8612; B01D 53/8671; B01D SEM-CONTINUOUS PROCESS 2253/108; B01D 2256/16; B01D 2257/55 (71) Applicant: Gelest Technologies, Inc., Morrisville, USPC .......................................................... 438/685 PA (US) See application file for complete search history. (72) Inventors: Barry C. Arkles, Pipersville, PA (US); (56) References Cited George A. Timberlake, Jr., Gilbertsville, PA (US) U.S. PATENT DOCUMENTS 4,668,502 A 5, 1987 Russotti (73) Assignee: Gelest Technologies, Inc., Morrisville, 7,087,102 B2 8/2006 Withers, Jr. et al. PA (US) (Continued) (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS U.S.C. 154(b) by 0 days. CN 101486444. A T 2009 CN 1023908O8 A 3, 2012 (21) Appl. No.: 14/540,466 WO 2005.005673 A2 1, 2005 (22) Filed: Nov. 13, 2014 OTHER PUBLICATIONS Prior Publication Data Martin et al., “Gas Separation by pressure Swing adsorption' (65) advances in cryogenic engineering, prenum press, NY 1986. US 2015/O158738A1 Jun. 11, 2015 (Continued) Related U.S. Application Data Primary Examiner — Mark A Laurenzi (60) Provisional application No. 61/912,791, filed on Dec. (74) Attorney, Agent, or Firm — Panitch Schwarze Belisario 6, 2013. & Nadel LLP Int. C. (51) ABSTRACT HOIL 2L/214 (2006.01) (57) COIG 7/00 (2006.01) A continuous or semi-continuous process for producing a high purity germane includes (a) preparing a reaction mixture (Continued) containing hydrogen and crude germane and (b) separating (52) U.S. C. the hydrogen from the crude germane by a pressure Swing CPC ............ COIG 17/003 (2013.01); B0ID53/047 adsorption process. The pressure Swing adsorption process (2013.01); B0ID 53/0462 (2013.01); COIB results in a hydrogen-rich product stream and a germane-rich 3/56 (2013.01); COIB 6/06 (2013.01); COIG product stream. The method further includes (c) purifying the 17/00 (2013.01); F25J 3/08 (2013.01); B01D germane-rich product stream by continuous distillation 2253/108 (2013.01); B01D 2256/16 (2013.01); thereof to remove impurities therefrom and to produce a high BOID 2257/55 (2013.01) purity germane containing less than 0.1 Volume percent of (58) Field of Classification Search impurities. CPC ............... B01D 53/46; B01D 2253/10; B01D 2257/00; B01D 2257/20; B01D 2257/204; 13 Claims, 3 Drawing Sheets Refrigerant German to recovery Ret or disposal - A. impurities to Disposal 28 Hydrogen 24 Purge Gas - 20 22 ------------------ --- i regenerable Hydrogen | WacuumCompressor pump with & | AdsorberBalance for Dryer Ho RenovaA. PSA E. 8C y 12 ws s: Crude as Germane-Containing Compressor & g 2 Reaction Mixture refrigeration Digermane s g Drier Cotection Acid Solution 28 BaseSolution 30 Sub-surface diptube High Purity 1. Gerare Aqueous effluent Make Tank 32 US 9,174,853 B2 Page 2 (51) Int. Cl. OTHER PUBLICATIONS BOLD 53/04 (2006.01) Jolly, “The Preparation of the Volatile Hydrides of Groups IV-A and BOLD 53/047 (2006.01) V-A by Means of Aqueous Hydroborate'. Journal of the American F25.3/08 (2006.01) Chemical Society, vol. 83, pp. 335-337 (1961). COIB 3/56 (2006.01) Knaebel, et al., “Pressure Swing Adsorption: Development of an COIB 6/06 (2006.01) Equilibrium Theory for Gas Separations”, Chemical Engineering Science, vol. 40, pp. 2351-2360 (1985). References Cited Sircar et al., “Purification of Hydrogen by Pressure Swing Adsorp (56) tion', Separation Science and Technology, vol. 35, pp. 667-687 U.S. PATENT DOCUMENTS (2000). Int'l Search Report and Written Opinion issued Mar. 6, 2015 in Int’l 2005/019 1854 A1* 9/2005 Withers, Jr. ............. C22B 41.00 Application No. PCT/US2014/066640. 438,685 2008/0299.037 A1 12/2008 Tezock * cited by examiner U.S. Patent Nov. 3, 2015 Sheet 2 of 3 US 9,174,853 B2 U.S. Patent US 9,174,853 B2 JosseuduuOO uunnoe/\ duund US 9,174,853 B2 1. 2 METHOD FOR PRODUCING HGH PURITY BRIEF DESCRIPTION OF THE SEVERAL GERMANEBY A CONTINUOUS OR VIEWS OF THE DRAWINGS SEM-CONTINUOUS PROCESS The following detailed description of preferred embodi CROSS-REFERENCE TO RELATED 5 ments of the present invention will be better understood when APPLICATIONS read in conjunction with the appended drawing. For the pur poses of illustrating the invention, there is shown in the draw This application claims priority to U.S. Provisional Patent ing an embodiment which is presently preferred. It is under Application No. 61/912,791, filed on Dec. 6, 2013, entitled stood, however, that the invention is not limited to the precise “Method for Producing High Purity Germane by a Continu 10 arrangements and instrumentalities shown. In the drawings: FIG. 1 is a schematic flow diagram of the process for ous or Semi-Continuous Process, the entire contents of producing high purity germane in accordance with an which are incorporated by reference herein. embodiment of the present invention; and BACKGROUND OF THE INVENTION FIG. 2A is a schematic flow diagram of the generation and 15 purification steps of a process for producing high purity ger mane in accordance with an embodiment of the present inven This invention involves a method for producing high purity tion, prior to the distillation steps; and germane by a continuous or semi-continuous process. The FIG.2B is a schematic flow diagram of the distillation steps typical preferred commercial method for producing germane of a process for producing high purity germane in accordance is an aqueous borohydride reduction of germanium dioxide, most often using sodium borohydride or potassium borohy with an embodiment of the present invention. dride. Examples of this process may be found in U.S. Pat. No. DETAILED DESCRIPTION OF THE INVENTION 4,668,502 of Russotti; U.S. Pat. No. 7,087,102 of Withers et al.; and U.S. Patent Application Publication No. 2008/ According to the invention, a method is provided for gen O299.037 of TezOck. 25 erating and purifying germane (GeH) by a continuous or Russotti, Withers et al. and Tezock are all directed to the semi-continuous process. yield and purification of germane from germanium dioxide. Referring to FIGS. 1-2B, the method comprises producing In particular, Withers et al. disclose a method for purifying a a germane-containing reaction mixture by reacting one or germane fluid, produced by a cryogenic-trapping technique. more germanium-containing compounds such as, for However, the co-product of the reduction, namely hydrogen 30 example, germanium oxide (also known as germanium diox gas, is not considered or discussed in detail in Russotti. With ide), alkali metal germanates (such as potassium germanate), ers et al. or Tezock. and/or compounds formed in situ from germanium tetrachlo In general, in Such reductions, impure germane leaves the ride, germanium or various germanides, with one or more primary process reactor entrained in a hydrogen gas stream at hydrogen-containing reducing agents in a reactor 10 to pro a volume concentration of approximately 2% to 20%. The 35 vide a reaction mixture. Preferably, the hydrogen-containing presence of the co-product hydrogen gas presents enormous reducing agent is a borohydride. Examples of reducing agents difficulties for high Volume production of germane, particu that may be used include Sodium borohydride, potassium larly if the purification is completed in a batch-wise low borohydride, lithium borohydride. The various components temperature condensation of the germane out of the hydrogen may be mixed together in ratios known in conventional reac stream. An article by W. Jolly published in the Journal of the 40 tion methods. Also, the various components may be added American Chemical Society discusses the formation of directly to the reactor 10 with good turbulent mixing or, hydrogen and removal of the germane from the hydrogen gas alternatively, may be fed through a static mixer (not shown) stream by cryogenic trapping (W. Jolly, JAm. Chem. Soc., V. before entering the reactor 10. 83, p. 335 (1961)). The reaction is preferably conducted in an aqueous While methods for removal of the hydrogen gas, such as 45 medium under conventional temperature and pressure condi membrane separation and absorption, are alternatives which tions. However, it will be understood that the reaction may may potentially allow for continuous purification of the ger instead be conducted in a non-aqueous medium, Such as an mane, such methods have not to date been reduced to practice. organic solvent, or utilizing a combination of aqueous and Accordingly, a method for producing high purity germane on non-aqueous media. Preferably, the method comprises pro a semi-continuous basis without the need for low temperature 50 ducing a germane-containing reaction mixture by borohy process conditions, such as those required for cryogenic trap dride reduction of germanium oxide or its hydrate germanium ping processes, would be desirable. hydroxide in an aqueous solution. However, it will be under stood by those skilled in the art that any known processes for BRIEF SUMMARY OF THE INVENTION producing germane-containing mixtures may be utilized. 55 The reaction mixture primarily contains germane (GeH) One aspect of the present invention is directed to a method and hydrogen (H), as well as carbon dioxide (CO), water for producing high purity germane containing less than 0.1 vapor (H2O), digeonane (GeH) and possibly other trace Volume percent of impurities. The method comprises: (a) gases and impurities. More particularly, in one embodiment, preparing a reaction mixture containing hydrogen and crude the reaction mixture contains 80% or greater, and more pref germane; (b) separating the hydrogen from the crude ger 60 erably 80% to 98% by volume hydrogen gas with the balance mane by a pressure Swing adsorption process, the pressure being germane, carbon dioxide, water vapor, digermane and Swing adsorption process resulting in a hydrogen-rich prod other trace gases and impurities.
Load more

Recommended publications
  • Standard Thermodynamic Properties of Chemical
    STANDARD THERMODYNAMIC PROPERTIES OF CHEMICAL SUBSTANCES ∆ ° –1 ∆ ° –1 ° –1 –1 –1 –1 Molecular fH /kJ mol fG /kJ mol S /J mol K Cp/J mol K formula Name Crys. Liq. Gas Crys. Liq. Gas Crys. Liq. Gas Crys. Liq. Gas Ac Actinium 0.0 406.0 366.0 56.5 188.1 27.2 20.8 Ag Silver 0.0 284.9 246.0 42.6 173.0 25.4 20.8 AgBr Silver(I) bromide -100.4 -96.9 107.1 52.4 AgBrO3 Silver(I) bromate -10.5 71.3 151.9 AgCl Silver(I) chloride -127.0 -109.8 96.3 50.8 AgClO3 Silver(I) chlorate -30.3 64.5 142.0 AgClO4 Silver(I) perchlorate -31.1 AgF Silver(I) fluoride -204.6 AgF2 Silver(II) fluoride -360.0 AgI Silver(I) iodide -61.8 -66.2 115.5 56.8 AgIO3 Silver(I) iodate -171.1 -93.7 149.4 102.9 AgNO3 Silver(I) nitrate -124.4 -33.4 140.9 93.1 Ag2 Disilver 410.0 358.8 257.1 37.0 Ag2CrO4 Silver(I) chromate -731.7 -641.8 217.6 142.3 Ag2O Silver(I) oxide -31.1 -11.2 121.3 65.9 Ag2O2 Silver(II) oxide -24.3 27.6 117.0 88.0 Ag2O3 Silver(III) oxide 33.9 121.4 100.0 Ag2O4S Silver(I) sulfate -715.9 -618.4 200.4 131.4 Ag2S Silver(I) sulfide (argentite) -32.6 -40.7 144.0 76.5 Al Aluminum 0.0 330.0 289.4 28.3 164.6 24.4 21.4 AlB3H12 Aluminum borohydride -16.3 13.0 145.0 147.0 289.1 379.2 194.6 AlBr Aluminum monobromide -4.0 -42.0 239.5 35.6 AlBr3 Aluminum tribromide -527.2 -425.1 180.2 100.6 AlCl Aluminum monochloride -47.7 -74.1 228.1 35.0 AlCl2 Aluminum dichloride -331.0 AlCl3 Aluminum trichloride -704.2 -583.2 -628.8 109.3 91.1 AlF Aluminum monofluoride -258.2 -283.7 215.0 31.9 AlF3 Aluminum trifluoride -1510.4 -1204.6 -1431.1 -1188.2 66.5 277.1 75.1 62.6 AlF4Na Sodium tetrafluoroaluminate
    [Show full text]
  • University of California Riverside
    UNIVERSITY OF CALIFORNIA RIVERSIDE Thermal Decomposition of Molecules Relevant to Combustion and Chemical Vapor Deposition by Flash Pyrolysis Time-of-Flight Mass Spectrometry A Dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry by Jessy Mario Lemieux December 2013 Dissertation Committee: Dr. Jingsong Zhang, Chairperson Dr. Christopher Bardeen Dr. David Bocian Copyright by Jessy Mario Lemieux 2013 The Dissertation of Jessy Mario Lemieux is approved: Committee Chairperson University of California, Riverside ACKNOWLEDGMENTS Professor Jingsong Zhang Dr. Steven Chambreau Dr. Kevin Weber Paul Jones Jeff Lefler Mike Fournier Stan Sheldon Professor Christopher Bardeen Professor David Bocian iv DEDICATION This work is dedicated to my parents who taught me the value of curiosity and learning and have always been there for me. v ABSTRACT OF THE DISSERTATION Thermal Decomposition of Molecules Relevant to Combustion and Chemical Vapor Deposition by Flash Pyrolysis Time-of-Flight Mass Spectrometry by Jessy Mario Lemieux Doctor of Philosophy, Graduate Program in Chemistry University of California, Riverside, December 2013 Dr. Jingsong Zhang, Chairperson Flash pyrolysis coupled with vacuum-ultraviolet photoionization time-of-flight mass spectrometry was used to study the thermal decomposition mechanisms of molecules relevant to fuel combustion and the chemical vapor deposition (CVD) of SiGe, SiC, and GeC. For combustion research, the thermal decomposition of benzyl radical, n- alkanes CnH2n+2 (n = 5-8 and 10), 1-butyl radical, and 1-pentyl radical was performed. Benzyl was confirmed to decompose primarily by ejection of H atom after significant isomerization with loss of methyl observed as a minor decomposition pathway.
    [Show full text]
  • CRC Handbook
    $0%"5",&:7"-6&4'035)&3.0%:/".*$4 5IF$PNNJUUFFPO%BUBGPS4DJFODFBOE5FDIOPMPHZ $0%"5" 1B CBS 4FFUIFSFGFSFODFGPSJOGPSNBUJPOPOUIFEFQFOEFODFPG IBTDPOEVDUFEBQSPKFDUUPFTUBCMJTIJOUFSOBUJPOBMMZBHSFFEWBMVFT HBTQIBTFFOUSPQZPOUIFDIPJDFPGTUBOEBSETUBUFQSFTTVSF GPS UIF UIFSNPEZOBNJD QSPQFSUJFT PG LFZ DIFNJDBM TVCTUBODFT 4VCTUBODFTBSFMJTUFEJOBMQIBCFUJDBMPSEFSPGUIFJSDIFNJDBMGPS 5IJT UBCMF QSFTFOUT UIF GJOBM SFTVMUT PG UIF QSPKFDU 6TF PG UIFTF NVMBTXIFOXSJUUFOJOUIFNPTUDPNNPOGPSN SFDPNNFOEFE JOUFSOBMMZ DPOTJTUFOU WBMVFT JT FODPVSBHFE JO UIF 5IFUBCMFJTSFQSJOUFEXJUIQFSNJTTJPOPG$0%"5" BOBMZTJT PG UIFSNPEZOBNJD NFBTVSFNFOUT EBUB SFEVDUJPO BOE QSFQBSBUJPOPGPUIFSUIFSNPEZOBNJDUBCMFT 5IFUBCMFJODMVEFTUIFTUBOEBSEFOUIBMQZPGGPSNBUJPOBU 3FGFSFODF , UIFFOUSPQZBU, BOEUIFRVBOUJUZ )¡ , o )¡ $PY +% 8BHNBO %% BOE.FEWFEFW 7" $0%"5",FZ7BMVFTGPS "WBMVFPGJOUIFȂ G)¡DPMVNOGPSBOFMFNFOUJOEJDBUFTUIFSFGFS 5IFSNPEZOBNJDT )FNJTQIFSF1VCMJTIJOH$PSQ /FX:PSL FODFTUBUFGPSUIBUFMFNFOU5IFTUBOEBSETUBUFQSFTTVSFJT ȂG ) ¡ , 4¡ , ))¡ , ¡ o o o o 4VCTUBODF 4UBUF L+ NPM + , NPM L+ NPM "H DS "H H "H BR "H$M DS o "M DS "M H "M BR o o "M' DS o "M 0 DS DPSVOEVN o "S H # DS SIPNCJD # H #' H o #0 DS o #F DS #F H #F0 DS o #S H #S o BR o #S M #S H $ DS HSBQIJUF $ H $0 H o $0 H o $0 BR VOEJTTPD o o $0 BR o o $B DS $B H $B BR o o $B0 DS o $E DS $E H $E BR o o $E0 DS o $E40 r) 0 DS o $M H $M o BR o o $M0 BR o $M H $T DS $T H $T BR o $V DS $0%"5",FZ7BMVFTGPS5IFSNPEZOBNJDT ȂG ) ¡ , 4¡
    [Show full text]
  • The Preparation and Properties of Derivatives of Germane
    THE PREPARATION AND PROPERTIES OF DERIVATIVES OF GERMANE by James Edward Griffiths, M.Sc. A Thesis submitted to the Faculty of Graduate Studies and Research of McGill University in partial fulfil­ ment of the requirements for the degree of Doctor of Philosophy. From the Inorganic Chemistry Laboratory under the supervision of Dr. M. Onyszchuk McGill University, Montreal, Canada. October, 1958 ACKNOWLEDGEMENTS The author wishes to express his gratitude to Dr. M. Onyszchuk for his advice and encourage.tœnt which made this investigation possible. The author is indebted to Dr. A. Taurins for his instruction in the use of the Infrared Spectrophotometer. Grateful acknowledgemmt is made to the National Research Council of Canada for financial assistance during the course of this investigation in the form of two studentships. TABLE OF CONTENTS INTRODUCTION ••••••••••••••••••••••••••••••••••••••••••••••••••••• 1 OJTLINE OF THE RESEARCH PROBLEM .................................. 12 EXPERIMENTAL ..................................................... 14 RESULTS .......................................................... 31 Reactions of gerrnwl chloride •••••••••••••••••••••••••••• 31 Preparation of Methylgermane •••••••••••••••••••••••••••• 41 Preparation of Methyldich1orogermane •••••••••••••••••••• 49 Preparation of Methylbromogermane ••••••••••••••••••••••• 55 Reactions of Methylbromogermane ••••••••••••••••••••••••• 58 Preparation of Trimethylchlorogermane ••••••••••••••••••• 63 Preparation of Trimethylbramogermane •••••••••••••••••••• 67 Preparation
    [Show full text]
  • This Table Gives the Standard State Chemical Thermodynamic Properties of About 2500 Individual Substances in the Crystalline, Liquid, and Gaseous States
    STANDARD THERMODYNAMIC PROPERTIES OF CHEMICAL SUBSTANCES This table gives the standard state chemical thermodynamic properties of about 2500 individual substances in the crystalline, liquid, and gaseous states. Substances are listed by molecular formula in a modified Hill order; all substances not containing carbon appear first, followed by those that contain carbon. The properties tabulated are: DfH° Standard molar enthalpy (heat) of formation at 298.15 K in kJ/mol DfG° Standard molar Gibbs energy of formation at 298.15 K in kJ/mol S° Standard molar entropy at 298.15 K in J/mol K Cp Molar heat capacity at constant pressure at 298.15 K in J/mol K The standard state pressure is 100 kPa (1 bar). The standard states are defined for different phases by: • The standard state of a pure gaseous substance is that of the substance as a (hypothetical) ideal gas at the standard state pressure. • The standard state of a pure liquid substance is that of the liquid under the standard state pressure. • The standard state of a pure crystalline substance is that of the crystalline substance under the standard state pressure. An entry of 0.0 for DfH° for an element indicates the reference state of that element. See References 1 and 2 for further information on reference states. A blank means no value is available. The data are derived from the sources listed in the references, from other papers appearing in the Journal of Physical and Chemical Reference Data, and from the primary research literature. We are indebted to M. V. Korobov for providing data on fullerene compounds.
    [Show full text]
  • Recent Advances of Group 14 Dimetallenes and Dimetallynes in Bond Activation and Catalysis Cite This: Chem
    Chemical Science View Article Online MINIREVIEW View Journal | View Issue Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis Cite this: Chem. Sci.,2021,12, 2001 All publication charges for this article Franziska Hanusch, Lisa Groll and Shigeyoshi Inoue * have been paid for by the Royal Society of Chemistry Since the first heavy alkene analogues of germanium and tin were isolated in 1976, followed by West's disilene in 1981, the chemistry of stable group 14 dimetallenes and dimetallynes has advanced immensely. Recent developments in this field veered the focus from the isolation of novel bonding motifs to mimicking transition metals in their ability to activate small molecules and perform catalysis. The potential of these homonuclear multiply bonded compounds has been demonstrated numerous Received 8th June 2020 times in the activation of H ,NH,CO and other small molecules. Hereby, the strong relationship Accepted 3rd August 2020 2 3 2 between structure and reactivity warrants close attention towards rational ligand design. This minireview DOI: 10.1039/d0sc03192e provides an overview on recent developments in regard to bond activation with group 14 dimetallenes rsc.li/chemical-science and dimetallynes with the perspective of potential catalytic applications of these compounds. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Introduction heavy p block elements in general) cannot form stable multiple bonds, was widely accepted.1–3 This rule was, however, Much of the early advances in heavier group 14 chemistry stem unequivocally disproved with the rst heavy alkene analogues from the vast richness of organic compounds and the motiva- of germanium and tin by Lappert in 1976, followed by West's tion of mimicking those with the heavier congeners of carbon.
    [Show full text]
  • Synthetic, Physical, and Photolytic Properties of Linear, Branched, and Cyclic Oligogermanes
    SYNTHETIC, PHYSICAL, AND PHOTOLYTIC PROPERTIES OF LINEAR, BRANCHED, AND CYCLIC OLIGOGERMANES By SANGEETHA P. KOMANDURI Bachelor of Science in Specialized Chemistry University of Illinois at Urbana-Champaign Urbana-Champaign, Illinois 2013 Submitted to the Faculty of the Graduate College of the Oklahoma State University in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY July, 2018 SYNTHETIC, PHYSICAL, AND PHOTOLYTIC PROPERTIES OF LINEAR AND CYCLIC OLIGOGERMANES Dissertation Approved: Dr. Charles S. Weinert Dissertation Adviser Dr. Allen W. Apblett Dr. Richard A. Bunce Dr. Toby L. Nelson Dr. John N. Veenstra ii ACKNOWLEDGEMENTS This work is dedicated to the many people who have supported and helped me during my time as a graduate student. First and foremost, I’d like to thank my committee members Dr. Bunce, Dr. Apblett, Dr. Nelson, and Dr. Veenstra for their assistance and the knowledge they have imparted onto me over the years. In addition to their help in the classroom, their advice has been vital. Of course the biggest influence on my time here has been my research advisor Dr. Weinert. He has provided me with the mentorship and practical knowledge which I have used daily in and outside of the lab. None of this work could have been completed without his valuable guidance and consistent help, all which has molded me into an independent researcher. Within the laboratory and the chemistry department at OSU, my colleges, friends, and staff members have given me great support during the technical aspects of my research. My lab mates Alex Shumaker, Miguel Leal, and Ardalan Hayatifar are the research family who encouraged, taught, and gave me the structural criticism to push me further and improve my skills.
    [Show full text]
  • Rational Synthesis and Properties of New Long-Chain Linear Oligomeric Germanium Compounds
    RATIONAL SYNTHESIS AND PROPERTIES OF NEW LONG-CHAIN LINEAR OLIGOMERIC GERMANIUM COMPOUNDS By KIMBERLY DIANE ROEWE Bachelor of Science in Chemistry Southwestern Oklahoma State University Weatherford, Oklahoma 2009 Submitted to the Faculty of the Graduate College of the Oklahoma State University in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY May, 2014 RATIONAL SYNTHESIS AND PROPERTIES OF NEW LONG-CHAIN LINEAR OLIGOMERIC GERMANIUM COMPOUNDS Dissertation Approved: Dr. Charles S. Weinert Dissertation Adviser Dr. Allen Apblett Dr. Richard Bunce Dr. Nicholas Materer Dr. Ulrich Melcher ii Name: KIMBERLY DIANE ROEWE Date of Degree: MAY, 2014 Title of Study: RATIONAL SYNTHESIS AND PROPERTIES OF NEW LONG-CHAIN LINEAR OLIGOMERIC GERMANIUM COMPOUNDS Major Field: CHEMISTRY Abstract: Germanium compounds with single germanium-germanium bonds contain interesting optical and electronic properties such as absorption within the UV/visible range and conductivity, which can also be seen in other heavier Group 14 oligomers. In comparison to the tin and silicon analogues, the reported methods for synthesizing the germanium compounds are minimal. The longest linear oligogermane completely characterized, including its structure, is the perphenylated pentagermane, Ge5Ph12. Due to their inherent properties, it is of interest to synthesize longer, linear oligomeric germanium compounds. It is proposed that if a long enough chain of germanium atoms is obtained, properties characteristic of polygermane species may also be achieved. Protection/deprotection strategies, using a masked Ge – H bond, were initially attempted, however only a linear pentagermane could be obtain. All products were also liquid, preventing complete characterization using X-ray crystallography. After synthetic efforts were shifted away from the protection/deprotection strategies, a successful strategy was achieved starting with a cyclic germanium species.
    [Show full text]
  • Vertex Edge Brochure
    ADVANCED LOW-LEVEL DETECTION With a low cost of ownership Honeywell Vertex™ Edge THE RELIABLE ADVANCED ENGINEERING PERFORMANCE FOR ACCURATE GAS AND VERSATILITY OF DETECTION HONEYWELL VERTEX™ — As the pioneer of Chemcassette® gas analyzers, WITH A LOWER COST AND we engineered Honeywell Vertex™ Edge to EASIER EXPERIENCE deliver an enhanced level of reliability. Introducing Honeywell Vertex™ Edge. This A CLEARLY VISIBLE STAIN — FOR LOW-LEVEL DETECTION YOU CAN COUNT ON With Honeywell Chemcassette® technology, the density of the stain on the tape is proportional to the concentration cost-effective toxic gas monitoring system of the gas, so visibility of the stain is critical. That’s why Honeywell Vertex™ Edge, unlike competing tape-based detects the ultrasensitive gases in your high- systems, generates a clear, easy-to-view stain that matches the severity of the gas release. With this precision, the tech operations, helping you protect people optical scanners in Honeywell Vertex™ Edge can measure the stain accurately and trigger the right alarm. and assets while reducing fab downtime. The Honeywell Vertex™ Edge platform delivers what you love about the original Honeywell Vertex™ system — plus additional features HONEYWELL VERTEX™ EDGE to make safety more affordable and straightforward: • Flexible gas sampling Monitor up to 40 toxic gases — all from one modular system. Start with as few as eight sampling points for continuous gas detection, and add up to 72 sampling points as your requirements change. Place OTHER SYSTEMS each point up to 400 feet (120 meters) away for ample reach. • The enhanced standard of accuracy and reliability Honeywell Vertex™ Edge uses authentic Chemcassette® technology, which shows the presence of gas quickly and definitively with a physical All stains are not created equal record — evidenced by a color change on chemically treated tape.
    [Show full text]
  • Metal Organics 3000B 9/11/10 10:02 AM Page 93
    1021_Metal-Organics 4000B_Metal Organics 3000B 9/11/10 10:02 AM Page 93 Gelest, Inc. Applications of Germanium Compounds Andrew E. Wille and Barry Arkles Gelest Inc. Germanium compounds have emerged as critically important materials in the fabrication of microelectronics, optics and sensors. Potential new applications in organic transformations and polymer synthesis have also been reported. This article highlights some of the chemistry associated with these applications. It also compares and contrasts the chemistry of germanium with the more widely understood chemistry of silicon. For readers with a deeper interest in the chemistry of germanium, comprehensive reviews provide a detailed description.1,2,3,4,5 Metallic Germanium and Metallization Chemistry Germanium is a semiconductor. In fact, germanium was the first material to be fabricated into practical semi- conductor devices, diodes. As a consequence, a significant body of literature relating to the electrical properties of germanium has developed. The mobility of holes in germanium is greater than that of silicon and of any other common semiconductor. The hole and electron mobilities are closer in germanium than other semiconductors, particularly at low temperatures. This has made germanium an attractive candidate for high performance CMOS technology. In high speed digital communications associated with broad-band and cell-phones, SiGe films are used to fabricate heterojunction bipolar transistors (HBTs). In other high speed applications SiGe films are deposited as molecular films which act as templates for the epitaxial deposition of silicon. The resulting lattice mismatch creates a strained silicon layer which exhibits enhanced electron mobility, providing improved device performance. SiGe technology has the potential to replace GaAs in many applications.
    [Show full text]
  • Low Temperature Epitaxy Growth and Kinetic Modeling of Sige for Bicmos Application
    Royal Institute of Technology Low Temperature Epitaxy Growth and Kinetic Modeling of SiGe for BiCMOS Application Arash Salemi Master Thesis Supervisor: Docent Henry Radamson Co-Supervisor: Dr. Mohammadreza Kolahdouz Examiner: Prof. Mikael Östling KTH, Royal Institute of technology Department of Integrated Devices and Circuits Stockholm, Sweden 2011 Abstract There is an ambition of continuously decreasing thermal budget in CMOS and BiCMOS processing, thus low temperature epitaxy (LTE) (350-650°C) with chemical vapor deposition (CVD) technique in order to have faster process with low cost. One of the growth issues at low temperatures is gas quality where the oxygen and moisture contamination becomes critical for the epilayers quality. If the level amount of contamination is not controlled, the silicon dioxide islands are formed and the oxygen level in the film will be high. This thesis is focused on two different aspects of “LTE”. The first focus of this thesis was to identify the effect of contamination on the strain and quality of the SiGe epilayers (prior and during epitaxy). The samples in this study were exposed to different oxygen and moisture partial pressures (2ppb-250 ppm range) at different exposure temperatures (350-650°C). The results revealed that presence of contamination even at low ranges (2-100 ppb) is not negligible and affects the strain. Parameters such as O2 exposure temperature and partial pressure, and SiGe layer’s growth temperature impacted the oxygen level and strain in the films. For oxygen levels below 100 ppb, High Resolution Scanning Microscopy (HRSEM) could not detect very small oxide island. By increasing the O2 partial pressure well above 100 ppb, the oxide islands are saturated at 0.08 µm2.
    [Show full text]
  • SPM Gas Capability List
    Gas Capability List ® for Chemcassette -based Monitors Gas Capability List T/N 971037 August, 2000 This technical note provides a listing of the Lowest Detectable Limit (LDL) and Full Scale (FS) for each Chemcassette area monitor. The table lists each gas calibration by instrument. Zellweger Analytics continues to develop new calibrations, detection ranges, and specialized alarm ranges. Contact your Zellweger representative for any specialized ranges not listed. Contents Gas Family Page(s) Amines 2 Diisocyanate 3 Hydrazines 4 Hydrides 5-6 Mineral Acids 7 Notes 8 technical note 971037 (8-00) - Page 1 of 8 Gas Capabilities List, Chemcassette®-Based Gas Monitors Single-Point Monitors Multi-Point Monitors Model IsoLogger® TLD SPM & SPM EGM System-16 CM4 Gas Name (Formula) 7100 ChemKey ChemKey Amines Family Ammonia (NH3) 2.5-200.0 ppm 2.6-75.0 ppm 2.6-75.0 ppm 4-250.0 ppm Ammonia-II 1.3-250.0 ppm 2.6-75.0 ppm 2.6-75.0 ppm 2.6-75.0 ppm 2.8-75.0 ppm 3-75 ppm Ammonia-II - low level 0.1-75.0 ppm *0.5-30.0 ppm Ammonia-II - ultra dry 2.6-75.0 ppm n-Butylamine (N-BA) 0.5-20.0 ppm 0.4-12.0 ppm 0.4-12.0 ppm 0.4-12.0 ppm Dimethylamine (DMA) - low level 0.1-6 ppm 0.1-6.0 ppm Methylene Dianiline (MDA) 3-60 ppb 3-60 ppb p-Phenylene Diamine (PPD) 4-200 ppb 2-60 ppb 2-60 ppb Toluene Diamine (TDA) 4-60 ppb 4-60 ppb Triethylamine (TEA) *0.5-15.0 ppm 0.3-35 ppm Trimethylamine (TMA) 2.4-100.0 ppm 1.1-30.0 ppm 1.1-30.0 ppm 1.1-30.0 ppm 2.9-100.0 ppm Bromine (Br2) 18-1000 ppb 11-300 ppb 11-300 ppb 11-300 ppb 15-1000 ppb Chlorine (Cl2) 0.2-10.0 ppm 0.1-3.0 ppm 0.1-3.0
    [Show full text]