EP0399021A1 - Organoaluminium, organogallium and organoindium compounds and their use for the gas-phase deposition of metal on substrates - Google Patents

Organoaluminium, organogallium and organoindium compounds and their use for the gas-phase deposition of metal on substrates

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Publication number
EP0399021A1
EP0399021A1 EP90900116A EP90900116A EP0399021A1 EP 0399021 A1 EP0399021 A1 EP 0399021A1 EP 90900116 A EP90900116 A EP 90900116A EP 90900116 A EP90900116 A EP 90900116A EP 0399021 A1 EP0399021 A1 EP 0399021A1
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EP
European Patent Office
Prior art keywords
compounds
formula
group
organometallic compounds
gallium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP90900116A
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German (de)
French (fr)
Inventor
Dietrich Erdmann
Ludwig Pohl
Martin Hostalek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
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Merck Patent GmbH
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Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP0399021A1 publication Critical patent/EP0399021A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C23C16/20—Deposition of aluminium only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi

Definitions

  • the invention relates to organometallic compounds which contain aluminum, gallium or indium as metals, and to the use of these compounds for the production of thin films or epitaxial layers by vapor deposition.
  • Such layers from either pure elements of the third group or from III-V combinations with other elements, e.g. Gallium arsenide, indium phosphide or gallium phosphide can be used to manufacture electronic and optoelectronic switching elements, compound semiconductors and lasers. These layers are deposited from the gas phase.
  • MOCVD Metal-Organic Chemical Vapor Deposition
  • Photo-MOVP Photo-Metal-Organic Vapor Phase
  • UV radiation can be decomposed, the Laser-Chemical Vapor Deposition (Laser CVD) method or the Metal-Organic Magnetron Scattering (MOMS) method in question.
  • Laser CVD Laser-Chemical Vapor Deposition
  • MOMS Metal-Organic Magnetron Scattering
  • the MOCVD method uses organometallic compounds that decompose when the metal is deposited at a temperature below 1100 ° C.
  • Typical apparatus currently used for MOCVD consists of a "bubbler" with a feed for the organometallic component, a reaction chamber containing the substrate to be coated and a source for a carrier gas which is said to be inert to the organometallic component .
  • the "bubbler" is on
  • the reaction or decomposition chamber preferably has a much higher temperature, which is below 1100 ° C, at which the organometallic compound decomposes completely and the metal is deposited.
  • the organometallic compound is brought into the vapor state by the carrier gas and is carried into the decomposition chamber with the carrier gas.
  • the mass flow of the steam is easy to control, and so is a controlled growth of the thin film
  • metal alkyls such as e.g. Trimethyl gallium, trimethyl aluminum or trimethyl indium are used.
  • these compounds are extremely sensitive to air, self-igniting and sometimes even decompose at room temperature. Therefore, complex precautionary measures are necessary for the manufacture, transport, storage and use of these connections.
  • Lewis bases such as e.g. Trimethylamine and triphenylphosphine are known
  • organometallic compounds of aluminum, gallium and indium which are stabilized intramolecularly, are outstandingly suitable for the vapor deposition.
  • Some intramolecularly stabilized compounds of this type are e.g. described in DE-OS 36 31 469.
  • new organometallic compounds are described with intramolecular stabilization via a nitrogen, phosphorus, arsenic or antimony atom, or else with intramolecular stabilization via fluorine atoms. All of these intramolecularly stabilized compounds have a high stability towards air and oxygen, therefore they are easy to handle and are ideal for gas phase separation.
  • the invention thus relates to the organometallic compounds of the formula I.
  • alkyl group or alkenyl group with up to 8 C atoms each independently of one another an alkyl group or alkenyl group with up to 8 C atoms, where these groups can be partially or completely fluorinated, a cycloalkyl or cyclo alkenyl group with 3-8 C atoms or a phenyl group, and
  • R 5 in each case denotes H or an alkyl group with 1-4 C atoms, which can also be partially or completely fluorinated.
  • the invention furthermore relates to the use of the compounds of the formula I for gas phase deposition and a process for producing thin films or epitaxial layers by gas phase deposition of the metal or a III-V combination of organometallic compounds, in which the compounds of the formula are used as organometallic substances I can be used.
  • the compounds of formula I are intramolecularly stabilized by electron transfer from nitrogen,
  • M means aluminum (Al), gallium (Ga) or indium (In), preferably Ga or In.
  • Y preferably denotes F or a perfluoroalkyl group with 1-7 C atoms and accordingly preferably denotes trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl, undecafluoropentyl, tridecafluorhexyl or pentadecafluoroheptyl.
  • Y preferably represents a -NR 3 R 4 group, further preferably also a -PR 3 R 4 or -AsR 3 R 4 group.
  • Partial formula Ia includes the compounds containing F or a perfluoroalkyl group.
  • R 1 and R 2 each independently of one another an alkyl group or alkenyl group having up to 8 carbon atoms, where these groups can be partially or completely fluorinated, a cycloalkyl or cycloalkenyl group 3-8 carbon atoms or a phenyl group, and
  • R 5 in each case denotes H or an alkyl group with 1-4 C atoms, which can also be partially or completely fluorinated, are particularly preferred.
  • R 5 represents either an H atom or an alkyl group, some of which are also or can be completely fluorinated, with up to 4 carbon atoms and accordingly preferably means methyl, Ethyl, propyl, butyl, trifluoromethyl, tetrafluoroethyl, pentafluoroethyl or heptafluoropropyl. If R 5 is a
  • R 5 in - (CHR 5 ) n - is an alkyl group, the other R 5 which may be present then mean H.
  • X is preferably oC 6 H 4 -
  • X also preferably denotes one of the following groupings (1) - (8) for -X-Y.
  • R 1 , R 2 , R 3 and R 4 in formula I can each represent a straight-chain or branched alkyl group with 1-8 C atoms, preferably with 1-4 C atoms. They are preferably straight-chain and accordingly preferably mean methyl, ethyl, propyl, butyl and also pentyl, hexyl, heptyl, octyl, isopropyl, sec-butyl, tert-butyl, 2-methylpentyl, 3-methylpentyl or 2-octyl .
  • the alkyl radicals can be partially or completely fluorinated and can mean, for example, monofluoromethyl, trifluoromethyl, difluoroethyl, trifluoroethyl, pentafluoroethyl or trifluoropropyl.
  • R 1 , R 2 , R 3 and / or R4 represent a cycloalkyl or cycloalkenyl group with 3-8 C atoms, they preferably mean cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, Cycloheptyl, Cycloheptenyl, Cycloheptadienyl, Cyclooctyl, Cyclooctenyl, Cyclooctadienyl, Cyclooctatrienyl or
  • R 1 , R 2 , R 3 and / or R 4 are preferably also alkenyl groups with 3-8 C atoms, preferably with 3-5 C atoms. Accordingly, they preferably mean propenyl, butenyl,
  • Pentenyl also hexenyl, heptenyl or octenyl.
  • R 1 , R 2 , R 3 and / or R 4 represent a phenyl group. This phenyl group can also be substituted. Since these substituents have no significant influence on the intended use, all substituents are permitted which have no disruptive influence on the decomposition reaction.
  • Formula Ia in which Y is a perfluoroalkyl group and R 1 and R 2 are also alkyl groups which are partially or completely fluorinated.
  • the compounds of the formulas I, Ia and Ib are outstandingly suitable for the MOCVD epitaxy or MOCVD method, since they decompose at higher temperatures with the release of the corresponding metal. They are also suitable for other methods of gas phase deposition such as PhotoMOVP, Laser CVD or MOMS. -
  • the reactions are preferably carried out in inert solvents. Suitable solvents are all those who do not interfere with the reaction and do not intervene in the reaction.
  • the reaction temperatures correspond essentially to those known from the literature for the preparation of similar compounds.
  • the intramolecularly stabilized, organometallic compounds of the formula I are used as starting compounds in the gas-phase deposition processes of organometallic compounds known per se.
  • one or more compounds of arsenic, antimony or phosphorus for example AsHo, As (CH 3 ) 3 , PH 3 or SbH, are used in the process according to the invention during the deposition process in the decomposition chamber 3 , added.
  • arsenic, antimony or phosphorus for example AsHo, As (CH 3 ) 3 , PH 3 or SbH.
  • Another variant of the process according to the invention consists in that during the deposition process in addition to the organometallic compounds according to the invention
  • Formula I adds dopants.
  • Volatile organometallic compounds of iron, magnesium, zinc or chromium are used as dopants.
  • Zn (CH 3 ) 2 , Mg (CH 3 ) 2 or Fe (C 5 H 5 ) 2 are, for example, preferred compounds. It is also possible to add the compounds of the formula I as dopants during the deposition process of other organometallic compounds.
  • the layers produced by the method according to the invention can be used for the production of electronic and optoelectronic switching elements, compound semiconductors or lasers.
  • Mp Means melting point and Kp. Boiling point.
  • n-butyllithium (in hexane) are refluxed in an ether / hexane solution (50 ml / 25 ml) for about 8 hours.
  • the mixture is then cooled to -40 ° and 1.62 g (12 mmol) of dirnethyl gallium chloride in 30 ml of hexane are added.
  • Precipitated lithium chloride is filtered off, the solvent is evaporated off and the residue is sublimed in vacuo.
  • O-trifluoromethylphenyl-dimethyl-gallium is obtained as a white solid, mp. 32 °.
  • the following are prepared analogously: o-trifluoromethylphenyl-diethylgallium
  • Example 2 To 1.23 g (177 mmol) of lithium in 60 ml of ether are added 13.81 g (69 mmol) of bromodimethylaniline in 100 ml of ether and the mixture is stirred at 20 ° for 12 hours. Then heated to boiling for 2 hours. After cooling, the solvent is removed in vacuo, hexane is added and the LiCl is filtered off. When cooling to -30 °, the corresponding Li compound crystallizes, which isolates and

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Composés organométalliques à stabilisation intramoléculaire et à structure cyclique ou bicyclique, et leur utilisation pour obtenir des couches minces et des couches épitaxiales par dépôt chimique en phase vapeur. Ces composés organométalliques correspondent à la formule (I), où M représente aluminium, indium ou gallium, Y représente -NR3R4, -PR3R4, -AsR3R4, -SbR3R4, -F ou un groupe perfluoralkyle avec 1 à 7 atomes de C, les symboles R1, R2, R3, R4 et X ayant les significations indiquées dans la revendication 1.Organometallic compounds with intramolecular stabilization and with a cyclic or bicyclic structure, and their use to obtain thin films and epitaxial layers by chemical vapor deposition. These organometallic compounds correspond to formula (I), where M represents aluminum, indium or gallium, Y represents -NR3R4, -PR3R4, -AsR3R4, -SbR3R4, -F or a perfluoroalkyl group with 1 to 7 C atoms, the symbols R1, R2, R3, R4 and X having the meanings given in claim 1.

Description

ALUMINIUM-, GALLIUM-, ODER INDIUM-ORGANISCHE VERBINDUNGEN  ALUMINUM, GALLIUM, OR INDIUM ORGANIC COMPOUNDS
UND IHRE VERWENDUNG ZUR GASPHASENABSCHEIDUNG DES AND THEIR USE FOR GAS PHASE DEPOSITION OF THE
METALLS AUF SUBSTRATEN METALS ON SUBSTRATES
Die Erfindung betrifft metallorganische Verbindungen, die Aluminium, Gallium oder Indium als Metalle enthalten, sowie die Verwendung dieser Verbindugen für die Herstellung dünner Filme oder epitaktischer Schichten durch Gasphasenabscheidung. The invention relates to organometallic compounds which contain aluminum, gallium or indium as metals, and to the use of these compounds for the production of thin films or epitaxial layers by vapor deposition.
Die Abscheidung solcher Schichten aus entweder reinen Elementen der dritten Gruppe oder aus III-V-Kombinationen mit anderen Elementen, wie z.B. Galliumarsenid, Indiumphosphid oder Galliumphosphid, kann zur Herstellung von elektronischen und optoelektronischen Schaltelementen, Verbindungshalbleitern und Lasern verwendet werden. Die Abscheidung dieser Schichten erfolgt aus der Gasphase. The deposition of such layers from either pure elements of the third group or from III-V combinations with other elements, e.g. Gallium arsenide, indium phosphide or gallium phosphide can be used to manufacture electronic and optoelectronic switching elements, compound semiconductors and lasers. These layers are deposited from the gas phase.
Die Eigenschaften dieser Filme hängen von den Abschei- dungsbedingungen und der chemischen Zusammensetzung des abgeschiedenen Films ab. The properties of these films depend on the deposition conditions and the chemical composition of the deposited film.
Für die Abscheidung aus der Gasphase kommen alle bekannten Methoden wie die Metal-Organic Chemical Vapour Deposition (MOCVD) Methode, die Photo-Metal-Organic Vapour Phase (Photo-MOVP) Methode, bei welcher die Substanzen durchFor the separation from the gas phase come all known methods such as the Metal-Organic Chemical Vapor Deposition (MOCVD) method, the Photo-Metal-Organic Vapor Phase (Photo-MOVP) method, in which the substances pass through
UV-Bestrahlung zersetzt werden, die Laser-Chemical Vapour Deposition (Laser CVD) Methode oder die Metal-Organic Magnetron Scattering (MOMS) Methode in Frage. Die Vorteile gegenüber anderen Methoden sind ein kontrollierbares UV radiation can be decomposed, the Laser-Chemical Vapor Deposition (Laser CVD) method or the Metal-Organic Magnetron Scattering (MOMS) method in question. The advantages over other methods are controllable
Schichtenwachstum, eine genaue Dotierungskontrolle sowie eine aufgrund der Normal- oder Niederdruckbedingungen einfache Handhabung und Produktionsfreundlichkeit. Bei der MOCVD-Methode werden metallorganische Verbindungen eingesetzt, die sich unter Abscheidung des Metalls bei einer Temperatur unterhalb 1100 °C zersetzen. Typische Apparaturen, die zur Zeit für MOCVD benutzt werden, bestehen aus einem "bubbler" mit einer Zufuhr für die metallorganische Komponente, einer Reaktionskammer, die das zu beschichtende Substrat enthält, sowie einer Quelle für ein Trägergas , das gegen die metallorganische Komponente inert sein soll. Der "bubbler" wird auf Layer growth, precise doping control and easy handling and ease of production due to the normal or low pressure conditions. The MOCVD method uses organometallic compounds that decompose when the metal is deposited at a temperature below 1100 ° C. Typical apparatus currently used for MOCVD consists of a "bubbler" with a feed for the organometallic component, a reaction chamber containing the substrate to be coated and a source for a carrier gas which is said to be inert to the organometallic component . The "bubbler" is on
einer konstanten, relativ niedrigen Temperatur gehalten, die vorzugsweise über dem Schmelzpunkt der metallorganischen Verbindung, aber weit unterhalb der Zersetzungstemperatur liegt. Die Reaktions- oder Zersetzungskammer hat vorzugsweise eine sehr viel höhere Temperatur, die unterhalb 1100 °C liegt, bei welcher die metallorganische Verbindung sich vollständig zersetzt und das Metall abgeschieden wird. Durch das Trägergas wird die metallorganische Verbindung in den Dampfzustand gebracht und mit dem Trägergas in die Zersetzungskammer geschleust. Der Massenfluß des Dampfes ist gut zu kontrollieren, und somit ist auch ein kontrolliertes Wachsen der dünnen maintained at a constant, relatively low temperature, which is preferably above the melting point of the organometallic compound, but far below the decomposition temperature. The reaction or decomposition chamber preferably has a much higher temperature, which is below 1100 ° C, at which the organometallic compound decomposes completely and the metal is deposited. The organometallic compound is brought into the vapor state by the carrier gas and is carried into the decomposition chamber with the carrier gas. The mass flow of the steam is easy to control, and so is a controlled growth of the thin
Schichten möglich. Layers possible.
Bislang wurden für die Gasphasenabscheidung hauptsächlich Metallalkyle wie z.B. Trimethylgallium, Trimethylaluminium oder Trimethyl indium verwendet. Diese Verbindungen sind jedoch extrem luftempfindlich, selbstentzündlich und teilweise bereits bei Raumtemperatur zersetzlich. Daher sind für die Herstellung, den Transport, die Lagerung und die Anwendung dieser Verbindungen aufwendige Vor- sichtsmaßnahmen notwendig. Es sind auch einige, etwas stabilere Addukte der Metallalkyle mit Lewisbasen wie z.B. Trimethylamin und Triphenylphosphin bekannt So far, mainly metal alkyls such as e.g. Trimethyl gallium, trimethyl aluminum or trimethyl indium are used. However, these compounds are extremely sensitive to air, self-igniting and sometimes even decompose at room temperature. Therefore, complex precautionary measures are necessary for the manufacture, transport, storage and use of these connections. There are also some, somewhat more stable adducts of the metal alkyls with Lewis bases such as e.g. Trimethylamine and triphenylphosphine are known
(z.B. beschrieben in GB 21 23 422, EP-A 108 469 oder EP-A 176 537), die jedoch aufgrund des geringen Dampf- druckes nur bedingt für die Gasphasenabscheidung  (e.g. described in GB 21 23 422, EP-A 108 469 or EP-A 176 537), but due to the low vapor pressure only to a limited extent for gas phase separation
geeignet sind. Aufgabe der vorliegenden Erfindung war es nun, MetallalkylVerbindungen zu finden, die einfach handhabbar und bei Raumtemperatur stabil sind und die sich aus der Gasphase zersetzen lassen, also für die verschiedenen Methoden der Gasphasenabscheidung geeignet sind. are suitable. It was an object of the present invention to find metal alkyl compounds which are easy to handle and stable at room temperature and which can be decomposed from the gas phase, that is to say are suitable for the various methods of gas phase deposition.
Es wurde nun gefunden, daß sich metallorganische Verbindungen von Aluminium, Gallium und Indium, die intramolekular stabilisiert sind, hervorragend für die Gasphasenabscheidung eignen. Einige intramolekular stabilisierte Verbindungen dieser Art sind z.B. in der DE-OS 36 31 469 beschrieben. In dieser Anmeldung werden jedoch neue metallorganische Verbindungen mit einer intramolekularen Stabilisierung über ein Stickstoff-, Phosphor-, Arsen- oder Antimon-Atom, oder auch mit einer intramolekularen Stabilisierung über Fluoratome beschrieben. Alle diese intramolekular stabilisierten Verbindungen weisen eine hohe Stabilität gegenüber Luft und Sauerstoff auf, daher sind sie einfach zu handhaben und eignen sich hervorragend für die Gasphasen- abscheidung. It has now been found that organometallic compounds of aluminum, gallium and indium, which are stabilized intramolecularly, are outstandingly suitable for the vapor deposition. Some intramolecularly stabilized compounds of this type are e.g. described in DE-OS 36 31 469. In this application, however, new organometallic compounds are described with intramolecular stabilization via a nitrogen, phosphorus, arsenic or antimony atom, or else with intramolecular stabilization via fluorine atoms. All of these intramolecularly stabilized compounds have a high stability towards air and oxygen, therefore they are easy to handle and are ideal for gas phase separation.
Gegenstand der Erfindung sind somit die metallorganischen Verbindungen der Formel I The invention thus relates to the organometallic compounds of the formula I.
worin wherein
M Aluminium, Indium oder Gallium, M aluminum, indium or gallium,
Y -NR3R4, -PR3R4, -AsR3R4, -SbR3R4, Y -NR 3 R 4 , -PR 3 R 4 , -AsR 3 R 4 , -SbR 3 R 4 ,
-F oder eine Perfluoralkylgruppe mit 1-7 C-Atomen, X im Falle Y = -F oder eine Perfluoralkylgruppe mit 1-7 C-Atomen: -F or a perfluoroalkyl group with 1-7 C atoms, X in the case of Y = -F or a perfluoroalkyl group with 1-7 C atoms:
-(CHR5)n mit n = 1, 2 , 3, 4, oder 5, o-(CH2)p-C6H4-(CH2)q-, - (CHR 5 ) n with n = 1, 2, 3, 4, or 5, o- (CH 2 ) p -C 6 H 4 - (CH 2 ) q -,
1,2-(CH2)p-C6H10-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 10 - (CH 2 ) q -,
1,2-(CH2)p-C6H8-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C6H6-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H8-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C5H6-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H4-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 4 - (CH 2 ) q -,
1,2-(CH2)p-C4H6-(CH2)q-, oder eine 1,2- (CH 2 ) p -C 4 H 6 - (CH 2 ) q -, or one
Einfachbindung, im Falle Y = -NR3R4, -PR3R4, -AsR3R4 oder Single bond, in the case of Y = -NR 3 R 4 , -PR 3 R 4 , -AsR 3 R 4 or
-SbR 3R4: o-C6H4-, -SbR 3 R 4: oC 6 H 4 -,
1,2-C6H10-, 1,2-C 6 H 10 -,
o-(CH2)r-C6H4-(CH2)s-, o- (CH 2 ) r -C 6 H 4 - (CH 2 ) s -,
1,2-(CH2)r-C6H10-(CH2)s-, 1,2- (CH 2 ) r -C 6 H 10 - (CH 2 ) s -,
1,2-(CH2)p-C6H8-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C6H6-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H8-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C5H6-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H4-(CH2)q- oder 1,2- (CH 2 ) p -C 5 H 4 - (CH 2 ) q - or
1,2-(CH2)p-C4H6-(CH2)q-, r und s jeweils unabhängig voneinander 1, 2 oder 3, p und q jeweils unabhängig voneinander 0, 1, 2 oder 3, R1, R2, R3 und R4 1,2- (CH 2 ) p -C 4 H 6 - (CH 2 ) q -, r and s each independently of one another 1, 2 or 3, p and q each independently of one another 0, 1, 2 or 3, R 1 , R 2 , R 3 and R 4
jeweils unabhängig voneinander eine Alkylgruppe oder Alkenylgruppe mit bis zu 8 C-Atomen, wobei diese Gruppen teilweise oder vollständig fluoriert sein können, eine Cycloalkyl- oder Cyclo- alkenylgruppe mit 3-8 C-Atomen oder eine Phenylgruppe, und  each independently of one another an alkyl group or alkenyl group with up to 8 C atoms, where these groups can be partially or completely fluorinated, a cycloalkyl or cyclo alkenyl group with 3-8 C atoms or a phenyl group, and
R5 jeweils H oder eine Alkylgruppe mit 1-4 C-Atomen, die auch teilweise oder vollständig fluoriert sein kann, bedeutet. R 5 in each case denotes H or an alkyl group with 1-4 C atoms, which can also be partially or completely fluorinated.
Ferner ist Gegenst.and der Erfindung die Verwendung der Verbindungen der Formel I zur Gasphasenabscheidung sowie ein Verfahren zur Herstellung dünner Filme oder epitaktischer Schichten durch Gasphasenabscheidung des Metalls oder einer III-V-Kombination aus metallorganischen Verbindungen, bei welchem als metallorganische Substanzen die Verbindungen der Formel I eingesetzt werden. Die Verbindungen der Formel I sind intramolekular stabilisiert durch Elektronenübertragung vom Stickstoff-, The invention furthermore relates to the use of the compounds of the formula I for gas phase deposition and a process for producing thin films or epitaxial layers by gas phase deposition of the metal or a III-V combination of organometallic compounds, in which the compounds of the formula are used as organometallic substances I can be used. The compounds of formula I are intramolecularly stabilized by electron transfer from nitrogen,
Phosphor-, Arsen-, Antimon- oder Fluoratom auf das Phosphorus, arsenic, antimony or fluorine atom on the
elektronenarme III B-Element. Sie besitzen daher eine hohe Stabilität gegenüber Luft und Sauerstoff. Sie sind nicht mehr selbstentzündlich und damit einfach zu handhaben. In der Gasphase jedoch lassen sich die erfindungsgemäßen Verbindungen leicht unter Abscheidung des Metalls zersetzen. Da die Verbindungen der Formel I stabile und gut abspaltbare Abgangsgruppen enthalten, resultiert ein geringerer Einbau an Kohlenstoff, was für die Qualität der Endprodukte große Vorteile hat. In Formel I bedeutet M Aluminium (AI), Gallium (Ga) oder Indium (In), vorzugsweise Ga oder In. electron-poor III B element. Therefore, they have a high stability against air and oxygen. They are no longer self-igniting and therefore easy to use. In the gas phase, however, the compounds according to the invention can easily be decomposed with the deposition of the metal. Since the compounds of the formula I contain stable and easily removable leaving groups, less carbon is incorporated, which has great advantages for the quality of the end products. In formula I, M means aluminum (Al), gallium (Ga) or indium (In), preferably Ga or In.
Y bedeutet vorzugsweise F oder eine Perfluoralkylgruppe mit 1-7 C-Atomen und bedeutet demnach bevorzugt Trifluormethyl, Pentafluorethyl, Heptafluorpropyl oder Nonafluorbutyl, Undecafluorpentyl, Tridecafluorhexyl oder Pentadecafluorheptyl. Y preferably denotes F or a perfluoroalkyl group with 1-7 C atoms and accordingly preferably denotes trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl, undecafluoropentyl, tridecafluorhexyl or pentadecafluoroheptyl.
Des weiteren stellt Y bevorzugt eine -NR3R4 Gruppe, ferner bevorzugt auch eine -PR3R4 oder -AsR3 R4 Gruppe. Teilformel Ia umfaßt die Verbindungen, die F oder eine Perfluoralkylgruppe enthalten. Diese Verbindungen Furthermore, Y preferably represents a -NR 3 R 4 group, further preferably also a -PR 3 R 4 or -AsR 3 R 4 group. Partial formula Ia includes the compounds containing F or a perfluoroalkyl group. These connections
IaYes
worin wherein
M AI, In oder Ga, M AI, In or Ga,
Y F, Trifluormethyl, Pentafluorethyl, Heptafluorpropyl, Nonafluorbutyl, Undecafluorpentyl, Tridecafluorhexyl oder Pentadecafluorheptyl, X -(CHR5)n mit n = 1, 2, 3, 4, oder 5, YF, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorhexyl or pentadecafluoroheptyl, X - (CHR 5 ) n with n = 1, 2, 3, 4, or 5,
o-(CH2)p-C6H4-(CH2)q-, o- (CH 2 ) p -C 6 H 4 - (CH 2 ) q -,
1,2-(CH2)p-C6H10-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 10 - (CH 2 ) q -,
1,2-(CH2)p-C6H8-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C6H6-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H8-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C5H6-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H4-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 4 - (CH 2 ) q -,
1,2-(CH2)p-C4H6-(CH2)q-, oder eine 1,2- (CH 2 ) p -C 4 H 6 - (CH 2 ) q -, or one
Einfachbindung, p und q jeweils unabhängig voneinander 0, 1, 2 oder 3, R 1 und R2 jeweils unabhängig voneinander eine Alkylgruppe oder Alkenylgruppe mit bis zu 8 C-Atomen, wobei diese Gruppen teilweise oder vollständig fluoriert sein können, eine Cycloalkyl- oder Cycloalkenylgruppe mit 3-8 C-Atomen oder eine Phenylgruppe, und Single bond, p and q each independently of one another 0, 1, 2 or 3, R 1 and R 2 each independently of one another an alkyl group or alkenyl group having up to 8 carbon atoms, where these groups can be partially or completely fluorinated, a cycloalkyl or cycloalkenyl group 3-8 carbon atoms or a phenyl group, and
R5 jeweils H oder eine Alkylgruppe mit 1-4 C-Atomen, die auch teilweise oder vollständig fluoriert sein kann, bedeutet, sind besonders bevorzugt. R 5 in each case denotes H or an alkyl group with 1-4 C atoms, which can also be partially or completely fluorinated, are particularly preferred.
Ferner sind die Verbindungen der Teilformel Ib bevorzugt, die als Y eine -NR3R4, -PR3R4, -AsR3R4 oder -SbR3R4 Preference is furthermore given to the compounds of sub-formula Ib which, as Y, are -NR 3 R 4 , -PR 3 R 4 , -AsR 3 R 4 or -SbR 3 R 4
Gruppe enthalten.  Group included.
worin wherein
M AI, In oder Ga, M AI, In or Ga,
Y -NR3R4 , -PR3R4 , -AsR3R4 oder -SbR3R4 , X o-C6H4.-, Y -NR 3 R 4 , -PR 3 R 4 , -AsR 3 R 4 or -SbR 3 R 4 , X oC 6 H 4 .-,
1'2-C6H10-' 1 ' 2-C 6 H 10-'
o-(CH2)r-C6H4-(CH2)s-, o- (CH 2 ) r -C 6 H 4 - (CH 2 ) s -,
1,2-(CH2)r-C6H10-(CH2)s-, 1,2- (CH 2 ) r -C 6 H 10 - (CH 2 ) s -,
1,2-(CH2)p-C6H8-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C6H6-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H8-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C5H6-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H4-(CH2)q- oder 1,2- (CH 2 ) p -C 5 H 4 - (CH 2 ) q - or
1,2-(CH2)p-C4H6-(CH2)q-, r und s jeweils unabhängig voneinander 1, 2 oder 3, p und q jeweils unabhängig voneinander 0, 1, 2 oder 1,2- (CH 2 ) p -C 4 H 6 - (CH 2 ) q -, r and s each independently 1, 2 or 3, p and q each independently 0, 1, 2 or
3 und  3 and
R1, R2 , R3 und R4 R 1 , R 2 , R 3 and R 4
jeweils unabhängig voneinander eine Alkylgruppe oder Alkenylgruppe mit bis zu 8 C-Atomen, wobei diese Gruppen teilweise oder vollständig fluoriert sein können, eine Cycloalkyl- oder Cycloalkenylgruppe mit 3-8 C-Atomen oder eine Phenylgruppe, bedeutet.  each independently represents an alkyl group or alkenyl group with up to 8 C atoms, these groups being able to be partially or completely fluorinated, a cycloalkyl or cycloalkenyl group with 3-8 C atoms or a phenyl group.
Ganz besonders bevorzugt sind unter den Verbindungen derAmong the compounds, the
Formel Ib diejenigen, m welchen Y = -NR 3R4 oder -PR3R4 bedeutet. In Formel I und Ia bedeutet X -(CHR5)n mit n = 1, 2, 3, 4 oder 5, vorzugsweise ist n = 3 oder 4. R5 stellt entweder ein H-Atom oder eine Alkylgruppe dar, die auch teilweise oder vollständig fluoriert sein kann, mit bis zu 4 C-Atomen und bedeutet demnach vorzugsweise Methyl, Ethyl, Propyl, Butyl, Trifluormethyl, Tetrafluorethyl, Pentafluorethyl oder Heptafluorpropyl . Falls R5 eineFormula Ib those where m is Y = -NR 3 R 4 or -PR 3 R 4 . In formula I and Ia, X denotes - (CHR 5 ) n with n = 1, 2, 3, 4 or 5, preferably n = 3 or 4. R 5 represents either an H atom or an alkyl group, some of which are also or can be completely fluorinated, with up to 4 carbon atoms and accordingly preferably means methyl, Ethyl, propyl, butyl, trifluoromethyl, tetrafluoroethyl, pentafluoroethyl or heptafluoropropyl. If R 5 is a
Alkyl- oder teilweise oder vollständig fluorierte Alkyl- gruppe ist, so ist vorzugsweie nur ein R 5 in -(CHR5)n- eine Alkylgruppe, die anderen, eventuell vorhandenen R 5 bedeuten dann H. Is alkyl or partially or completely fluorinated alkyl group, then preferably only one R 5 in - (CHR 5 ) n - is an alkyl group, the other R 5 which may be present then mean H.
In Formel I und Ib bedeutet X vorzugsweise o-C6H4-, In formula I and Ib, X is preferably oC 6 H 4 -,
1,2-C6H10- oder auch o-(CH2)r-C6H4-(CH2)S- oder 1,2-C 6 H 10 - or also o- (CH 2 ) rC 6 H 4 - (CH 2 ) S - or
1,2-(CH2) -C6H10-(CH2)s-, wobei r und s jeweils unabhängig voneinander 1, 2 oder 3, vorzugsweise 1 oder 2 bedeuten. 1,2- (CH 2 ) -C 6 H 10 - (CH 2 ) s -, where r and s each independently represent 1, 2 or 3, preferably 1 or 2.
Für X in Formel Ia sind vor allem auch die GruppenFor X in formula Ia, the groups are especially also
o-(CH2)p-C6H4-(CH2)q - und 1,2-(CH2)p-C6H10 -(CH2)q bevor- zugt, worin p und q jeweils unabhängig voneinander 0,o- (CH 2 ) p -C 6 H 4 - (CH 2 ) q - and 1,2- (CH 2 ) p -C 6 H 10 - (CH 2 ) q are preferred, wherein p and q are each independent from each other 0,
1, 2, oder 3, vorzugsweise 0, 1 oder 2 bedeuten. Ganz besonders bevorzugt für X in Teilformel Ia ist die Einfachbindung. 1, 2 or 3, preferably 0, 1 or 2. The single bond is very particularly preferred for X in partial formula Ia.
In den Formeln I, Ia und Ib bedeutet X ferner auch bevorzugt eine der folgenden Gruppierungen (1)-(8) für -X-Y. In the formulas I, Ia and Ib, X also preferably denotes one of the following groupings (1) - (8) for -X-Y.
In den Formeln (1), (2), (4) und (5) können die Doppelbindungen auch in allen anderen möglichen Positionen stehen. p und q in Formel I bedeuten vorzugsweise 1 oder 2. In formulas (1), (2), (4) and (5) the double bonds can also be in all other possible positions. p and q in formula I are preferably 1 or 2.
Dabei sind diejenigen Verbindungen bevorzugt, bei denen eine der Gruppen p und q 0 ist und die andere 1 oder 2 bedeutet. Die Reste R 1, R2, R3 und R4 in Formel I können jeweils eine geradkettige oder verzweigte Alkylgruppe mit 1-8 C-Atomen, vorzugsweise mit 1-4 C-Atomen bedeuten. Sie sind vorzugsweise geradkettig und bedeuten demnach bevorzugt Methyl, Ethyl, Propyl, Butyl ferner auch Pentyl, Hexyl, Heptyl, Octyl, iso-Propyl, sek.-Butyl, tert.-Butyl, 2-Methylpentyl, 3-Methylpentyl oder 2-Octyl. Die Alkyl- reste können teilweise oder auch vollständig fluoriert sein und z.B. Monofluormethyl, Trifluormethyl, Difluorethyl, Trifluorethyl, Pentafluorethyl oder Trifluor- propyl bedeuten. Falls R 1, R2, R3 und/oder R4 eine Cycloalkyl- oder Cycloalkenylgruppe mit 3-8 C-Atomen bedeuten, so bedeuten sie vorzugsweise Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclopentenyl, Cyclohexyl, Cyclohexenyl, Cyclohexadienyl, Cycloheptyl, Cycloheptenyl, Cycloheptadienyl, Cyclooctyl, Cyclooctenyl, Cyclooctadienyl, Cyclooctatrienyl oder Those compounds are preferred in which one of the groups p and q is 0 and the other is 1 or 2. The radicals R 1 , R 2 , R 3 and R 4 in formula I can each represent a straight-chain or branched alkyl group with 1-8 C atoms, preferably with 1-4 C atoms. They are preferably straight-chain and accordingly preferably mean methyl, ethyl, propyl, butyl and also pentyl, hexyl, heptyl, octyl, isopropyl, sec-butyl, tert-butyl, 2-methylpentyl, 3-methylpentyl or 2-octyl . The alkyl radicals can be partially or completely fluorinated and can mean, for example, monofluoromethyl, trifluoromethyl, difluoroethyl, trifluoroethyl, pentafluoroethyl or trifluoropropyl. If R 1 , R 2 , R 3 and / or R4 represent a cycloalkyl or cycloalkenyl group with 3-8 C atoms, they preferably mean cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, Cycloheptyl, Cycloheptenyl, Cycloheptadienyl, Cyclooctyl, Cyclooctenyl, Cyclooctadienyl, Cyclooctatrienyl or
Cyclooctatetraenyl.  Cyclooctatetraenyl.
Vorzugsweise stellen R 1, R2, R3 und/oder R4 auch Alkenylgruppen mit 3-8 C-Atomen, vorzugsweise mit 3-5 C-Atomen dar. Sie bedeuten demnach vorzugsweise Propenyl, Butenyl,R 1 , R 2 , R 3 and / or R 4 are preferably also alkenyl groups with 3-8 C atoms, preferably with 3-5 C atoms. Accordingly, they preferably mean propenyl, butenyl,
Pentenyl ferner Hexenyl, Heptenyl oder Octenyl. Pentenyl also hexenyl, heptenyl or octenyl.
Weiterhin sind Verbindungen der Formel I bevorzugt, worin.Compounds of the formula I are furthermore preferred in which.
R 1, R2, R3 und/oder R4 eine Phenylgruppe bedeuten. Diese Phenylgruppe kann auch εubstiuiert vorliegen. Da diese Substiuenten keinen wesentlichen Einfluß auf den angestrebten Verwendungszweck ausüben, sind alle Substituenten erlaubt, die keinen störenden Einfluß auf die Zersetzungsreaktion haben. Besonders bevorzugt sind auch die Verbindungen der R 1 , R 2 , R 3 and / or R 4 represent a phenyl group. This phenyl group can also be substituted. Since these substituents have no significant influence on the intended use, all substituents are permitted which have no disruptive influence on the decomposition reaction. The compounds of
Formel Ia, worin Y eine Perfluoralkylgrupe und R1 und R2 ebenfalls Alkylgruppen bedeuten, die teilweise oder auch vollständig fluoriert sind. Formula Ia, in which Y is a perfluoroalkyl group and R 1 and R 2 are also alkyl groups which are partially or completely fluorinated.
Folgende Verbindungen der Formeln 7-27 stellen eine kleinere Gruppe von besonders bevorzugten Verbindungen der Formel I dar: The following compounds of the formulas 7-27 represent a smaller group of particularly preferred compounds of the formula I:
00
χ * χ *
Al(CF3)3 17 Ga(CF3)3 18Al (CF 3 ) 3 17 Ga (CF 3 ) 3 18
In(CF3)3 19In (CF 3 ) 3 19
(C2F5)2M-(-CH2)n-F 20 (C 2 F 5 ) 2 M - (- CH 2 ) n -F 20
M(C2F5)3 21M (C 2 F 5 ) 3 21
M [-(CH2)n-CF3]3 22 M [- (CH 2 ) n -CF 3 ] 3 22
23 V 23 V
Die Verbindungen der Formeln I, Ia und Ib sind hervorragend für die MOCVD-Epitaxie bzw. MOCVD-Methode geeignet, da sie sich bei höheren Temperaturen unter Freisetzung des entsprechenden Metalles zersetzen. Sie sind ebenfalls für die anderen Methoden der Gasphasenabscheidung wie Photo- MOVP, Laser-CVD oder MOMS geeignet. - The compounds of the formulas I, Ia and Ib are outstandingly suitable for the MOCVD epitaxy or MOCVD method, since they decompose at higher temperatures with the release of the corresponding metal. They are also suitable for other methods of gas phase deposition such as PhotoMOVP, Laser CVD or MOMS. -
Die Verbindungen der Formeln I, Ia und Ib werden nach an sich bekannten Methoden hergestellt, wie sie in der Literatur (z.B. G. Bahr, P. Burbar, Methoden der organischen Chemie, Band XIII/4, Georg Thieme Verlag, Stuttgart (1970)) beschrieben sind, und zwar unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann man auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen. So können Verbindungen der Formeln I, Ia und Ib z.B. The compounds of the formulas I, Ia and Ib are prepared by methods known per se, as described in the literature (for example G. Bahr, P. Burbar, Methods of Organic Chemistry, Volume XIII / 4, Georg Thieme Verlag, Stuttgart (1970) ) are described, namely under reaction conditions which are known and suitable for the reactions mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail. For example, compounds of the formulas I, Ia and Ib
hergestellt werden, indem man Metallalkylchloride mit einem Alkalimetallorganyl der entsprechenden Lewisbase oder eine Grignard-Verbindung in einem inerten Lösungs- mittel umsetzt. are prepared by reacting metal alkyl chlorides with an alkali metal organyl of the corresponding Lewis base or a Grignard compound in an inert solvent.
Die Umsetzungen erfolgen vorzugsweise in inerten Lösungsmitteln. Als Lösungsmittel kommen dabei alle diejenigen in Frage, die die Umsetzung nicht stören und nicht in das Reaktionsgeschehen eingreifen. Die Reaktionstemperaturen entsprechen im wesentlichen denen, die aus der Literatur für die Herstellung ähnlicher Verbindungen bekannt sind. The reactions are preferably carried out in inert solvents. Suitable solvents are all those who do not interfere with the reaction and do not intervene in the reaction. The reaction temperatures correspond essentially to those known from the literature for the preparation of similar compounds.
Beim erfindungsgemäßen Verfahren zur Herstellung dünner Filme oder epitaktischer Schichten auf beliebigen Substraten setzt man bei den an sich bekannten Gasphasen- abscheidungs-Prozessen von metallorganischen Verbindungen als Ausgangsverbindungen die intramolekular stabilisierten, metallorganischen Verbindungen der Formel I ein. In the process according to the invention for the production of thin films or epitaxial layers on any substrates, the intramolecularly stabilized, organometallic compounds of the formula I are used as starting compounds in the gas-phase deposition processes of organometallic compounds known per se.
Zur Herstellung von Verbindungshalbleitem optischen und optoelektronischen Bauteilen werden beim erfindungsgemäßen Verfahren während des Abscheidungsprozesses in der Zer- setzungskammer eine oder mehrere unter den angewandten Reaktionsbedingungen gasförmige Verbindungen des Arsens, Antimons oder Phosphors, beispielsweise AsHo, As(CH3 )3, PH3 oder SbH3, zugesetzt. Eine weitere Variante des erfindungsgemäßen Verfahrens besteht darin, daß man während des Abscheidungsprozesses zusätzlich zu den erfindungsgemäßen metallorganischen Verbindungen der To produce compound semiconductors, optical and optoelectronic components, one or more compounds of arsenic, antimony or phosphorus, for example AsHo, As (CH 3 ) 3 , PH 3 or SbH, are used in the process according to the invention during the deposition process in the decomposition chamber 3 , added. Another variant of the process according to the invention consists in that during the deposition process in addition to the organometallic compounds according to the invention
Formel I Dotierstoffe zusetzt. Als Dotierstoffe werden dabei flüchtige metallorganische Verbindungen von Eisen, Magnesium, Zink oder Chrom eingesetzt. Als bevorzugte Verbindungen gelten dabei z.B. Zn(CH3)2, Mg(CH3)2 oder Fe(C5H5)2. Ferner ist es möglich, die Verbindungen der Formel I als Dotierstoffe während des Abscheidungsprozesses anderer metallorganischer Verbindungen zuzusetzen. Formula I adds dopants. Volatile organometallic compounds of iron, magnesium, zinc or chromium are used as dopants. Zn (CH 3 ) 2 , Mg (CH 3 ) 2 or Fe (C 5 H 5 ) 2 are, for example, preferred compounds. It is also possible to add the compounds of the formula I as dopants during the deposition process of other organometallic compounds.
Die nach den erfindungsgemäßen Verfahren hergestellten Schichten können verwendet werden für die Herstellung von elektronischen und optoelektronischen Schaltelementen, Verbindungshalbleitern oder Lasern. The layers produced by the method according to the invention can be used for the production of electronic and optoelectronic switching elements, compound semiconductors or lasers.
Da bei den momentan im Einsatz befindlichen Epitaxieanlagen aus thermodynamischen Gründen nur ca. 1-10 % der eingesetzten freien Metallalkyle als Epitaxieschicht auf dem Substrat abgeschieden werden kann, stellt die Vernichtung der überschüssigen Metallalkyle, die aufgrund ihrer extremen Empfindlichkeit nicht zurückgewonnen werden können, ein erhebliches Problem dar. Die erfin- dungsgemäßen Verbindungen der Formel I eröffnen dagegen aufgrund ihrer hohen Stabilität neue Möglichkeiten zur gefahrlosen Vernichtung oder zur Rückgewinnung der wertvollen III B-Verbindungen. Since only about 1-10% of the free metal alkyls used can be deposited as epitaxial layers on the substrate in the epitaxy systems currently in use for thermodynamic reasons, the destruction of the excess metal alkyls, which cannot be recovered due to their extreme sensitivity, represents a considerable amount The compounds of the formula I according to the invention, on the other hand, open up new possibilities for safe destruction or for recovery of the valuable III B compounds due to their high stability.
Die folgenden Beispiele sollen die Erfindung näher erläutern. Temperaturangaben erfolgen immer in GradThe following examples are intended to explain the invention in more detail. Temperatures are always in degrees
Celsius. Fp. bedeutet Schmelzpunkt und Kp. Siedepunkt. Celsius. Mp. Means melting point and Kp. Boiling point.
Beispiel 1 example 1
2,92 g (20 mmol) Trifluormethylbenzol und 13,3 ml 2.92 g (20 mmol) trifluoromethylbenzene and 13.3 ml
(1,5 N = 20 mmol) n-Butyllithium (in Hexan) werden in einer Ether/Hexan-Lösung (50 ml/25 ml) ca. 8 Stunden unter Rückfluß erhitzt. Man kühlt dann auf -40° und gibt 1,62 g (12 mmol) Dirnethylgalliumchlorid in 30 ml Hexan zu. Ausgefallenes Lithiumchlorid wird abfiltriert, das Lösungsmittel abgedampft und der Rückstand im Vakuum sublimiert. Man erhält o-Trifluormethylphenyl-dimethyl- gallium als weißen Feststoff, Fp. 32°. Analog werden hergestellt: o-Trifluormethylphenyl-diethylgallium (1.5 N = 20 mmol) n-butyllithium (in hexane) are refluxed in an ether / hexane solution (50 ml / 25 ml) for about 8 hours. The mixture is then cooled to -40 ° and 1.62 g (12 mmol) of dirnethyl gallium chloride in 30 ml of hexane are added. Precipitated lithium chloride is filtered off, the solvent is evaporated off and the residue is sublimed in vacuo. O-trifluoromethylphenyl-dimethyl-gallium is obtained as a white solid, mp. 32 °. The following are prepared analogously: o-trifluoromethylphenyl-diethylgallium
o-Trifluormethylphenyl-dipropylgallium o-trifluoromethylphenyl dipropyl gallium
o-Trifluormethylphenyl-dibutylgallium o-trifluoromethylphenyl dibutyl gallium
o-Trifluormethylphenyl-dimethylaluminium o-trifluoromethylphenyl dimethyl aluminum
o-Trifluormethylphenyl-diethylaluminium o-trifluoromethylphenyl diethyl aluminum
o-Trifluormethylphenyl-dipropylaluminium o-trifluoromethylphenyl dipropyl aluminum
o-Trifluormethylphenyl-di-iso-butylaluminium o-trifluoromethylphenyl-di-iso-butyl aluminum
o-Trifluormethylphenyl-dimethylindium o-trifluoromethylphenyl dimethyl indium
o-Trifluormethylphenyl-diethylindium o-trifluoromethylphenyl diethylindium
o-Trifluormethylphenyl-di-iso-propylindium o-trifluoromethylphenyl-di-iso-propylindium
o-Trifluormethylphenyl-dibutylindium o-trifluoromethylphenyl dibutylindium
3,3,3-Trifluorpropyl-dimethylgallium 3,3,3-trifluoropropyl dimethyl gallium
3,3,3-Trifluorpropyl-diethylgällium  3,3,3-trifluoropropyl diethyl gallium
3,3,3-Trifluorpropyl-methylethylgallium  3,3,3-trifluoropropyl methyl ethyl gallium
3,3,3-Trifluorpropyl-dipropylgallium 3,3,3-trifluoropropyl dipropyl gallium
3,3,3-Trifluorpropyl-di-sek.-butylgallium 3,3,3-trifluoropropyl di-sec-butyl gallium
3,3,3-Trifluorpropyl-dipeήtylgallium 3,3,3-trifluoropropyldipetyl gallium
3,3,3-Trifluorpropyl-dimethylaluminium 3,3,3-trifluoropropyl dimethyl aluminum
3,3,3-Trifluorpropyl-dipropylaluminium3,3,3-trifluoropropyl dipropyl aluminum
3,3,3-Trifluorpropyl-diethylindium 3,3,3-trifluoropropyl diethylindium
3,3,3-Trifluorpropyl-di-iso-propylindium 3,3,3-trifluoropropyl-di-iso-propylindium
3-Monofluorpropyl-dimethylgallium 3-monofluoropropyl dimethyl gallium
3-Monofluorpropyl-dimethylaluminium 3-monofluoropropyl dimethyl aluminum
3-Monofluorpropyl-dimethylindium 3-monofluoropropyl dimethyl indium
3-Monofluorpropyl-diethylgallium 3-monofluoropropyl diethyl gallium
3-Monofluorpropyl-diethylaluminium  3-monofluoropropyl diethyl aluminum
3-Monofluorpropyl-diethylindium 2-Monofluorethyl-dimethylgallium 3-monofluoropropyl diethylindium 2-monofluoroethyl dimethyl gallium
2-Monofluorethyl-diethylgallium 2-monofluoroethyl diethyl gallium
2-Monofluorethyl-dipropylgallium 2-monofluoroethyl dipropyl gallium
2-Monofluorethyl-dimethylaluminium 2-monofluoroethyl dimethyl aluminum
2-Monofluorethyl-diethylaluminium 2-monofluoroethyl diethyl aluminum
2-Monofluorethyl-di-tert.-butylaluminium  2-monofluoroethyl di-tert-butyl aluminum
2-Monofluorethyl-diethylindium  2-monofluoroethyl diethylindium
2-Monofluorethyl-dipentylindium  2-monofluoroethyl dipentylindium
Beispiel 2 Zu 1,23 g (177 mmol) Lithium in 60 ml Ether gibt man 13,81 g (69 mmol) Bromdimethylanilin bei 100 ml Ether und rührt 12 Stunden bei 20°. Anschließend erhitzt man 2 Stunden zum Sieden. Nach dem Abkühlen wird das Lösungsmittel im Vakuum entfernt, Hexan zugegeben und das LiCl abfiltriert. Beim Kühlen auf -30° kristallisiert die entsprechende Li-Verbindung aus, die isoliert und Example 2 To 1.23 g (177 mmol) of lithium in 60 ml of ether are added 13.81 g (69 mmol) of bromodimethylaniline in 100 ml of ether and the mixture is stirred at 20 ° for 12 hours. Then heated to boiling for 2 hours. After cooling, the solvent is removed in vacuo, hexane is added and the LiCl is filtered off. When cooling to -30 °, the corresponding Li compound crystallizes, which isolates and
getrocknet wird. is dried.
Anschließend gibt man bei -40° 4,6 g (34 mmol) Dimethylgalliumchlorid in 80 ml Pentan zu einer Suspension von 4,8 g (37,8 mmol) dieser Li-Verbindung in Pentan. Danach rührt man 12 Stunden bei Raumtemperatur und erhitzt noch 2 Stunden unter Rückfluß. Das LiCl wird abfiltriert, das Lösungsmittel im Vakuum abgezogen, der Rückstand wird mit Pentan/Toluol (20/1) versetzt und auf -30° gekühlt. Dabei kristallisiert o-Dimethylaminophenyldimethylgallium aus, welches nach Isolation einen Schmelzpunkt von 104° besitzt. Analog werden hergestellt: o-Dirnethylaminophenyl-diethylgallium Subsequently, 4.6 g (34 mmol) of dimethyl gallium chloride in 80 ml of pentane are added to a suspension of 4.8 g (37.8 mmol) of this Li compound in pentane at -40 °. The mixture is then stirred at room temperature for 12 hours and refluxed for a further 2 hours. The LiCl is filtered off, the solvent is removed in vacuo, the residue is mixed with pentane / toluene (20/1) and cooled to -30 °. In the process, o-dimethylaminophenyldimethylgallium crystallizes out, which after isolation has a melting point of 104 °. The following are prepared analogously: o-Dirnethylaminophenyl-diethylgallium
o-Dimethylaminophenyl-dipropylgallium o-dimethylaminophenyl dipropyl gallium
o-Dimethylaminophenyl-dibutylgallium o-dimethylaminophenyl dibutyl gallium
o-Dimethylaminophenyl-dimethylindium o-dimethylaminophenyldimethylindium
o-Dimethylaminophenyl-diethylindium o-dimethylaminophenyl-diethylindium
o-Dimethylaminophenyl-di-iso-propylindium o-dimethylaminophenyl-di-iso-propylindium
o-Dimethylaminophenyl-dibutylindium o-dimethylaminophenyl dibutylindium
o-Dirnethylaminophenyl-dimethylaluminium o-Dirnethylaminophenyl dimethyl aluminum
o-Dimethylaminophenyl-diethylaluminium o-dimethylaminophenyl diethyl aluminum
o-Dimethylaminophenyl-dipropylaluminium o-dimethylaminophenyl dipropyl aluminum
o-Dimethylaminophenyl-di-tert.-butylaluminium o-dimethylaminophenyl-di-tert-butyl aluminum
o-Dimethylaminophenyl-dipentylaluminium o-Diethylaminophenyl-dimethylgallium o-dimethylaminophenyl-dipentylaluminium o-diethylaminophenyl-dimethylgallium
o-Diethylaminophenyl-diethylaluminium o-diethylaminophenyl-diethyl aluminum
o-Diethylaminophenyl-dipropylindium o-Dipropylaminophenyl-dimethylindium o-diethylaminophenyl-dipropylindium o-dipropylaminophenyl-dimethylindium
o-Dipropylaminophenyl-diethylgallium o-Dipropylaminophenyl-diethylgallium
o-Dipropylaminophenyl-di-iso-propylaluminium o-Dimethylaminomethylbenzyl-dimethylaluminium o-Dipropylaminophenyl-di-iso-propylaluminium o-Dimethylaminomethylbenzyl-dimethylaluminium
o-Dimethylaminomethylbenzyl-diethylgallium o-dimethylaminomethylbenzyl-diethylgallium
o-Dimethylaminomethylbenzyl-dipropylindium o-dimethylaminomethylbenzyl dipropylindium
1,2-Diethylaminomethylcyclohexylmethyl-dimethylgallium 1,2-Diethylaminomethylcyclohexylmethyl-diethylgallium 1,2-Diethylaminomethylcyclohexylmethyl-diethylaluminium 1,2-Diethylaminomethylcyclohexylmethyl-dipropylaluminium 1,2-Diethylaminomethylcyclohexylmethyl-dibutylindium 1,2-Diethylaminomethylcyclohexylmethyl-dimethylindium 1,2-Diethylaminomethylcyclohexylmethyl-dimethylgallium 1,2-Diethylaminomethylcyclohexylmethyl-diethylgallium 1,2-Diethylaminomethylcyclohexylmethyl-diethylaluminium 1,2-Diethylaminomethylcyclohexylmethyl-dipropylaluminium 1,2-Diethylaminomethylcyclohexylmethyl-dibutylmethyl-Diethylaluminium-1,2-Diethylaminomethyl
1,2-Dimethylaminomethylcyclopentyl-dimethylgallium 1,2-dimethylaminomethylcyclopentyl dimethyl gallium
1,2-Dimethylaminomethylcyclopentyl-diethylindium 1,2-dimethylaminomethylcyclopentyl diethylindium
1,2-Dimethylaminomethylcyclopentyl-dipropylaluminium. Beispiel 3 1,2-dimethylaminomethylcyclopentyl dipropyl aluminum. Example 3
Zu einem Gemisch aus 45 ml Ether/Hexan (2:1) und 14,7 ml (1,5 N = 22 mmol) n-Butyllithium gibt man bei -50° 5,25 g (22 mmol) o-Trifluormethylbenzylbromid in 10 ml Ether/ Hexan. Nach 15minütigem Rühren werden 2,1 g (16 mmol)5.25 g (22 mmol) of o-trifluoromethylbenzyl bromide in 10 are added to a mixture of 45 ml of ether / hexane (2: 1) and 14.7 ml (1.5 N = 22 mmol) of n-butyllithium at -50 ° ml ether / hexane. After stirring for 15 minutes, 2.1 g (16 mmol)
Dimethylgalliumchlorid in 20 ml Hexan zugegeben. Anschließend läßt man das Reaktionsgemisch auf Raumtemperatur kommen, rührt 24 Stunden, filtriert das LiCl ab und entfernt das Lösungsmittel. Nach Sublimation im Vakuum erhält man o-Trifluormethylbenzyl-dimethylgallium mit Fp. 35°-38°. Dimethyl gallium chloride in 20 ml of hexane was added. The reaction mixture is then allowed to come to room temperature, stirred for 24 hours, the LiCl is filtered off and the solvent is removed. After sublimation in vacuo, o-trifluoromethylbenzyldimethylgallium with mp. 35 ° -38 ° is obtained.
Analog werden hergestellt: o-Trifluormethylbenzyl-diethylgallium The following are prepared analogously: o-trifluoromethylbenzyl-diethylgallium
o-Trifluormethylbenzyl-dipropylgallium o-trifluoromethylbenzyl dipropyl gallium
o-Trifluormethylbenzyl-dibutylgallium o-trifluoromethylbenzyldibutylgallium
o-Trifluormethylbenzyl-dimethylaluminium o-trifluoromethylbenzyl dimethyl aluminum
o-Trifluormethylbenzyl-diethylaluminium o-trifluoromethylbenzyl diethyl aluminum
o-Trifluormethylbenzyl-dipropylaluminium o-trifluoromethylbenzyl dipropyl aluminum
o-Trifluormethylbenzyl-dibutylaluminium o-trifluoromethylbenzyl dibutyl aluminum
o-Trifluormethylbenzyl-dipentylaluminium o-trifluoromethylbenzyl dipentyl aluminum
o-Trifluormethylbenzyl-ethyl-propylaluminium o-trifluoromethylbenzyl-ethyl-propyl aluminum
o-Trifluormethylbenzyl-dimethylindium o-trifluoromethylbenzyldimethylindium
o-Trifluormethylbenzyl-diethylindium o-trifluoromethylbenzyl diethylindium
o-Trifluormethylbenzyl-di-iso-propylindium o-(2,2,2-Trifluorethyl)-benzyl-dimethylgallium o-trifluoromethylbenzyl-di-iso-propylindium o- (2,2,2-trifluoroethyl) -benzyl-dimethylgallium
o-(2,2,2-Trifluorethyl)-benzyl-diethylgallium  o- (2,2,2-trifluoroethyl) benzyl diethyl gallium
o-(2,2,2-Trifluorethyl)-benzyl-diethylaluminium  o- (2,2,2-trifluoroethyl) benzyl diethyl aluminum
o-(2,2,2-Trifluorethyl)-benzyl-methyl-ethylaluminium o-(2,2,2-Trifluorethyl)-benzyl-dipropylindium  o- (2,2,2-trifluoroethyl) benzyl methyl ethyl aluminum o- (2,2,2-trifluoroethyl) benzyl dipropylindium
o-(2,2,2-Trifluorethyl)-benzyl-dimethylindium o- (2-Monofluorethyl)-benzyl-diethylgalliumo- (2,2,2-trifluoroethyl) benzyl dimethyl indium o- (2-monofluoroethyl) benzyl diethyl gallium
o- (2-Monofluorethyl)-benzyl-dimethylindium o- (2-monofluoroethyl) benzyl dimethyl indium
o- (2-Monofluorethyl)-benzyl-dipentylaluminium o- (2-Monofluorethyl)-phenyl-dimethylgalliumo- (2-monofluoroethyl) benzyl dipentyl aluminum o- (2-monofluoroethyl) phenyl dimethyl gallium
o- (2-Monofluorethyl)-phenyl-di-iso-propylaluminiumo- (2-Monofluorethyl)-phenyl-diethylindium o- (3-Monofluorpropyl -phenyl-dimethylgallium o- (2-monofluoroethyl) phenyl-di-iso-propylaluminium- (2-monofluoroethyl) -phenyl-diethylindium o- (3-monofluoropropyl-phenyl-dimethylgallium
o- (3-Monofluorpropyl -phenyl-methyl-ethylgalliumo- (3-Monofluorpropyl -phenyl-diethylaluminiumo- (3-Monofluorpropyl -phenyl-di-tert.-butylaluminiumo- (3-Monofluorpropyl -phenyl-dipropylindiumo- (3-Monofluoropropylphenyl-methyl-ethylgallium- (3-Monofluoropropylphenyl-diethylaluminiumo- (3-Monofluoropropylphenyl-di-tert-butylaluminium- (3-Monofluoropropylphenyl-dipropylindium
o- (3-Monofluorpropyl -phenyl-diethylindium o- ( 3-Monofluorpropyl -benzyl-dimethylgallium o- (3-monofluoropropylphenyl diethylindium o- (3-monofluoropropylbenzyldimethylgallium
o- (3-Monofluorpropyl -benzyl-dimethylaluminium o- (3-Monofluorpropyl -benzyl-dimethylindium o- (3-monofluoropropylbenzyldimethylaluminium o- (3-monofluoropropylbenzyldimethylindium
o- (3-Monofluorpropyl -benzyl-diethylindium o- (3-monofluoropropylbenzyl diethylindium
o- (3-Monofluorpropyl -benzyl-diethylaluminium o- (3-Monofluorpropyl -benzyl-dipropylgallium o- (3-monofluoropropylbenzyl-diethylaluminium o- (3-monofluoropropylbenzyl-dipropylgallium
o- (3-Monofluorpropyl -benzyl-di-iso-propylgalliumo- (3-Monofluorpropyl -benzyl-dibutylaluminium o- (3-Monofluoropropyl-benzyl-di-iso-propyl-gallium- (3-Monofluoropropyl-benzyl-dibutyl aluminum
Beispiel 4 Example 4
Zu einem Gemisch aus 20 ml Benzol und 1 g (5,66 mmol) GaCl3 gibt man langsam bei -70 °C 1,95 g (8,48 mmol) (CF3)2 Cd . DME (DME = Dimethoxyethan) in 20 ml Benzol. Nach Erwärmen auf Raumtemperatur erhält man durch fraktionierte Destillation das Tris-(trifluormethyl)gallium. 1.95 g (8.48 mmol) of (CF 3 ) 2 Cd are slowly added to a mixture of 20 ml of benzene and 1 g (5.66 mmol) of GaCl 3 at -70 ° C. DME (DME = dimethoxyethane) in 20 ml of benzene. After warming to room temperature, the tris (trifluoromethyl) gallium is obtained by fractional distillation.
Analog werden hergestellt: The following are produced analogously:
Tris-(trifluormethyl)indium Tris (trifluoromethyl) indium
Tris-(pentafluorethyl)gallium Tris (pentafluoroethyl) gallium
Tris-(pentafluorethyl)indium Tris (pentafluoroethyl) indium
Tris-(heptafluorpropyl)gallium  Tris (heptafluoropropyl) gallium
Tris-(heptafluorpropyl)indium Tris (heptafluoropropyl) indium

Claims

Patentansprüche 1. Metallorganische Verbindungen der Formel I Y1. Organometallic compounds of the formula I Y
worin wherein
M Aluminium, Indium oder Gallium, -NR 3R4, -PR 3R4, -AsR 3R4, -SbR3R4, M aluminum, indium or gallium, -NR 3 R 4 , -PR 3 R 4 , -AsR 3 R 4 , -SbR 3 R 4 ,
-F oder eine Perfluoralkylgruppe mit 1-7 C-Atomen,  -F or a perfluoroalkyl group with 1-7 C atoms,
X im Falle Y = -F oder eine Perfluoralkylgruppe mit 1-7 C-Atomen: X in the case of Y = -F or a perfluoroalkyl group with 1-7 C atoms:
-(CHR5) mit n = 1, 2, 3, 4, oder 5, o-(CH2)p-C6H4-(CH2)q-, - (CHR 5 ) with n = 1, 2, 3, 4, or 5, o- (CH 2 ) p -C 6 H 4 - (CH 2 ) q -,
1,2-(CH2)p-C6H10-(CH2)q-' 1,2- (CH 2 ) p -C 6 H 10 - (CH 2 ) q - '
1,2-(CH2)p-C6H8 -(CH2)q-' 1,2- (CH 2 ) p -C 6 H 8 - (CH 2 ) q - '
1,2-(CH2)p-C6H6-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H8-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C5H6-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H4-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 4 - (CH 2 ) q -,
1,2-(CH2)p-C4H6-(CH2)q-, oder eine 1,2- (CH 2 ) p -C 4 H 6 - (CH 2 ) q -, or one
Einfachbindung, im Falle Y = -NR3R4, -PR3R4, -AsR3R4 oder -SbR3R4 : o-C6H4-' Single bond, in the case of Y = -NR 3 R 4 , -PR 3 R 4 , -AsR 3 R 4 or -SbR 3 R 4 : oC 6 H 4 - '
1,2-C6H10-, 1,2-C 6 H 10 -,
o-(CH2)r-C6H4-(CH2)s-, o- (CH 2 ) r -C 6 H 4 - (CH 2 ) s -,
1,2-(CH2)r-C6H10-(CH2)s-, 1,2- (CH 2 ) r -C 6 H 10 - (CH 2 ) s -,
1,2-(CH2)p-C6H8-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 8 - (CH 2 ) q -,
1,2-(CH2)p-C6H6-(CH2)q-, 1,2- (CH 2 ) p -C 6 H 6 - (CH 2 ) q -,
1,2-(CH2)p-C5H8-(CH2)q-, 1,2- (CH 2 ) p -C 5 H 8 - (CH 2 ) q -,
1,-2-(CH2)p-C5H6-(CH2)q-, 1, -2- (CH 2 ) p -C 5 H 6 - (CH 2 ) q -,
1,2-(CH2)P -C5H4-(CH2)q- - oder 1,2- (CH 2 ) P -C 5 H 4 - (CH 2 ) q - - or
1,2-(CH2)p-C4H6-(CH2)q-, r und s jeweils unabhängig voneinander 1 , 2 oder 3, p und q jeweils unabhängig voneinander 0, 1, 2 1,2- (CH 2 ) p -C 4 H 6 - (CH 2 ) q -, r and s each independently of one another 1, 2 or 3, p and q each independently 0, 1, 2
oder 3, R 1, R2, R3 und R4 or 3, R 1 , R 2 , R 3 and R 4
jeweils unabhängig voneinander eine Alkylgruppe oder Alkenylgruppe mit bis zu  each independently an alkyl group or alkenyl group with up to
8 C-Atomen, wobei diese Gruppen teilweise oder vollständig fluoriert sein können, eine Cycloalkyl- oder Cycloalkenylgruppe mit 3-8 C-Atomen oder eine Phenylgruppe, und R5 jeweils H oder eine Alkylgruppe mit 8 carbon atoms, these groups being partially or completely fluorinated, a cycloalkyl or cycloalkenyl group having 3-8 carbon atoms or a phenyl group, and R 5 each being H or an alkyl group
1-4 C-Atomen, die auch teilweise oder vollständig fluoriert sein kann, bedeutet. 1-4 carbon atoms, which can also be partially or completely fluorinated.
2. Verwendung der metallorganischen Verbindungen der Formel I nach Anspruch 1 zur Gasphasenabscheidung des Metalls der III. Hauptgruppe oder einer III-V- Kombination auf Substraten. 2. Use of the organometallic compounds of the formula I according to claim 1 for the vapor phase deposition of the metal of III. Main group or a III-V combination on substrates.
3. Verwendung der metallorganischen Verbindungen der Formel I nach Anspruch 1 zur Abscheidung epitaktischer Schichten. 3. Use of the organometallic compounds of the formula I according to claim 1 for the deposition of epitaxial layers.
4. Verfahren zur Herstellung dünner Filme auf Substraten durch Gasphasenabscheidung des Metalls der III. Hauptgruppe oder einer III-V-Kombination aus metallorganischen Verbindungen, dadurch gekennzeichnet, daß als metallorganische Verbindungen die Verbindungen der Formel I nach Anspruch 1 eingesetzt werden. 4. Process for the production of thin films on substrates by vapor deposition of the metal of III. Main group or a III-V combination of organometallic compounds, characterized in that the compounds of formula I according to claim 1 are used as organometallic compounds.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man zur Herstellung von Verbindungshalbleitern, optischen und optoelektronischen Bauteilen während des Abscheidungsprozesses eine oder mehrere unter den angewandten Reaktionsbedingungen gasförmige Verbindungen des Arsens, Antimons oder Phosphors zuführt. 5. The method according to claim 4, characterized in that one or more gaseous compounds of arsenic, antimony or phosphorus are fed under the applied reaction conditions for the production of compound semiconductors, optical and optoelectronic components during the deposition process.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man zusätzlich zu den metallorganischen Verbindungen der Formel I während des AbscheidungsProzesses Dotierstoffe zusetzt. 6. The method according to claim 4, characterized in that in addition to the organometallic compounds of the formula I, dopants are added during the deposition process.
7. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Verbindungen der Formel I nach Anspruch 1 als Dotierstoffe während des Abscheidungsprozesses von anderen metallorganischen Verbindungen zugesetzt werden. 7. The method according to claim 4, characterized in that the compounds of formula I according to claim 1 are added as dopants during the deposition process of other organometallic compounds.
EP90900116A 1988-12-10 1989-11-27 Organoaluminium, organogallium and organoindium compounds and their use for the gas-phase deposition of metal on substrates Withdrawn EP0399021A1 (en)

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