WO2014105272A1 - Élimination de composés oxygénés à partir de composés organométalliques - Google Patents

Élimination de composés oxygénés à partir de composés organométalliques Download PDF

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Publication number
WO2014105272A1
WO2014105272A1 PCT/US2013/069110 US2013069110W WO2014105272A1 WO 2014105272 A1 WO2014105272 A1 WO 2014105272A1 US 2013069110 W US2013069110 W US 2013069110W WO 2014105272 A1 WO2014105272 A1 WO 2014105272A1
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Prior art keywords
organometallic compound
compound
hydrated
organometallic
alkyl group
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PCT/US2013/069110
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English (en)
Inventor
Samuel A. Sangokoya
Jamie R. Strickler
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Albemarle Corp
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Albemarle Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/062—Al linked exclusively to C

Definitions

  • This invention relates to removal of oxygenates from organometallic compounds, especially from trihydrocarbyl organometallic compounds.
  • Hydrocarbyl compounds of aluminum, gallium, and indium, especially the trialkyl compounds are useful in electronics applications, in particular for chemical vapor deposition (CVD) of aluminum, indium, or gallium and for aluminum-containing, indium-containing, or gallium-containing films.
  • the substances used must be relatively free of impurities.
  • impurities include organosilicon, alkylated metal alkoxides, other alkylated metallic compounds such as hydrides or halides of Ti, Fe, Cu Na, etc., and hydrocarbon solvents. Of these the most difficult ones to remove are the alkylated metal alkoxides, which are often inevitably formed, even during a purification process.
  • U.S. 4,650,895 describes addition of water to a solution of an organometallic compound, especially to less reactive higher alkylated organometallic compounds, to effect partial hydrolysis of the organometallic compound and thereby afford removal of metallic impurities from the organometallic compound.
  • TMA trimethylaluminum
  • GB 2432364 to Rohm and Haas describes the removal of oxygenates from R 3 AI in the presence of a catalyst composition (AICI 3 , KF, etc.) and a higher alkylaluminum.
  • Oxygen if present in any of the aluminum, gallium, or indium source compounds, becomes incorporated into the crystal lattice of the film being grown, where the oxygen interferes with the electronic behavior of the film. Accordingly, methods for providing organometallic compounds having very low oxygen content are desired.
  • This invention provides processes for removing oxygenated impurities from organometallic compounds.
  • the process is straightforward, effective, and involves relatively inexpensive reagents.
  • the oxygenated impurities can be removed without introducing substances that are difficult to separate from the organometallic compounds.
  • An embodiment of this invention is a process for removing oxygenated impurities from an organometallic compound.
  • the process is conducted in an inert environment, and comprises contacting the organometallic compound and at least one deoxygenating agent, to form a mixture comprising a deoxygenated organometallic compound; and separating at least a portion of the deoxygenated organometallic compound from any solids present in said mixture to form a purified organometallic compound.
  • the deoxygenating agent is either a hydrated inorganic compound or a hydrated organic compound, and the organometallic compound is represented by the formula
  • M is aluminum, gallium, or indium
  • each R is, independently, a hydrogen atom, a C1-C12 alkyl group, a C 6 -Ci4 aryl group, or a C7-C16 aryl-alkyl group, with the proviso that at least one of R is not a hydrogen atom.
  • the inert environment in which the processes of this invention are conducted is a moisture-free, oxygen free environment such as argon, nitrogen or helium. It is preferred that the components used in the processes of this invention as well as the resultant products of the processes be handled in an inert environment.
  • the operations described herein are conducted under conventional inert atmospheres using suitably anhydrous materials.
  • the term "substantial absence” indicates that the substances or types of substances, except for adventitious impurities, are not present during, or introduced into, the processes of this invention.
  • exposure of organometallic compounds to molecular oxygen ((3 ⁇ 4) forms hydrocarbyl metal hydrocarbyloxides (e.g. , an alkyl aluminum alkoxide) from the at least some of the organometallic compounds.
  • hydrocarbyl metal hydrocarbyloxides e.g. , an alkyl aluminum alkoxide
  • R 3 M some of the R groups react with O2 to form OR groups (oxygenates).
  • the deoxygenating agent reacts directly with or complexes the hydrocarbyl metal hydrocarbyloxides and/or forms a small amount of aluminoxanes, galloxanes, or indinoxanes, which are believed to sequester hydrocarbyl metal hydroc arbyloxides .
  • This invention provides processes for removing oxygenated impurities from an organometallic compound.
  • the process is conducted in an inert environment, and comprises contacting the organometallic compound and at least one deoxygenating agent, to form a mixture comprising a deoxygenated organometallic compound; and separating at least a portion of the deoxygenated organometallic compound from any solids present in said mixture to form a purified organometallic compound.
  • the deoxygenating agent is either a hydrated inorganic compound or a hydrated organic compound.
  • the deoxygenating agents used in the practice of this invention are at least one hydrated inorganic compound and/or at least one hydrated organic compound. These compounds generally lose their water of hydration relatively easily.
  • the hydrated inorganic compounds are hydrates of alkali metal hydroxides or alkaline earth metal hydroxides, hydrates of inorganic salts, and hydrated or partially hydrated inorganic oxides.
  • Suitable hydrated alkali metal hydroxides or alkaline earth metal hydroxides include lithium hydroxide monohydrate, sodium hydroxide monohydrate and dihydrate, potassium hydroxide dihydrate, barium hydroxide octahydrate, calcium hydroxide hydrates, magnesium hydroxide hydrates, and cesium hydroxide monohydrate, and the like.
  • Preferred hydroxides are the alkali metal hydroxides, especially lithium hydroxide monohydrate.
  • Suitable hydrated inorganic salts include hydrated sulfate salts and hydrated chlorides, such as hydrated copper sulfate, hydrated aluminum sulfate, hydrated iron(III) sulfate, hydrated lithium chloride, hydrated aluminum chloride, and the like.
  • Suitable hydrated or partially hydrated inorganic oxides include hydrates of alumina, silica, aluminosilicates (zeolites or molecular sieves), and the like. Molecular sieves with larger pore sizes (e.g. , 5 A or 10A) are preferred. A preferred inorganic oxide is alumina (wet alumina).
  • Hydrated organic compounds include gas hydrates and wet hydrocarbons.
  • Gas hydrates suitable for use in this invention include hydrated carbon dioxide, hydrated methane, hydrated ethane, hydrated propane, hydrated isobutane, and the like.
  • Wet hydrocarbons that can be used in the practice of this invention include hydrated pentane, hydrated cyclopentane, hydrated hexanes, hydrated octane, hydrated benzene, hydrated toluene, and the like.
  • the use of gas hydrates and/or certain wet hydrocarbons may introduce impurities that are difficult to separate from the organometallic compound.
  • the organometallic compound is represented by the formula
  • M is aluminum, gallium, or indium
  • each R is, independently, a hydrogen atom, a C1-C12 alkyl group, a C 6 -Ci4 aryl group, or a C7-C16 aryl-alkyl group, with the proviso that at least one of R is not a hydrogen atom.
  • the organometallic compound is represented by the formula R 3 M in which M is aluminum, gallium, or indium, preferably aluminum; and each R is, independently, a hydrogen atom, a Ci-Ci 2 alkyl group, a C 6 -Ci4 aryl group with or without one or more alkyl substituents, or a C7-C16 aryl-alkyl group with or without one or more alkyl substituents, with the proviso that at least one of R is not a hydrogen atom.
  • the alkyl groups may be straight-chain, branched, or cyclic, preferably a straight-chain.
  • R is preferably a Ci- C12 alkyl group, especially a Ci-C 6 alkyl group, more preferably a methyl or ethyl group, especially a methyl group.
  • Suitable organometallic compounds when M is aluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tripentylaluminum, tricyclopentylaluminum, trihexylaluminum, tricyclohexylaluminum, tri(methylcyclohexyl)aluminum, triheptylaluminum, trioctylaluminum, trinonylaluminum, tridecylaluminum, tri(undecyl)aluminum, tri(dodecyl)aluminum, triphenylaluminum, tritolylaluminum, trixylylaluminum, tri(ethylphenyl)aluminum, trinaphthylaluminum, tribenzylaluminum, dimethylaluminum hydride, diethylaluminum hydride, methylaluminum dihydr
  • Suitable organometallic compounds when M is gallium include trimethylgallium, triethylgallium, tripropylgallium, triisobutylgallium, tripentylgallium, tricyclopentylgallium, trihexylgallium, tricyclohexylgallium, tri(methylcyclohexyl)gallium, triheptylgallium, trioctylgallium, trinonylgallium, tridecylgallium, tri(undecyl)gallium, tri(dodecyl)gallium, triphenylgallium, tritolylgallium, trixylylgallium, tri(ethylphenyl)gallium, trinaphthylgallium, tribenzylgallium, dimethylgallium hydride, diethylgalllium hydride, methylgallium dihydride, ethy
  • Suitable organometallic compounds when M is indium include trimethylindium, triethylindium, tripropylindium, triisobutylindium, tripentylindium, tricyclopentylindium, trihexylindium, tricyclohexylindium, tri(methylcyclohexyl)indium, triheptylindium, trioctylindium, trinonylindium, tridecylindium, tri(undecyl)indium, tri(dodecyl)indium, triphenylindium, tritolylindium, trixylylindium, tri(ethylphenyl)indium, trinaphthylindium, tribenzylindium, dimethylindium hydride, diethylindium hydride, methylindium dihydride, ethylindium dihydride, dipropylindium hydride, diisobutylindium hydride, isobutylindium dihydride, dicyclohex
  • the organometallic compounds in the process of this invention typically have less than about 5 wt , preferably less than 2.5 wt , more preferably less than 1 wt , still more preferably less than about 0.5 wt of metallic impurities, and most preferably less than about 0.25 wt of metallic impurities, which metallic impurities generally include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and the like.
  • the amount of deoxygenating agent depends on the amount of oxygen-containing impurities in the organometallic compound, and the amount of water in the deoxygenating agent.
  • the deoxygenating agent is generally used in an amount of about 30 wt or less, e.g. , about 0.1 wt to about 30 wt , preferably about 5 wt or less, e.g. , 0.1 wt to about 5 wt , and more preferably about 3 wt or less, e.g. , about 0.1 wt to about 3 wt , relative to the organometallic compound.
  • the deoxygenating agent is still more preferably about 0.25 wt to about 1.5 wt relative to the organometallic compound.
  • the amount refers to the total amount of deoxygenating agent(s) used. As more deoxygenating agent is used, more of the organometallic compound may be lost. Thus it is advantageous to use as little deoxygenating agent as possible. While larger amounts of deoxygenating agent are more likely to remove all of the oxygen-containing impurities, as more deoxygenating agent is used, more of the organometallic compound is consumed.
  • the temperature is generally in the range of about -20°C to about 140°C.
  • the temperature is in the range of about -5°C to about 40°C, more preferably in the range of about 5°C to about 30°C.
  • Ambient temperatures about 18°C to about 25 °C are often preferred.
  • the processes of this invention are conducted in the absence of solvent, because any solvent introduced will need to be separated from the organometallic compound.
  • there is less than about 0.5 mole of solvent per mole of organometallic compound more preferably, less than about 0.25 mole, still more preferably, less than about 0.10 mole, even more preferably less than about 0.05 mole, especially preferably less than about 0.01 mole of solvent per mole of organometallic compound.
  • the processes of this invention are conducted in the substantial absence of solvent.
  • the deoxygenating agent is added to the organometallic compound. Other methods can be used, such as co-feeding the organometallic compound and the deoxygenating agent. In at least some instances, the contacting should be gradual, to minimize heat evolution due to the exothermicity of the reaction.
  • the processes of this invention are preferably conducted at atmospheric pressure, although subatmospheric or superatmospheric pressure can be employed if needed or desired.
  • mixtures are formed, which typically contain a deoxygenated organometallic compound and solids. Often, a small amount of aluminoxane, galloxane, or indinoxane will be present.
  • the deoxygenated organometallic compound can be separated from the solids by conventional methods such as decantation, filtration, and/or distillation. Preferred methods include a separation step such as decantation followed by distillation of the organometallic compound. After separating the deoxygenated organometallic compound from any solids present in said mixture, a purified organometallic compound is obtained.
  • the purified organometallic compound preferably has an oxygenate content of about 5 ppm or less, more preferably about 2.5 ppm or less, still more preferably about 1 ppm or less, as measured spectroscopically.
  • Lithium hydroxide monohydrate (LHM, 0.24 g) was added to trimethylaluminum (TMA, 15.6 g) at room temperature (RT) during 2 hours. The mixture obtained was heated at 80°C with stirring for 3 hours. After cooling, the mixture was filtered, and the product (14.4 g, 92 % recovery) was analyzed and determined by J H NMR to contain ⁇ 0.2 ppm oxygenates as oxygen atoms.
  • Example 1 An attempt to repeat Example 1 was made by replacing LHM with water. An addition of water directly to the TMA at -25 °C was aborted, because even at such a low temperature, the reaction was dangerously violent.
  • the TMA was diluted with toluene (16 g). Ordinarily it is counterintuitive to add an hydrocarbon since this will have to be removed prior to use in electronic applications. Water (0.2 g) was added during about 4 hours. Lots of solid was produced. 1 H NMR of the supernatant of this mixture showed about the same oxygen content as the starting material.
  • the invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.
  • the term "about" modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about”, the claims include equivalents to the quantities.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

Cette invention concerne un procédé pour éliminer des impuretés oxygénées à partir d'un composé organométallique. Le procédé est effectué dans un environnement inerte, et comprend la mise en contact du composé organométallique et d'au moins un agent de désoxygénation, pour former un mélange comprenant un composé organométallique désoxygéné ; et la séparation d'au moins une partie du composé organométallique désoxygéné à partir de toutes matières solides présentes dans ledit mélange pour former un composé organométallique purifié. L'agent de désoxygénation est soit un composé inorganique hydraté soit un composé organique hydraté, et le composé organométallique est représenté par la formule R3M dans laquelle M représente l'aluminium, le gallium ou l'indium, et chaque R représente indépendamment un atome d'hydrogène, un groupe alkyle en C1-C12, un groupe aryle en C6-C14 ou un groupe aryl-alkyle en C7-C16, avec la condition qu'au moins un R ne représente pas un atome d'hydrogène.
PCT/US2013/069110 2012-12-31 2013-11-08 Élimination de composés oxygénés à partir de composés organométalliques Ceased WO2014105272A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11532806B2 (en) 2014-04-01 2022-12-20 The Research Foundation For The State University Of New York Electrode materials that include an active composition of the formula MgzMxOy for group II cation-based batteries

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0116319A2 (fr) * 1983-02-09 1984-08-22 Sumitomo Chemical Company, Limited Procédé de préparation de composés de métaux à haute pureté
US5041583A (en) * 1990-06-28 1991-08-20 Ethyl Corporation Preparation of aluminoxanes
EP0523525A1 (fr) * 1991-07-17 1993-01-20 Japan Pionics Co., Ltd. Procédé pour la purification de composants organométalliques gazeux
JP2006342101A (ja) * 2005-06-09 2006-12-21 Shin Etsu Chem Co Ltd 有機金属化合物の製造方法
GB2432364A (en) 2005-11-18 2007-05-23 Rohm & Haas Elect Mat Improved method for purifying organometallic compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0116319A2 (fr) * 1983-02-09 1984-08-22 Sumitomo Chemical Company, Limited Procédé de préparation de composés de métaux à haute pureté
US4650895A (en) 1983-02-09 1987-03-17 Sumitomo Chemical Company, Limited Process for producing high purity metallic compound
US5041583A (en) * 1990-06-28 1991-08-20 Ethyl Corporation Preparation of aluminoxanes
EP0523525A1 (fr) * 1991-07-17 1993-01-20 Japan Pionics Co., Ltd. Procédé pour la purification de composants organométalliques gazeux
JP2006342101A (ja) * 2005-06-09 2006-12-21 Shin Etsu Chem Co Ltd 有機金属化合物の製造方法
GB2432364A (en) 2005-11-18 2007-05-23 Rohm & Haas Elect Mat Improved method for purifying organometallic compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.S. ROBERTS ET AL., J. CRYST. GROWTH, vol. 195, 1998, pages 668 - 675
R.W. FREER ET AL., ADV. MATER., vol. 7, 1995, pages 478 - 481

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11532806B2 (en) 2014-04-01 2022-12-20 The Research Foundation For The State University Of New York Electrode materials that include an active composition of the formula MgzMxOy for group II cation-based batteries

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