WO2004002946A1 - Neue erdalkalimetallkomplexe und ihre verwendung - Google Patents
Neue erdalkalimetallkomplexe und ihre verwendung Download PDFInfo
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- WO2004002946A1 WO2004002946A1 PCT/EP2003/006501 EP0306501W WO2004002946A1 WO 2004002946 A1 WO2004002946 A1 WO 2004002946A1 EP 0306501 W EP0306501 W EP 0306501W WO 2004002946 A1 WO2004002946 A1 WO 2004002946A1
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- WIPO (PCT)
- Prior art keywords
- formula
- compounds
- compound
- barium
- strontium
- Prior art date
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- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims description 26
- 150000001342 alkaline earth metals Chemical class 0.000 title claims description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 229910052788 barium Inorganic materials 0.000 claims abstract description 16
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000013522 chelant Substances 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 4
- 150000002466 imines Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 239000000543 intermediate Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 4
- 241000239226 Scorpiones Species 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- -1 organometallic alkaline earth metal compounds Chemical class 0.000 description 14
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 11
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- ACAQYOZKHRCWCZ-UHFFFAOYSA-N 8-methoxy-2,2-dimethyloctane-3,5-dione Chemical compound COCCCC(=O)CC(=O)C(C)(C)C ACAQYOZKHRCWCZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000004658 ketimines Chemical group 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- OFXSXYCSPVKZPF-UHFFFAOYSA-N methoxyperoxymethane Chemical compound COOOC OFXSXYCSPVKZPF-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003437 strontium Chemical class 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
Classifications
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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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
- C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/04—Calcium compounds
Definitions
- the invention relates to new, evaporable chelate complexes of calcium, barium and strontium, a process for their preparation, their use for the deposition of layers containing calcium, barium or strontium and intermediates for the preparation of the compounds.
- MOCVD metal-organic chemical vapor deposition
- the organometallic alkaline earth metal compounds have a high volatility, which facilitates sublimation and transport to the deposition site, that they can be thermally decomposed at a relatively low temperature, for example in the range of 450 ° C, and that they separate for certain applications in the form of the oxides, but not, for example, in other decomposition products such as carbonates.
- Alkaline earth metal beta diketonates and certain derivatives have already been used for the MOCVD process.
- Classic are complexes of alkaline earth metals with 1, 1, 6, 6-tetramethyl heptanedionate.
- such complexes can exist as oligomers. These show unsatisfactory volatility and stability.
- the tetramethylheptanedionate complex compounds were used in the form of Lewis base adducts, for example as an adduct with polyethers or polyamines. Such complexes still have stability problems.
- Barium and strontium compounds with ligands that have three coordination sites have also been proposed.
- the object of the present invention is to provide alkaline earth metal compounds which are very suitable for metal-organic chemical phase deposition and are particularly suitable for the production of ceramic thin films. This object is achieved by the compounds of the present invention.
- the compounds according to the invention correspond to the formula (I), M (R) 2 .
- 'M is calcium, strontium and barium.
- R stands for a beta-ketiminate compound (ie the ligand has a keto group and an imino group) in which • the nitrogen atom of the imine function is substituted by a group of the formula (CH 2 ) m NR 1 2 where m is 2 to 4 and R 1 is a Cl-C3 alkyl group, and in which the carbon chain is substituted by R 2 0 (CH 2 ) n , where R 2 is C1-C3 alkyl and n is 2 to 4.
- M preferably stands for strontium and barium. The invention is further explained on the basis of this preferred embodiment.
- the compounds according to the invention have the peculiarity that the anions in the compound of the formula (I) have four coordination sites for an interaction with the metal cation: the keto group; the imino group; the Nitrogen atom of the aminoalkyl group attached to the imine function; and the oxygen atom of the alkoxyalkyl group which is bonded to the carbon chain (“backbone”), preferably via the carbon atom of the ketimine group.
- the keto group the imino group
- Nitrogen atom of the aminoalkyl group attached to the imine function
- oxygen atom of the alkoxyalkyl group which is bonded to the carbon chain (“backbone”), preferably via the carbon atom of the ketimine group.
- m is calcium and preferably barium and strontium
- R 1 and R 2 have the meaning given above
- R 3 is Cl-C4-alkyl.
- the symmetrical representation of the drawing of the molecule should not mean that there is actually a symmetrical arrangement of the atoms in the three-dimensional structure of the respective molecule.
- the lines drawn between the nitrogen and oxygen atoms and the metal cation indicate that a particularly strong interaction is assumed between them.
- R 1 groups on the nitrogen atoms can be the same or different, but are preferably the same and are in particular methyl or ethyl.
- R 3 particularly preferably represents t-butyl.
- n is preferably 3.
- the metallic alkaline earth metal or a hydride thereof which is advantageously finely divided, can be prepared using the method described above.
- the acidic proton is reduced to hydrogen
- the alkaline earth metal is oxidized to the alkaline earth metal cation or the hydride anion is hydrogen, and the desired complex compound according to the invention is formed.
- an alkaline earth metal salt can be reacted with a salt which contains the ligand as an anion, e.g. B. the Li salt (obtainable by reaction of BuLi and the ligand).
- N ', N' -dialkylaminoalkylimino) -8-alkoxy-5-alkanone compound is reacted in a corresponding manner with the most finely divided alkaline earth metal or the hydride.
- Bariu (II) bis [2, 2-dimethyl-5-N- (N ', N' - dimethylaminopropylimino) -8-methoxy-5-octanonate] and strontium (II) bis are very particularly preferably prepared in this way [2,2-dimethyl-5-N- (N 1 , N '-dimethylaminopropylimino) -8-methoxy-5-octanonate].
- ketimine compounds of the formula RH which can be used in the preparation of the complex compounds, where R has the meaning given above, and in particular N ', N' - (dialkylaminoalkylimino) -8-alkoxy-5-alkanone compounds of the formula (II) are also new and are also an important intermediate of the invention.
- R 2 0 (CH 2 ) n C (NCH 2 CH 2 CH 2 R 1 2 ) CH 2 C (O) R 3 apply to R 1 , R 2 , R 3 and n the above meanings.
- the ketimine compounds can be prepared as described below.
- the beta-diketo compound corresponding to the ketimine compound is produced.
- the synthesis is possible via a claise condensation of a ketone with an omega alkoxy carboxylic acid ester.
- the ketone and the omega alkoxycarboxylic acid ester are selected so that the alkyl group of the ketone, the alkyl group the omega alkoxy group and the alkylene chain between the omega alkoxy group and the ester function corresponds to the desired substituents in the ketimine compound to be produced.
- the claise condensation is carried out with heating in the presence of sodium hydride in a solvent, for example in dirthhoxyethane.
- the reaction mixture is worked up, for. B. with aqueous hydrochloric acid.
- the beta-diketo compound prepared in this way can be reacted at elevated temperature with a diamine of the desired chain length.
- a nitrogen atom of this diamine must be substituted by two hydrogen atoms and reacts with a keto group of the beta-diketo compound with elimination of water to form the desired ketimine compound.
- the preparation of the ketimine compounds is based on the preparation of 2,2-dimethyl-5-N- (N 1 , N '-dimethylaminopropyl-imino) -8-methoxy-5-octanone, the particularly preferred ligand for the complexation of the alkaline earth metals , explained further.
- the first stage involves the preparation of 2,2-dimethyl-8-methoxyoctan-3, 5-dione. It can be performed as described by WS Rees Jr., CR Caballero and W. Hesse in Angew. Chem. 104 (1992), No. 6, pages 786 to 788.
- ketimine compounds can be produced analogously.
- the ketimine compounds are not only useful for the preparation of Ba, Sr or Ca complex compounds, but also also for the production of compounds or complexes with other metals.
- alkaline earth metal complexes according to the invention can be used for all those applications in which alkaline earth metal organic compounds are used with the aim of depositing an alkaline earth metal.
- alkaline earth metal deposition is not limited to metallic alkaline earth metal here, but is also intended to include cations of alkaline earth metals.
- a preferred area of application for the alkaline earth metal complexes according to the invention is the deposition of layers which contain the alkaline earth metal in the form of oxides.
- the alkaline earth metal complexes according to the invention are particularly preferably used in the MOCVD process for the production of thin layers which contain the alkaline earth metal, preferably barium and / or strontium in oxidic form.
- Such layers are used, for example, in high-temperature superconductor technology.
- Barium titanate and barium strontium titanate layers are one example.
- Such layers are required, for example, in DRAM technology.
- Such DRAMs have plugs made of polysilicon, which, insulated by a nitride layer, have a platinum coating.
- the platinum layer is coated with a barium strontium titanate layer.
- This can be done using the alkaline earth metal complexes according to the invention in accordance with the MOCVD process.
- MOCVD processes are usually carried out in a vacuum apparatus in which the alkaline earth metal complex compound or a mixture of such compounds is evaporated at low pressure.
- the complex compound is then decomposed and separates in the case of the alkaline earth metal complexes according to the invention on the substrate, for. B. the DRAM, ceramic layers containing the alkaline earth metal in oxidic form.
- Thermal decomposition can also be induced by radiation or photolysis. Another method of decomposition tongue is the plasma-induced decomposition, see also the US patent ' 5,451,434.
- the decomposition is preferably in inert gas, e.g. B. N 2 or Ar performed. If desired, you can also use a reactive gas, e.g. B. 0 2 . This can help maintain good oxide layers. Of course, oxidative aftertreatment can also be provided.
- metals are to be additionally deposited, other commercially available metal compounds can be used simultaneously, before or after the decomposition of the complexes according to the invention, e.g. B. Titanium compounds. Are suitable for. B. the amine pyrrolyl titans mentioned in DE 41 20 344.
- the alkaline earth metal complexes according to the invention are particularly advantageous when used in the MOCVD process, because they are volatile even at low temperatures, are thermally stable, have a stable vapor pressure, and can be decomposed neatly into ceramic oxide layers.
- the compounds are also very useful in the presence of moisture.
- Ketone side 1.84 (p, 2H, -CH 2 central); 1.11 (s, 9H, -CH 3 t-butyl) in ppm against TMS.
- Example 1.1 7.7399 g (38.6 mmol) of the in Example 1.1.
- 2-dimethyl-8-methoxy-3, 5-octanedione and 4.9 ml (3.979 g, 38.9 mmol) of freshly distilled N, N-dimethylaminopropylamine were placed under a dry nitrogen atmosphere in a 25 ml round bottom flask which was equipped with a reflux condenser and magnetic stirrer. The solution was heated to reflux (130 ° C) with vigorous stirring for 18 hours. The mixture was then cooled to room temperature and an equivalent volume of demineralized water was added.
- aqueous phase was then extracted twice with diethyl ether (25 ml each) and the combined organic extracts were dried over anhydrous magnesium sulfate. After filtration, the solvent was removed in vacuo and the residue was distilled in a dynamic vacuum.
- Example 1.2 0.807 g (5.88 mmol) of finely comminuted metallic barium and 3.714 g (13.1 mmol) of the in Example 1.2. prepared octanons were placed under a dry nitrogen atmosphere in a 25 ml round bottom flask equipped with a mechanical stirrer. The suspension was stirred at room temperature until the solid metallic barium had reacted. A highly viscous brown oil was obtained after a reaction time of about 1 week.
- Example 1.2 0.708 g (8.08 mmol) of finely divided metallic strontium and 4.92 g (17.3 mmol) of that in Example 1.2. produced Octanons were added under a dry nitrogen atmosphere in a 25 ml round bottom flask equipped with a mechanical stirrer. The suspension was stirred at room temperature until the solid metallic strontium had completely reacted. A highly viscous oil was obtained after a reaction time of about 1 week.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003242738A AU2003242738A1 (en) | 2002-06-28 | 2003-06-20 | Novel alkaline earth metal complexes and use thereof |
KR10-2004-7020825A KR20050014872A (ko) | 2002-06-28 | 2003-06-20 | 신규한 알칼리토금속 착체 및 그 이용 |
JP2004516624A JP2005531619A (ja) | 2002-06-28 | 2003-06-20 | 新規アルカリ土類金属錯体及びその使用 |
EP03761477A EP1519914A1 (de) | 2002-06-28 | 2003-06-20 | Neue erdalkalimetallkomplexe und ihre verwendung |
US11/022,674 US7132556B2 (en) | 2002-06-28 | 2004-12-28 | Alkaline earth metal complexes and their use |
HK05109292A HK1077292A1 (en) | 2002-06-28 | 2005-10-20 | Alkaline earth metal complexes and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10229040A DE10229040A1 (de) | 2002-06-28 | 2002-06-28 | Neue Erdalkalimetallkomplexe und ihre Verwendung |
DE10229040.7 | 2002-06-28 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/022,674 Continuation US7132556B2 (en) | 2002-06-28 | 2004-12-28 | Alkaline earth metal complexes and their use |
Publications (1)
Publication Number | Publication Date |
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WO2004002946A1 true WO2004002946A1 (de) | 2004-01-08 |
Family
ID=29795933
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/006501 WO2004002946A1 (de) | 2002-06-28 | 2003-06-20 | Neue erdalkalimetallkomplexe und ihre verwendung |
Country Status (11)
Country | Link |
---|---|
US (1) | US7132556B2 (de) |
EP (1) | EP1519914A1 (de) |
JP (1) | JP2005531619A (de) |
KR (1) | KR20050014872A (de) |
CN (1) | CN1291972C (de) |
AU (1) | AU2003242738A1 (de) |
DE (1) | DE10229040A1 (de) |
HK (1) | HK1077292A1 (de) |
MY (1) | MY134966A (de) |
TW (1) | TWI257393B (de) |
WO (1) | WO2004002946A1 (de) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7132556B2 (en) * | 2002-06-28 | 2006-11-07 | Solvay Barium Strontium Gmbh | Alkaline earth metal complexes and their use |
KR100799083B1 (ko) * | 2006-08-04 | 2008-01-29 | 테크노세미켐 주식회사 | 신규한 베타-디케톤 화합물 및 이의 제조방법 |
US7691984B2 (en) | 2007-11-27 | 2010-04-06 | Air Products And Chemicals, Inc. | Metal complexes of tridentate β-ketoiminates |
US7947814B2 (en) | 2006-04-25 | 2011-05-24 | Air Products And Chemicals, Inc. | Metal complexes of polydentate beta-ketoiminates |
US8617305B2 (en) | 2011-01-25 | 2013-12-31 | Air Products And Chemicals, Inc. | Metal complexes for metal-containing film deposition |
US8722933B2 (en) | 2009-03-11 | 2014-05-13 | Air Products And Chemicals, Inc. | Method for preparing metal complexes of polydentate beta-ketoiminates |
US9079923B2 (en) | 2010-08-05 | 2015-07-14 | Air Products And Chemicals, Inc. | Multidentate ketoimine ligands for metal complexes |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7323581B1 (en) * | 1990-07-06 | 2008-01-29 | Advanced Technology Materials, Inc. | Source reagent compositions and method for forming metal films on a substrate by chemical vapor deposition |
US7205422B2 (en) * | 2004-12-30 | 2007-04-17 | Air Products And Chemicals, Inc. | Volatile metal β-ketoiminate and metal β-diiminate complexes |
US8092870B2 (en) * | 2008-04-11 | 2012-01-10 | Air Products And Chemicals, Inc. | Preparation of metal oxide thin film via cyclic CVD or ALD |
US20100119726A1 (en) * | 2008-11-07 | 2010-05-13 | Air Products And Chemicals, Inc. | Group 2 Metal Precursors For Deposition Of Group 2 Metal Oxide Films |
JP5544198B2 (ja) * | 2010-03-17 | 2014-07-09 | 株式会社Adeka | β−ケトイミン化合物、金属錯体及び薄膜形成用原料 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0369297A1 (de) * | 1988-11-14 | 1990-05-23 | Air Prod & Chem | Flüchtige beta-Ketoimine und ihre Metallkomplexe |
US5008415A (en) * | 1988-11-14 | 1991-04-16 | Air Products And Chemicals, Inc. | Volatile fluorinated β-ketoimines and associated metal complexes |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3594216A (en) * | 1969-06-19 | 1971-07-20 | Westinghouse Electric Corp | Vapor phase deposition of metal from a metal-organic beta-ketoamine chelate |
DE4120344A1 (de) | 1990-06-26 | 1992-01-02 | Kali Chemie Ag | Verfahren zur abscheidung von titan, zirkonium oder hafnium enthaltenden schichten |
DE4108731A1 (de) * | 1991-03-18 | 1992-09-24 | Solvay Barium Strontium Gmbh | Neuartige erdalkalimetall-heptandionat-verbindungen |
JP3227891B2 (ja) * | 1993-04-20 | 2001-11-12 | 三菱マテリアル株式会社 | 新規な有機金属錯体とその配位子 |
JP3904255B2 (ja) | 1995-11-14 | 2007-04-11 | 株式会社Adeka | β−ジケトン化合物およびその金属錯体 |
EP1184365A3 (de) * | 2000-08-26 | 2003-08-06 | Samsung Electronics Co., Ltd. | Metall-Vorläufer der Gruppe IV und ein Chemical-Vapor-Deposition-Verfahren mit diesem |
KR100807947B1 (ko) * | 2001-01-30 | 2008-02-28 | 삼성전자주식회사 | 비대칭형 β-케토이미네이트 리간드 화합물의 제조방법 |
DE10229040A1 (de) * | 2002-06-28 | 2004-01-29 | Solvay Barium Strontium Gmbh | Neue Erdalkalimetallkomplexe und ihre Verwendung |
-
2002
- 2002-06-28 DE DE10229040A patent/DE10229040A1/de not_active Withdrawn
-
2003
- 2003-06-20 EP EP03761477A patent/EP1519914A1/de not_active Withdrawn
- 2003-06-20 KR KR10-2004-7020825A patent/KR20050014872A/ko not_active Application Discontinuation
- 2003-06-20 CN CNB038153173A patent/CN1291972C/zh not_active Expired - Fee Related
- 2003-06-20 JP JP2004516624A patent/JP2005531619A/ja active Pending
- 2003-06-20 WO PCT/EP2003/006501 patent/WO2004002946A1/de active Application Filing
- 2003-06-20 AU AU2003242738A patent/AU2003242738A1/en not_active Abandoned
- 2003-06-26 TW TW092117401A patent/TWI257393B/zh not_active IP Right Cessation
- 2003-06-27 MY MYPI20032427A patent/MY134966A/en unknown
-
2004
- 2004-12-28 US US11/022,674 patent/US7132556B2/en not_active Expired - Fee Related
-
2005
- 2005-10-20 HK HK05109292A patent/HK1077292A1/xx not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0369297A1 (de) * | 1988-11-14 | 1990-05-23 | Air Prod & Chem | Flüchtige beta-Ketoimine und ihre Metallkomplexe |
US5008415A (en) * | 1988-11-14 | 1991-04-16 | Air Products And Chemicals, Inc. | Volatile fluorinated β-ketoimines and associated metal complexes |
Non-Patent Citations (2)
Title |
---|
NEUMAYER, D A ET AL: "Approaches to alkaline earth metal-organic chemical vapor deposition precursors. Synthesis and characterisation of barium fluoro-beta-letoiminate complexes having appended poyether "lariats"", INORGANIC CHEMISTRY., vol. 37, no. 21, 1998, AMERICAN CHEMICAL SOCIETY. EASTON., US, pages 5625 - 5633, XP002261922, ISSN: 0020-1669 * |
SCHULZ, D L ET AL: "Barium beta-ketoiminate complexes containing appended ether "lariats". Synthesis, characterization, and implementation as fluorine-free barium MOCVD precursors", CHEMISTRY OF MATERIALS., vol. 5, no. 11, 1993, AMERICAN CHEMICAL SOCIETY, WASHINGTON., US, pages 1605 - 1617, XP002261923, ISSN: 0897-4756 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7132556B2 (en) * | 2002-06-28 | 2006-11-07 | Solvay Barium Strontium Gmbh | Alkaline earth metal complexes and their use |
US7947814B2 (en) | 2006-04-25 | 2011-05-24 | Air Products And Chemicals, Inc. | Metal complexes of polydentate beta-ketoiminates |
KR100799083B1 (ko) * | 2006-08-04 | 2008-01-29 | 테크노세미켐 주식회사 | 신규한 베타-디케톤 화합물 및 이의 제조방법 |
US7691984B2 (en) | 2007-11-27 | 2010-04-06 | Air Products And Chemicals, Inc. | Metal complexes of tridentate β-ketoiminates |
US7723493B2 (en) | 2007-11-27 | 2010-05-25 | Air Products And Chemicals, Inc. | Metal complexes of tridentate BETA -ketoiminates |
US8722933B2 (en) | 2009-03-11 | 2014-05-13 | Air Products And Chemicals, Inc. | Method for preparing metal complexes of polydentate beta-ketoiminates |
US9079923B2 (en) | 2010-08-05 | 2015-07-14 | Air Products And Chemicals, Inc. | Multidentate ketoimine ligands for metal complexes |
US8617305B2 (en) | 2011-01-25 | 2013-12-31 | Air Products And Chemicals, Inc. | Metal complexes for metal-containing film deposition |
Also Published As
Publication number | Publication date |
---|---|
AU2003242738A1 (en) | 2004-01-19 |
MY134966A (en) | 2008-01-31 |
CN1291972C (zh) | 2006-12-27 |
CN1665775A (zh) | 2005-09-07 |
HK1077292A1 (en) | 2006-02-10 |
TWI257393B (en) | 2006-07-01 |
US7132556B2 (en) | 2006-11-07 |
TW200403249A (en) | 2004-03-01 |
EP1519914A1 (de) | 2005-04-06 |
KR20050014872A (ko) | 2005-02-07 |
DE10229040A1 (de) | 2004-01-29 |
JP2005531619A (ja) | 2005-10-20 |
US20050170092A1 (en) | 2005-08-04 |
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