Classifications

• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/10—Inorganic compounds or compositions
  • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
• • 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
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
  • C30B25/02—Epitaxial-layer growth

Definitions

• the invention relates to the use of element-organic compounds which contain phosphorus or arsenic as an element for the deposition of the group V element or also a III-V combination from the gas phase or in a vacuum, and a process for the production of thin films or layers by separating elements from elemental organic compounds from the gas phase or in a vacuum.
• MOCVD Metal-Organic Chemical Vapor Deposition
• Photo-MOVP Photo-Metal-Organic Vapor Phase
• Laser CVD Laser Chemical Vapor Deposition
• MOMS Metal-Organic Magnetron Sputtering
• organometallic compounds are used which decompose at a temperature below 1100 ° C. upon deposition of the metal.
• Typical apparatuses which are currently used for MOCVD consist of a "bubbler" with a feed for the organometallic component, a reaction chamber which contains the substrate to be coated, and a source for a carrier gas which acts against the organometallic component nente should be inert.
• the "bubbler” is kept 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 can be controlled well, and thus controlled growth of the thin layers is also possible.
• R straight-chain or branched-chain alkyl with 1-14 C atoms, which can also be partially or completely fluorinated,
• R 3 , R 4 are hydrogen or alkyl, which can also be partially or completely fluorinated, with 1-8 C-atoms and the proviso that up to three residues of
• R 1 , R 2 , R 3 , R 4 can simultaneously be hydrogen.
• the invention furthermore relates to a method for producing layers on substrates by gas phase or vacuum deposition of elements from element-organically see connections, which is characterized in that as. elemental compound uses compounds of formula I, these initially at temperatures between 100 ° and 800 ° C in situ in compounds of formula III
• HM (R ') 2 HI with R' hydrogen or straight-chain or branched alkyl having 1-14 C atoms, which can also be partially or completely fluorinated,
• the principle of the new process is that the stable compounds of the formula I disintegrate during the MOCVD process by ß-elimination.
• a stock of typically 1 to 10 kg of a highly toxic group V-H compound is completely dispensed with.
• a characteristic of the precursor compounds of the formula I is the presence of at least one C — H bond on the ⁇ -position C atoms in the organic radical.
• the compounds of the formula I are known, but not in connection with the deposition processes mentioned.
• the compounds of the formula I have three radicals R, these radicals may be the same or different, but at least one radical must be a branched alkyl radical which has at least one CH bond on the ⁇ -carbon atom.
• M means phosphorus or arsenic, preferably arsenic.
• the radicals R are each, independently of one another, a straight-chain or branched alkyl group having 1-14 C atoms, preferably 1-10 C atoms.
• the alkyl groups are preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, sec-butyl, tert-butyl, 2-methylpentyl, 3-methylpentyl or 2-octyl.
• the alkyl radicals can also be partially or completely fluorinated and then preferably mean monofluoromethyl, difluoromethyl, trifluoromethyl, difluoroethyl, pentafluoroethyl, trifluoropropyl, heptafluoropropyl, nonafluorobutyl or undecafluoropentyl.
• At least one of the radicals R has structure II
• R 1 , R 2 , R 3 and R 4 mean H or alkyl with 1-8 C atoms, it being possible for the alkyl groups to be partially or completely fluorinated.
• the preferred groups already mentioned come into consideration. Up to 3 residues of R 1 , R 2 , R 3 and R 4 can be used simultaneously
• two radicals are hydrogen at the same time.
• a radical R preferably represents a group with the structure II, the other two radicals are preferably straight-chain alkyl groups.
• n-alkyl means straight-chain alkyl or fluoroalkyl.
• R, R 1 , R 2 , R 3 and R 4 have the meanings already given in the formulas I and II and are also the subject of the present inventions.
• Preferred compounds of the formula IV are, for example, the compounds of the formulas (3), (9), (11), (12), (14), (16), (21) and (22).
• the known compounds of the formula I and the new compounds of the formula IV 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. You can also make use of variants which are known per se and are not mentioned here in detail.
• So compounds of the formulas I and IV z. B. be produced by reacting appropriate Group V- (alkyl) chlorides with an alkali metal organyl or a Grignard compound in an inert solvent.
• 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 organo-element compounds according to the invention prove to be stable under inert gas conditions at room temperature, but can be decomposed at elevated temperature. In addition, they show only a low vapor pressure at room temperature in comparison to PH 3 or AsH 3 . Their solubility in organic solvents such as aliphatic or aromatic hydrocarbons or ether is excellent. In particular, the compounds of the formulas I and IV have a significantly lower toxicity than the highly toxic group VH compounds.
• the process according to the invention consists in using organic compounds of these elements which are suitable for ⁇ -elimination, that is to say elemental organic compounds of the formula I, for the production of layers on substrates by gas phase or vacuum deposition of elements such as phosphorus or arsenic.
• HM (R ') 2 HI with R' hydrogen or straight-chain or branched alkyl having 1-14 C atoms, which may also be partially or completely fluorinated, transferred in situ and then decomposed and deposited on the substrate.
• reaction conditions for the deposition can be chosen analogously to the values familiar from the literature and the person skilled in the art.
• one or more compounds which are gaseous under the reaction conditions can be used in the process according to the invention during the deposition process in the decomposition chamber
• Elements of the periodic table preferably metal-organic compounds of aluminum, gallium or indium, can be added.
• Standard substances such as trimethyl gallium or trimethyl indium are just as possible as intramolecularly stabilized compounds (GB 21 23 422, EP-A 108 469, EP-A 176 537, DE-OS 36 31 469, DE-OS 38 41) 643).
• dopants can be added to the deposition process.
• Volatile organometallic compounds of iron, magnesium, zinc or chromium are used as dopants.
• the preferred compounds are, for example, Zn (CH 3 ) 2 , Zn (C 2 H 5 ) 2 Mg (C 5 H 5 ) 2 or Fe (C 5 H 5 ) 2 .
• Mp melting point and boiling point.
• Solvent is distilled off completely and thermal decomposition commences at 120 ° -130 ° C. with distillation of the isobutyl bromide formed. The remaining phase is fractionated and clear diisobutylarsen bromide is obtained.
• a Grignard solution is prepared from ethyl bromide, magnesium and diethyl ether.
• the diisobutylarsen bromide obtained in a) (diluted with ether) is added dropwise to this Grignard solution.
• the mixture is stirred under reflux overnight, "the solvent is distilled off and all other volatile constituents are condensed into a receiver cooled with liquid nitrogen. After fractionation, water-clear monoethyldiisobutylarsine is obtained.
• the triethylarsine is prepared from triethylaluminum, arsenic trichloride and KC1 in petroleum ether in 70% yield.
• a Grignard solution is prepared from 1.62 mol of tert-butyl chloride, 2.43 mol of magnesium in 1000 ml of diethyl ether. 0.66 mol (C 2 H 5 ) 2 AsBr in 1000 ml of diethyl ether are added dropwise to this solution.
• the further workup is carried out analogously to Example 3 b) and water-clear diethyl tert-butylarsine with a boiling point of 42 ° C./1 mbar is obtained.

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• 1992
  • 1992-04-30 DE DE19924214224 patent/DE4214224A1/de active Granted
• 1993
  • 1993-04-23 WO PCT/EP1993/000986 patent/WO1993022473A1/de not_active Ceased
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