CN101775041B - 2-acyl 1,3-indane dione silver compound with stable organic phosphine, preparation method and application thereof - Google Patents
2-acyl 1,3-indane dione silver compound with stable organic phosphine, preparation method and application thereof Download PDFInfo
- Publication number
- CN101775041B CN101775041B CN2009102645749A CN200910264574A CN101775041B CN 101775041 B CN101775041 B CN 101775041B CN 2009102645749 A CN2009102645749 A CN 2009102645749A CN 200910264574 A CN200910264574 A CN 200910264574A CN 101775041 B CN101775041 B CN 101775041B
- Authority
- CN
- China
- Prior art keywords
- silver
- ethanoyl
- indane dione
- indane
- organic phosphine
- 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.)
- Expired - Fee Related
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229940100890 silver compound Drugs 0.000 title claims abstract description 19
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 30
- 239000004332 silver Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- -1 2-ethanoyl-1,3-indane dione silver Chemical compound 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 28
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000002902 organometallic compounds Chemical class 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 238000005352 clarification Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical group CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005138 cryopreservation Methods 0.000 description 1
- DVIDIZXCFDHODG-UHFFFAOYSA-N cyclopentylphosphane Chemical class PC1CCCC1 DVIDIZXCFDHODG-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Abstract
The invention discloses a 2-acyl 1,3-indane dione silver compound with stable organic phosphine, a preparation method and the application thereof in preparing silver film, which relate to a metal organic compound and a synthesis method thereof. The 2-acyl 1,3-indane dione silver compound is shown as the accompanying drawing. The compound has the advantages of good stability, low decomposition temperature, simple synthesis, convenient operation, high yield, low cost and the like, and can serve as the material for preparing silver film.
Description
One, technical field:
The present invention relates to a metal-organic complex, its preparation method, specifically relate to containing of stable organic phosphine of multiple substituent 2-acyl group-1,3-indane dione silver compound, its preparation method and the application aspect the silver-colored thin-film material of preparation thereof.
Two, background technology:
For product: still do not have report on the document, institute's synthetic is a kind of 2-acyl group-1 of new stable organic phosphine, the 3-indane dione silver compound.For method, synthetic at present these title complexs generally will carry out under the anhydrous and oxygen-free condition.For application, the synthetic 2-of institute acyl group-1,3-indane dione silver compound are a kind of new title complexs, thus also not with it as the grow report of metallic film material aspect of precursor.
Argent is the best a kind of metal (resistivity: 1.59 μ Ω cm) of electroconductibility in all metals; So it also is a kind of very promising interconnection material that is applied to VLSI; Adopt silver as interconnection material than adopting copper at the transport delay aspect of performance 7% improvement to be arranged as interconnection material, so people such as YosiShacham-Diamand has proposed the Ag interconnection technique.Be that the device of lead can bear than copper to be the more intensive circuit configuration of lead device, can also further to reduce the number of required metal level with silver.The application of this new type of metal interconnection technique will further improve the interconnection performance, and will greatly promote the development of interconnection technique from now on.([1] Kodas T.T., Hampden-Smith M.J., The Chemistry of Metal CVD, VCH, Weinheim, 1994; [2] Huang Hao, Wei Liang, Tang's electricity, the progress and the trend of semiconductor alloy interconnection integrated technology, metal heat treatmet, 2004,29 (8): 26-31; [3] Yosi Shacham Diamand, Alexandra Inbern, Ielena Sverdlov, et al., J.Electrochemical Soc., 2000,147 (9): 3345-3349)
Metal organic chemical vapor deposition (MOCVD) is the high-quality mf technology of a kind of very effective preparation.Because it has faster sedimentation rate, step coverage and higher aspect ratio preferably in the multiwalled metallization structure.The MOCVD growth of silver film is main is to research and develop out more many, precursor more suitably, to various deposition reaction Study on Conditions and optimization, and the further investigation that process, mechanism, reaction Kinetics Model and the reaction of deposition reaction are controlled etc.Yet, be will seek suitable a metal-organic complex as presoma with the key of mocvd method growing film material.The presoma of silver roughly is divided into following several types: LAgOOCR, LAg (Cyclopentadienyl), L
nAg (beta-diketonate), AgX.
Silver?carboxylates L·Ag(β-diketonates) L·Ag(Cyclopentadienyl)
For example, Voorhoeve etc. ([1] Kodas T.T., Hampden-Smith M.J., The Chemistryof Metal CVD, VCH, Weinheim, 1994) have reported and have used the fluorochemical of silver to prepare silverskin as presoma that concrete reaction equation is following:
Si(s)+4AgF→4Ag(s)+SiF
4(s)
The temperature of reaction that this reaction needed is very high (600 ℃), in addition, because silicon substrate can be participated in reaction, so can certain corrodibility be arranged to substrate.Beach etc. ([1] Kodas T.T., Hampden-Smith M.J., The Chemistry of Metal CVD, VCH, Weinheim, 1994) use cyclopentadiene and organic phosphine to synthesize a series of organic silver title complex as part, and have applied for patent.
Physics and chemical property for the MOCVD presoma have strict requirement, and how one of them main challenge synthesizes suitable precursor if coming from.A suitable presoma should possess following condition: stable under (1) room temperature.(2) suitable volatility: the MOCVD growth for Thin Film needs a kind of precursor of easy handling, and like liquid state or solid-state, it will have enough volatility to obtain its steam below 200 ℃.(3) suitable reactivity: precursor can react at substrate surface, but reactive behavior can not be too strong, is unlikely in leading to the pipeline of reaction chamber, just to decompose.(4) very high purity: the purity of film has very large influence to the performance of material, and film requires cleaning in the extreme, does not contain pollutent.In order to reach this requirement, all impurity all must strictly be controlled, and gets rid of outside reaction chamber.(5) less environmental influence: what environmental problem became in this day and age becomes more and more important, so precursor is nontoxic or low toxicity as far as possible, residue preferably can reclaim or be easy to aftertreatment.(6) suitable cost: in order to be applied to suitability for industrialized production, presoma preferably can synthesize in a large number, is in kilogram at least, and adopts simple as far as possible synthesis step.([4] J.Rickerby; J.H.G.Steinke; Current Trends in Patterning with Copper, Chem.Rev., 2002; 102:1525-1549) people are in order to search out suitable presoma, constantly have in recent years some new Ag title complexs report successively as: with schiff bases and organic phosphine is the silver complex of part.([5]Thomas?Haase，Thomas?Haase’s?doctor?thesis，Technische
Chemnitz，2004)
Three, summary of the invention:
The purpose of this invention is to provide little, the simple synthetic method of a kind of pollution to substrate; Technological operation is simple; Productive rate is high, the stable organic phosphine that cost is low contain multiple substituent 2-acyl group-1,3-indane dione silver compound and compound method thereof with in the application for preparing aspect the silver-colored thin-film material.
The 2-acyl group-1 of stable organic phosphine of the present invention, the 3-indane dione silver compound is represented with formula:
Wherein
N=1,2 or 3
R′＝OCH
3、OCH
2CH
3、CH
3、C
2H
5、
I-Pr, n-Bu, t-Bu, Cy or Ph
As a kind of optimal way, above-mentioned R is CH
3O, CH
3, C
2H
5
A kind of 2-acyl group-1 for preparing stable organic phosphine, the method for 3-indane dione silver compound is characterized in that its step is following:
(1), prepare 2-acyl group-1,3-indane dione silver: under protection of inert gas, with 2-acyl group-1,3-indenes diketone and triethylamine add alcoholic solvent to dissolving clearly; Under 0 ℃～-40 ℃ temperature and lucifuge condition, drip with the molten clear Silver Nitrate of acetonitrile/alcohol mixed solvent to above-mentioned clear liquid, drip the back and stirred 2～3 hours; Cross and filter white solid, wash twice respectively with ethanol, ether, drain that solid is an off-white color behind the solvent, the solid of gained is a 2-acyl group-1, the 3-indane dione silver; Above-mentioned 2-acyl group-1, mol ratio is 1: 1: 1 in 3-indenes diketone, triethylamine, the Silver Nitrate reaction process; Reaction equation is following
(2), the 2-acyl group-1 of stable organic phosphine, the compound method of 3-indane dione silver compound: with 2-acyl group-1, the mixture of 3-indane dione silver and organophosphorus ligand [purchasing] places anhydrous organic solvent to stir; At 0 ℃～-40 ℃ following stirring reactions more than 4 hours; After reaction finishes, cross and filter settled solution, solvent is drained, promptly obtain title complex with oil pump; 2-acyl group-1, mol ratio is that 1: 1～1: 3 and preparation process are carried out under inert atmosphere and lucifuge condition in 3-indane dione silver and the organophosphorus ligand reaction process.
Above-mentioned alcoholic solvent can be methyl alcohol, ethanol etc.
Above-mentioned acetonitrile/alcohol mixed solvent can dissolve clear Silver Nitrate and get final product, and does not have designated ratio.
Above-mentioned rare gas element is a nitrogen, and argon gas etc., anhydrous organic solvent are methylene dichloride or chloroform or 1, the 2-ethylene dichloride.
The above-mentioned title complex that obtains characterizes it with detection meanss such as nuclear-magnetism, infrared, mass spectrum, ultimate analyses, proves our expected compound.
Above-mentioned 2-acyl group-1; The 3-indane dione silver compound utilizes metal organic chemical vapor deposition (MOCVD) means to prepare silver-colored thin-film material as presoma, and concrete operations are referring to document (J.Rickerby, J.H.G.Steinke; Current Trends in Patterning with Copper; Chem.Rev., 2002,102:1525-1549)
ESEM is the electron beam that utilizes immobilized or do a branch of fine focus of raster scanning at sample surfaces; The bombardment sample surfaces produces various signals (photon of secondary electron, backscattered electron, Auger electron, characteristic X-ray and different-energy etc.); Utilize the electromagnetic lens system imaging, the instrument that solid material is analyzed.Be widely used in scientific domains such as biology, geology, solid-state physics, electronics and material.These experiments are to be used for analyzing at the film-formation result of the various presomas of chemical vapor deposition experiment and the surface topography of film.
With title complex (CH
3O)
3PAgC
11H
7O
3Be example, can analyze that the film surface appearance that utilizes metal organic chemical vapor deposition (MOCVD) means to prepare is fine, explain that these a series of title complexs can be used as precursor and are used to prepare silver-colored thin-film material from Fig. 1.
| Title | Chemical molecular formula | Purchase company | PIN |
| Trimethyl-phosphine | CH 3) 3P | Alfa | 30143 |
| Triethyl phosphine | (C 2H 5) 3P | Alfa | 30177 |
| Trimethyl phosphite | CH 3O) 3P | Alfa | 30132 |
| Triethyl-phosphite | C 6H 15O 3P | Alfa | L00339 |
| Tri isopropyl phosphine | [(CH 3) 2CH] 3P | Alfa | 41684 |
| Tri-n-butyl phosphine | C 12H 27P | Alfa | A12649 |
| Three tertiary butyl phosphines | [(CH 3) 3C] 3P | Alfa | 10178 |
| Triphenylphosphine | (C 6H 5) 3P | Alfa | A14089 |
| Three cyclopentyl phosphines | (C 5H 9) 3P | Cyanogen specialization worker ltd | Do not have |
Beneficial effect:
1, for product: still do not have report on the document, institute's synthetic is a kind of 2-acyl group-1 of new stable organic phosphine, the 3-indane dione silver compound.
2, for method: synthetic at present these title complexs generally will carry out under the anhydrous and oxygen-free condition.
3, for application: the synthetic 2-of institute acyl group-1,3-indane dione silver compound are a kind of new title complexs, thus also not with it as the grow report of metallic film material aspect of precursor.
4, the present invention compared with prior art has following remarkable advantage:
(1) the 2-acyl group-1 of stable organic phosphine of the present invention; The 3-indane dione silver compound has stability and lower decomposition temperature preferably; Degradation production all is a gaseous state, and little to the pollution of substrate, so can be used as precursor with methods such as the chemical vapour deposition silver-colored thin-film material of growing.
(2) simple synthetic method, technological operation is simple, and productive rate is high, and cost is low.
Four, description of drawings
Fig. 1 is the SEM figure of silver-colored film
The hydrogen spectrogram of Fig. 2 embodiment 3 title complexs
The hydrogen spectrogram of Fig. 3 embodiment 4 title complexs
The hydrogen spectrogram of Fig. 4 embodiment 5 title complexs
The hydrogen spectrogram of Fig. 5 embodiment 6 title complexs
The hydrogen spectrogram of Fig. 6 embodiment 7 title complexs
The hydrogen spectrogram of Fig. 7 embodiment 8 title complexs
Fig. 8 is the carbon spectrogram of embodiment 3 title complexs
Fig. 9 is the carbon spectrogram of embodiment 4 title complexs
Figure 10 is the carbon spectrogram of embodiment 5 title complexs
Figure 11 is the carbon spectrogram of embodiment 6 title complexs
Figure 12 is the carbon spectrogram of embodiment 7 title complexs
Figure 13 is the carbon spectrogram of embodiment 8 title complexs
Five, embodiment:
2-acyl group-1,3-indenes diketone synthetic
Get the there-necked flask of a 500ml, connect the nitrogen protection pipe, substitute gas three times, (7.4680g 0.32mol), substitutes gas twice, N to add sodium
2Under add C
2H
5OH (14.9607g, 0.32mol), exsiccant toluene (20ml) and benzene (250ml), stirring at normal temperature 1h is warming up to 70 ℃, stirs 4h; Intact to the sodium primitive reaction, be chilled to room temperature, slowly add dimethyl phthalate (72.1604g, 0.32mol) (18.8583g, mixture 0.32mol) are warming up to 85 ℃ with acetone; Stir 20h, the outstanding steaming except that desolvating obtains yellow solid, join in the 1.5L zero(ppm) water, and hold over night, separatory is removed layer oily matter; The upper strata stillness of night to PH=3-4, produces yellow solid with hcl acidifying, leaves standstill 24h, filters, and gets yellow solid; Drying, water and recrystallizing methanol obtain the glassy yellow solid, 11.43g, productive rate: 18.7%.110 ℃ of Mp.:109, fusing point consistent with literature value (Ercules E.S.Teotonio, Hermi F.Brito, Hans Viertler, et al., Polyhedron, 2006,25:3488-3494).
2-acyl group-1,3-indane dione silver synthetic
Get the there-necked flask of a 100ml, connect the nitrogen protection pipe, substitute gas three times, there-necked flask is wrapped with masking foil, lucifuge, N
2Under add AgNO
3(1.0110g, 5.95mmol), CH
3OH (15ml), CH
3(0.2443g, 5.95mmol), 0 ℃ is stirred 20min down to CN, dissolves clearly, is colourless transparent solution, is made as solution A.
Get the there-necked flask of a 50ml, plug the nitrogen protection pipe, substitute gas three times, N
2Under add 2-acyl group-1,3-indenes diketone (1.1200g, 5.95mmol), CH
3OH (10ml), (C
2H
5)
3(0.6022g, 5.95mmol), stirring at normal temperature 10min dissolves clearly N, is red solution.N
2Down inferior solution is joined among the A, produce yellow mercury oxide immediately, ice bath stirs 2h, filters with sand core funnel, and methyl alcohol is washed 2 times, in solid transfer to the schlenk pipe, and vacuum-drying 12h under the room temperature.Obtain 1.31g (75%).Lucifuge, cryopreservation.
Embodiment 3.
Ph
3PAgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.2048g (0.78mmol) the triphenylphosphine achromaticity and clarification liquid of 20mL methylene dichloride, be added drop-wise to 0.2304g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride; In the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.43g, i.e. title complex.Productive rate: 98%.Mp.：202?203℃?dec.Anal.calcd.For?C
29H
22O
3AgP：C，62.49；H，3.98.Found：C，62.64；H，3.87.
1H?NMR(CDCl
3)：δ2.6(s，3H，CH
3-H)，7.4?7.6(m，19H，Ph-H).
13C{H}NMR(CDCl
3)：δ28.5(CH
3)，109.4(C)，120.7(C
6H
4)，129.3(J
PC＝10.7Hz，C
6H
5)，130.4(J
PC＝38.9Hz，C
6H
5)，131.2(J
PC＝1.97Hz，C
6H
5)，132.1(C
6H
4)，134.1(J
PC＝16.5Hz，C
6H
5)，196.1(C＝O).IR(KBr)data(cm
-1)：3444(w)，3053(m)，1765(w)，1670(m)，1625(s)，1589(s)，1508(m)，1479(m)，1435(s)，1357(m)，1096(m)，882(m)，733(s)，693(s)，524(s)，506(m).
Embodiment 4.
(Ph
3P)
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.3704g (1.41mmol) the triphenylphosphine achromaticity and clarification liquid of 20mL methylene dichloride, be added drop-wise to 0.2083g (0.71mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride; In the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.57g, i.e. title complex.Productive rate: 98%.Mp.：219?220℃?dec.Anal.calcd.for?C
47H
37O
3AgP
2：C，68.87；H，4.55.Found：C，68.43；H，4.45.
1H?NMR(CDCl
3)：δ2.4(s，3H，CH
3-H)，7.2?7.4(m，34H，Ph-H).
13C{H}NMR(CDCl
3)：δ29.0(CH
3)，109.5(C)，120.0(C
6H
4)，128.7(J
PC＝9.6Hz，C
6H
5)，130.2(C
6H
5)，131.4(C
6H
4)，132.7(J
PC＝26.6Hz，C
6H
5)，134.1(J
PC＝16.7Hz，C
6H
5)，194.8(C＝O).IR(KBr)data(cm
-1)：3447(w)，3050(m)，1760(w)，1670(m)，1625(s)，1590(s)，1520(m)，1479(m)，1434(s)，1363(m)，1095(m)，880(m)，744(m)，694(s)，513(m).
(CH
3O)
3PAgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.1412g (1.14mmol) P (OCH of 20mL methylene dichloride
3)
3Achromaticity and clarification liquid is added drop-wise to 0.3358g (1.14mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get weak yellow liquid 0.46g, i.e. title complex.Productive rate: 97%.Anal.calcd.forC
14H
16O
6AgP：C，40.12；H，3.85.Found：C，40.01；H，3.88.
1H?NMR(CDCl
3)：δ2.5(s，3H，CH
3-H)，3.7(d，9H，CH
3O-H，J
PH＝13.5Hz)，7.4?7.5(m，4H，Ph-H).
13C{H}NMR(CDCl
3)：δ27.7(CH
3)，51.3(J
PC＝4.3Hz，CH
3/CH
3O-)，108.8(C)，120.1(C
6H
4)，131.8(C
6H
4)，137.6(C
6H
4)，139.1(C
6H
4)，192.2(C＝O)，194.9(C＝O).IR(KBr)data(cm
-1)：3481(w)，2951(m)，2842(m)，1766(w)，1676(m)，1626(s)，1589(s)，1505(m)，1440(s)，1354(m)，1341(m)，1185(m)，1150(m)，1015(s)，883(m)，796(s)，766(s)，732(s)，529(s).
Embodiment 6.
[(CH
3O)
3P]
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.1898g (1.53mmol) P (OCH of 20mL methylene dichloride
3)
3Achromaticity and clarification liquid is added drop-wise to 0.2258g (0.76mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get weak yellow liquid 0.40g, i.e. title complex.Productive rate: 96%.Anal.calcd.forC
17H
25O
9AgP
2：C，37.59；H，4.64.Found：C，37.09；H，4.34.
1H?NMR(CDCl
3)：δ2.5(s，3H，CH
3-H)，3.6(d，18H，CH
3O-H，J
PH＝12.9Hz)，7.4?7.5(m，4H，Ph-H).
13C{H}NMR(CDCl
3)：δ28.2(CH
3)，50.6(J
PC＝5.0Hz，CH
3/CH
3O-)，108.6(C)，119.7(C
6H
4)，131.4(C
6H
4)，138.6(C
6H
4)，193.1(C＝O)，194.4(C＝O).IR(KBr)data(cm
-1)：3473(w)，2950(m)，2842(m)，1764(w)，1673(s)，1625(s)，1589(s)，1520(m)，1428(m)，1353(m)，1341(m)，1185(m)，1150(m)，1012(s)，881(m)，791(s)，754(s)，734(s)，528(s).
Embodiment 7.
(C
2H
5O)
3PAgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.1680g (1.01mmol) P (OC of 20mL methylene dichloride
2H
5)
3Achromaticity and clarification liquid is added drop-wise to 0.2983g (1.01mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.46g, i.e. title complex.Productive rate: 98%.Anal.calcd.forC
17H
22O
6AgP：C，44.27；H，4.81.Found：C，44.55；H，4.45.
1H?NMR(CDCl
3)：δ1.3(t，9H，CH
3/CH
3CH
2O-，J
HH＝7.0Hz)，2.5(s，3H，CH
3-H)，4.0?4.1(m，6H，CH
2/CH
3CH
2O-)，7.4?7.5(m，4H，Ph-H).
13C{H}NMR(CDCl
3)：δ16.0(J
PC＝6.7Hz，CH
3/CH
3CH
2O-)，27.9(CH
3)，61.0(J
PC＝5.0Hz，CH
2/CH
3CH
2O-)，108.8(C)，120.1(C
6H
4)，131.6(C
6H
4)，137.6(C
6H
4)，139.2(C
6H
4)，192.4(C＝O)，194.5(C＝O)，195.1(C＝O).IR(KBr)data(cm
-1)：3479(w)，2981(s)，2934(m)，2903(m)，1765(w)，1678(s)，1626(s)，1589(s)，1505(m)，1435(s)，1340(m)，1150(m)，1096(m)，1014(s)，948(s)，882(m)，790(s)，732(s)，530(m).
[(C
2H
5O)
3P]
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.2585g (1.56mmol) P (OC of 20mL methylene dichloride
2H
5)
3Achromaticity and clarification liquid is added drop-wise to 0.2295g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.48g, i.e. title complex.Productive rate: 98%.Anal.calcd.forC
23H
37O
9AgP
2：C，44.03；H，5.94.Found：C，43.95；H，5.81.
1H?NMR(CDCl
3)：δ1.3(t，18H，CH
3/CH
3CH
2O-，J
HH＝7.0Hz)，2.5(s，3H，CH
3-H)，4.0(m，12H，CH
2/CH
3CH
2O-)，7.4?7.5(m，4H，Ph-H).
13C{H}NMR(CDCl
3)：δ16.0(J
PC＝6.1Hz，CH
3/CH
3CH
2O-)，28.0(CH
3)，60.2(J
PC＝5.9Hz，CH
2/CH
3CH
2O-)，108.5(C)，119.7(C
6H
4)，131.4(C
6H
4)，138.4(C
6H
4)，194.4(C＝O).IR(KBr)data(cm
-1)：3490(w)，2981(s)，2934(m)，2902(m)，1763(w)，1675(s)，1627(s)，1590(s)，1522(m)，1432(s)，1353(m)，1161(m)，1020(s)，943(s)，881(m)，774(s)，734(s)，529(m).
[(CH
3)
3P]
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.1187g (1.56mmol) P (CH of 20mL methylene dichloride
3)
3Achromaticity and clarification liquid is added drop-wise to 0.2295g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.34g, i.e. title complex.Productive rate: 98%.
Embodiment 10.
[(C
2H
5)
3P]
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.1843g (1.56mmol) P (C of 20mL methylene dichloride
2H
5)
3Achromaticity and clarification liquid is added drop-wise to 0.2295g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.40g, i.e. title complex.Productive rate: 96%.
[(C
3H
7)
3P]
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.2500g (1.56mmol) P (C of 20mL methylene dichloride
3H
7)
3Achromaticity and clarification liquid is added drop-wise to 0.2295g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.45g, i.e. title complex.Productive rate: 94%.
Embodiment 12.
[(C
4H
9)
3P]
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.3156g (1.56mmol) P (C of 20mL methylene dichloride
4H
9)
3Achromaticity and clarification liquid is added drop-wise to 0.2295g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.53g, i.e. title complex.Productive rate: 97%.
Embodiment 13.
[PCy
3]
2AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.3718g (1.56mmol) PCy of 20mL methylene dichloride
3Achromaticity and clarification liquid is added drop-wise to 0.2295g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride, in the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.59g, i.e. title complex.Productive rate: 98%.
Embodiment 14.
[Ph
3P]
3AgC
11H
7O
3Synthetic
At N
2Under the atmosphere, will be dissolved in 0.6144g (2.34mmol) the triphenylphosphine achromaticity and clarification liquid of 20mL methylene dichloride, be added drop-wise to 0.2304g (0.78mmol) the 2-acyl group-1 that is dissolved in the 10mL methylene dichloride; In the 3-indane dione silver suspension-s; Stir under 0 ℃ and got yellow clear liquor in 1 hour, under nitrogen protection, filter, take out with oil pump and desolvate; Get faint yellow solid 0.83g, i.e. title complex.Productive rate: 98%.
Embodiment 15.
Respectively with the title complex of embodiment 3-14 preparation as presoma, with method ([4] J.Rickerby, the J.H.G.Steinke of chemical vapour deposition; Current Trends in Patterning with Copper; Chem.Rev., 2002,102:1525-1549) the silver-colored thin-film material of growing.Under following optimum condition: substrate: Si, SiO
2Carrier gas: N
2, Ar gas, the gasification temperature of presoma: 150～300 ℃, growth temperature: 300～500 ℃; The flow of carrier gas is: 25～50sccm, the title complex of embodiment 3-14 preparation all can successes deposits high-quality silver-colored film.Wherein, film presents good shape characteristic (like Fig. 1).
Claims (6)
1. the 2-ethanoyl-1 of a stable organic phosphine, the 3-indane dione silver compound is characterized in that representing with formula:
Wherein
N=1,2 or 3
R′＝OCH
3、OCH
2CH
3、CH
3、C
2H
5、
I-Pr, n-Bu, t-Bu, Cy or Ph.
2. the 2-ethanoyl-1 of stable organic phosphine according to claim 1, the 3-indane dione silver compound is characterized in that described R ' is CH
3O, CH
3Or C
2H
5
3. 2-ethanoyl-1 for preparing like each described stable organic phosphine of claim 1-2, the method for 3-indane dione silver compound is characterized in that step is following:
(1), prepare 2-ethanoyl-1,3-indane dione silver: under protection of inert gas, with 2-ethanoyl-1,3-indenes diketone and triethylamine add alcoholic solvent to dissolving clearly; Under 0 ℃～-40 ℃ temperature and lucifuge condition, drip with the molten clear Silver Nitrate of acetonitrile/alcohol mixed solvent to above-mentioned clear liquid, drip the back and stirred 2～3 hours; Cross and filter white solid, wash twice respectively with ethanol, ether, drain that solid is an off-white color behind the solvent, the solid of gained is a 2-ethanoyl-1, the 3-indane dione silver; Above-mentioned 2-ethanoyl-1, mol ratio is 1: 1: 1 in 3-indenes diketone, triethylamine, the Silver Nitrate reaction process;
(2), with 2-ethanoyl-1, the mixture of 3-indane dione silver and organophosphorus ligand places anhydrous organic solvent to stir; At 0 ℃～-40 ℃ following stirring reactions more than 4 hours; After reaction finishes, cross and filter settled solution, drain solvent, promptly obtain title complex; 2-ethanoyl-1, mol ratio is that 1: 1～1: 3 and preparation process are carried out under inert atmosphere and lucifuge condition in 3-indane dione silver and the organophosphorus ligand reaction process.
4. method according to claim 3 is characterized in that: described inert atmosphere is a nitrogen.
5. method according to claim 3 is characterized in that: described anhydrous organic solvent is methylene dichloride or chloroform or 1, the 2-ethylene dichloride.
6. 2-ethanoyl-1 like each described stable organic phosphine of claim 1-2, the application of 3-indane dione silver compound aspect the silver-colored thin-film material of preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102645749A CN101775041B (en) | 2009-12-28 | 2009-12-28 | 2-acyl 1,3-indane dione silver compound with stable organic phosphine, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102645749A CN101775041B (en) | 2009-12-28 | 2009-12-28 | 2-acyl 1,3-indane dione silver compound with stable organic phosphine, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101775041A CN101775041A (en) | 2010-07-14 |
| CN101775041B true CN101775041B (en) | 2012-01-11 |
Family
ID=42511643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102645749A Expired - Fee Related CN101775041B (en) | 2009-12-28 | 2009-12-28 | 2-acyl 1,3-indane dione silver compound with stable organic phosphine, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101775041B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268026B (en) * | 2011-06-14 | 2014-01-29 | 南京航空航天大学 | Organic-phosphine-stabilized alkyl-substituted imide silver complex and synthesis method and application thereof |
-
2009
- 2009-12-28 CN CN2009102645749A patent/CN101775041B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101775041A (en) | 2010-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6184403B1 (en) | MOCVD precursors based on organometalloid ligands | |
| US7186835B2 (en) | Composition comprising amino-imine compounds | |
| EP1688426B1 (en) | Organometallic complexes and their use as precursors to deposit metal films | |
| KR101062591B1 (en) | Chemical Vapor Deposition Precursor for the Deposition of Tantalum-based Materials | |
| US6099903A (en) | MOCVD processes using precursors based on organometalloid ligands | |
| CN101775041B (en) | 2-acyl 1,3-indane dione silver compound with stable organic phosphine, preparation method and application thereof | |
| WO2016180297A1 (en) | Metal bridge site fused ring compound, and intermediate, preparation method and use thereof | |
| KR100298125B1 (en) | Organocuprous precursors for chemical deposition of copper | |
| KR20000013302A (en) | Glass copper precursor for chemical vapor deposition | |
| US6369256B1 (en) | Self-reducible copper(II) source reagents for chemical vapor deposition of copper metal | |
| US6340768B1 (en) | MOCVD precursors based on organometalloid ligands | |
| KR101074310B1 (en) | Copper complexes and process for formation of copper-containing thin films by using the same | |
| CN102268026B (en) | Organic-phosphine-stabilized alkyl-substituted imide silver complex and synthesis method and application thereof | |
| CN101585857B (en) | Organic phosphine stabilized N-hydroxysuccinimide silver complex, synthesis method and application thereof | |
| KR20200124484A (en) | Copper alkoxyalkylamide complexes, preparation method thereof and process for thin film formation using the same | |
| CN101270127B (en) | Succinimide silver complex with steady organo-phosphines, synthesizing method and application thereof | |
| KR20100099322A (en) | Material for formation of nickel-containing film, and method for production thereof | |
| CN102093430A (en) | Organic phosphine-stabilized alkyl silver disulfonate complex, and synthetic method and application thereof | |
| KR100704464B1 (en) | Copper aminoalkoxide complexes, preparation method thereof and process for the formation of copper thin film using the same | |
| KR100611730B1 (en) | Precursors for preparing the pure silver thin-film in the chemical vapor deposition method and manufacturing method thereof | |
| KR100600468B1 (en) | Process for producing cycloalkene copper precursors | |
| JP2762917B2 (en) | Material and method for forming platinum film by metal organic chemical vapor deposition | |
| JP2001140075A (en) | Organocopper complex for copper thin film deposition | |
| KR20220018546A (en) | Methods of making metal or semimetal-containing films | |
| Jakob et al. | Phosphane-and phosphite-silver (I) phenolates: Synthesis, characterization and their use as CVD precursors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20100714 Assignee: JIANGSU MO OPTO-ELECTRONIC MATERIAL CO., LTD. Assignor: Nanjing University of Aeronautics and Astronautics Contract record no.: 2013320000200 Denomination of invention: 2-acyl 1,3-indane dione silver compound with stable organic phosphine, preparation method and application thereof Granted publication date: 20120111 License type: Exclusive License Record date: 20130322 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120111 Termination date: 20141228 |
|
| EXPY | Termination of patent right or utility model |