CN114989226B - Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum - Google Patents

Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum Download PDF

Info

Publication number
CN114989226B
CN114989226B CN202210830414.1A CN202210830414A CN114989226B CN 114989226 B CN114989226 B CN 114989226B CN 202210830414 A CN202210830414 A CN 202210830414A CN 114989226 B CN114989226 B CN 114989226B
Authority
CN
China
Prior art keywords
platinum
cyclopentadienyl
halide
trimethyl
reaction
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.)
Active
Application number
CN202210830414.1A
Other languages
Chinese (zh)
Other versions
CN114989226A (en
Inventor
孙明明
韩露
朱志伟
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.)
Suzhou Sinocompound Technology Co ltd
Original Assignee
Suzhou Sinocompound Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suzhou Sinocompound Technology Co ltd filed Critical Suzhou Sinocompound Technology Co ltd
Priority to CN202210830414.1A priority Critical patent/CN114989226B/en
Publication of CN114989226A publication Critical patent/CN114989226A/en
Application granted granted Critical
Publication of CN114989226B publication Critical patent/CN114989226B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • 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
    • C23C16/08—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 metal halides
    • C23C16/14—Deposition of only one other metal element
    • 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

Landscapes

  • 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)

Abstract

The invention relates to a platinum precursor, a preparation method and application of trimethyl cyclopentadienyl platinum. The preparation method of the platinum precursor comprises the following steps: reacting platinum halide with cyclopentadienyl alkali metal salt in a protective atmosphere to prepare cyclopentadienyl platinum halide; reacting cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum; under the existence of Lewis acid, trimethyl cyclopentadienyl platinum and alkyl halide are subjected to Friedel-crafts reaction to prepare a platinum precursor. The preparation method of the platinum precursor has simple process, high material activity in each step of reaction, no need of large excess of methylating reagent, and the method also reduces various complex dangerous operations generated by preparing trimethyl platinum iodide, improves the safety coefficient of the reaction and provides possibility for industrial production.

Description

Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum
Technical Field
The invention relates to the field of organic metal compounds, in particular to a platinum precursor, a preparation method and application of trimethyl cyclopentadienyl platinum.
Background
The precursor is one of the important materials for manufacturing chips, and is mainly used for vapor deposition coating processes, including Physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), atomic vapor deposition (ALD), and the like, to form various thin film layers meeting the semiconductor manufacturing requirements, and also for semiconductor epitaxial growth, etching, ion implantation doping, cleaning, and the like.
Chemical vapor deposition is a technique for depositing a thin film of metal on a surface. In chemical vapor deposition, chemical vapor deposition precursors, also known as chemical vapor deposition compounds, decompose by thermochemical, photochemical or plasma activation to form a film having a desired composition. For example, a chemical vapor deposition precursor can be contacted with a substrate heated above the decomposition temperature of the precursor to form a metal or metal oxide film on the substrate.
Trimethyl (methylcyclopentadienyl) platinum (IV) compounds ((MeCp) PtMe) 3 ) Is a promising precursor for platinum chemical vapor deposition. The compound is reported to be stable to air, water and temperatures below 150 ℃. In addition, as (MeCp) PtMe 3 Platinum nanocrystals, which have excellent catalytic activity in the hydrogen-silicon addition, can be repeatedly prepared in a coordinating solvent (e.g., ethylene glycol, glycerol) or a non-coordinating solvent (e.g., diphenylmethane) by conventional heating, photolysis, or microwave irradiation as a starting material.
The conventional preparation process of trimethyl (methylcyclopentadienyl) platinum (IV) compounds is as follows: reacting potassium platinochloride with excessive methyllithium, quenching with 1, 2-dibromoethane, adding potassium iodide to obtain trimethyl platinum iodide, reacting with methyl cyclopentadiene sodium salt or lithium salt, and purifying to obtain the final product. In the method, the methyl lithium is greatly excessive, so that quenching operation is difficult, and industrial amplification is difficult to realize due to the safety problem in the process of preparing trimethyl platinum iodide.
Disclosure of Invention
In view of this, it is necessary to provide a method for preparing a platinum precursor with a simple process and a high safety margin.
In addition, a preparation method of trimethylcyclopentadienyl platinum and a preparation method of a metal film are also needed to be provided.
A preparation method of a platinum precursor comprises the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt in a protective atmosphere to prepare cyclopentadienyl platinum halide;
reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum;
and carrying out Friedel-crafts reaction on the trimethylcyclopentadienyl platinum and the alkyl halide in the presence of Lewis acid to prepare a platinum precursor.
In one embodiment, the cyclopentadienyl alkali metal salt is selected from at least one of cyclopentadienyl lithium, cyclopentadienyl sodium and cyclopentadienyl potassium.
In one embodiment, the platinum halide is platinum tetrachloride.
In one embodiment, the methylating agent is selected from at least one of methyllithium and trimethylaluminum.
In one embodiment, the alkyl halide is at least one selected from methyl bromide and methyl iodide, and the platinum precursor is trimethyl (methylcyclopentadienyl) platinum.
In one embodiment, after the step of performing friedel-crafts reaction on the trimethylcyclopentadienylplatinum and the alkyl halide, the method further comprises the following steps:
adding a quenching agent into a system after the Friedel-crafts reaction to quench the reaction, and then passing through a silica gel column, removing a solvent, and sublimating and purifying.
In one embodiment, the molar ratio of the platinum halide to the cyclopentadienyl alkali metal salt is 1 (1.1 to 1.5).
In one embodiment, in the step of reacting the platinum halide with the cyclopentadienyl alkali metal salt, the reaction temperature is-10 ℃ to 0 ℃, and the reaction time is 30min to 120min.
In one embodiment, the molar ratio of the cyclopentadienyl platinum halide to the methyl group in the methylating agent is 1 (3.3 to 3.6).
In one embodiment, the step of reacting the cyclopentadienyl platinum halide with a methylating agent comprises: adding the methylating agent into the cyclopentadienyl platinum halide at 0-25 ℃, and then reacting for 12h-24h at 10-30 ℃.
In one embodiment, the molar ratio of the trimethylcyclopentadienyl platinum to the Lewis acid and the alkyl halide is 1 (0.1 to 0.5) to (1.5 to 2).
In one embodiment, the step of subjecting the trimethylcyclopentadienylplatinum to a friedel-crafts reaction with an alkyl halide comprises: adding the trimethylcyclopentadienyl platinum into the mixture system of the Lewis acid and the alkyl halide at the temperature of 0-30 ℃, and then reacting for 12h-24h at the temperature of 10-30 ℃.
In one embodiment, the lewis acid is selected from at least one of aluminum trichloride, iron trichloride, tin tetrachloride, and zinc chloride.
A preparation method of trimethylcyclopentadienyl platinum comprises the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt under a protective atmosphere to prepare cyclopentadienyl platinum halide; and
and reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum.
A preparation method of a metal film comprises the following steps:
preparing a platinum precursor by adopting the preparation method; and
the platinum precursor is decomposed to form a film on the substrate.
The preparation method takes platinum halide as a raw material, and the platinum halide reacts with cyclopentadienyl alkali metal salt under the protective atmosphere to obtain cyclopentadienyl platinum halide; then reacting with a methylating agent to generate trimethyl cyclopentadienyl platinum; finally, under the action of Lewis acid, the platinum precursor is subjected to Friedel-crafts reaction with alkyl halide to prepare a platinum precursor, and when the alkyl halide is methyl halide, a target product trimethyl (methyl cyclopentadienyl) platinum (IV) can be obtained. The method has simple process, high material activity in each step of reaction, no need of large excess of methylating reagent, and reduced complex dangerous operations caused by preparation of trimethyl platinum iodide, improved safety coefficient of reaction, and possibility of industrial production.
Drawings
FIG. 1 is a diagram of trimethyl (methylcyclopentadienyl) platinum prepared in example 1 1 HNMR spectrogram;
FIG. 2 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 1 13 CNMR spectrogram;
FIG. 3 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 2 1 HNMR spectrogram;
FIG. 4 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 2 13 CNMR spectrogram;
FIG. 5 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 3 1 HNMR spectrogram;
FIG. 6 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 3 13 CNMR spectrogram;
FIG. 7 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 4 1 HNMR spectrogram;
FIG. 8 is a photograph of trimethyl (methylcyclopentadienyl) platinum prepared in example 4 13 CNMR spectrogram;
FIG. 9 is a photograph of trimethyl (methylcyclopentadienyl) platinum prepared in example 5 1 HNMR spectrogram;
FIG. 10 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 5 13 CNMR spectrogram.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Herein, room temperature means a temperature of 10 ℃ to 30 ℃.
Aiming at the problems of complex operation, high risk, difficult industrial application and the like in the traditional preparation process of trimethyl (methylcyclopentadienyl) platinum (IV), the invention provides the preparation method which has simple process and high safety and can realize industrial production.
Specifically, a method for preparing a platinum precursor according to an embodiment includes the steps of:
step S110: under the protection atmosphere, reacting platinum halide with cyclopentadienyl alkali metal salt to prepare cyclopentadienyl platinum halide.
Wherein the platinum halide is platinum tetrachloride (PtCl) 4 ). The platinum tetrachloride is cheap and easily available, has wide sources and is beneficial to reducing the cost. Further, platinum tetrabromide and platinum tetraiodide have high activities, and impurities substituted with two cyclopentadienes are easily generated. Therefore, in the present embodiment, the platinum halide is preferably platinum tetrachloride.
Specifically, the protective atmosphere may be nitrogen, argon, helium, or the like.
In some embodiments, the cyclopentadienyl alkali metal salt is selected from cyclopentadienyl lithium (formula C) 5 H 5 Li, commonly abbreviated as CpLi, where Cp − Is cyclopentadiene anion), sodium cyclopentadienyl (chemical formula C) 5 H 5 Na, commonly abbreviated as CpNa) and cyclopentadienyl potassium (formula C) 5 H 5 K, often abbreviated CpK). Experiments prove that in the preparation process of cyclopentadienyl platinum halide, the cyclopentadienyl alkali metal salt has higher reaction activity than other substances, such as cyclopentadienyl trimethyl silicon. The cyclopentadienyl trimethyl silicon hardly reacts due to insufficient activity, so that a target product is difficult to obtain. The cyclopentadienyl lithium, the cyclopentadienyl sodium and the cyclopentadienyl potassium are adopted as cyclopentadienyl alkali metal salts, so that a target product with higher yield can be obtained, and the final product has darker color due to stronger alkalinity. In addition, cyclopentadienyl lithium is preferably selected in consideration of ease of preparation.
Specifically, the cyclopentadienyl platinum halide has the chemical formula CpPtX 3 Structural formula is
Figure 530845DEST_PATH_IMAGE001
. Reacting platinum halide with cyclopentadienyl alkali metal salt to prepare cyclopentadienyl platinum halide, wherein the reaction formula is as follows: ptX 4 +CpY→CpPtX 3 + YX, wherein Y is an alkali metal, such as Li, na, K, etc., and X is a halogen, such as Cl, etc.
In some embodiments, the molar ratio of platinum halide to cyclopentadienyl alkali metal salt is 1 (1.1 to 1.5). In a particular example, the molar ratio of platinum halide to cyclopentadienyl alkali metal salt is in the range of 1.1, 1.
In some embodiments, the step of reacting platinum halide with the cyclopentadienyl alkali metal salt is carried out at a temperature of-10 ℃ to 0 ℃ for a reaction time of 30min to 120min. In a specific example, in the step of reacting the platinum halide with the cyclopentadienyl alkali metal salt, the reaction temperature is in the range of-10 ℃, -8 ℃, -5 ℃, -3 ℃, -1 ℃, 0 ℃ or any two of these values. The reaction time is 30min, 45min, 60min, 75min, 90min, 105min, 120min or the range formed by any two of the values.
Further, in some embodiments, the step of reacting the platinum halide with the cyclopentadienyl alkali metal salt under a protective atmosphere comprises:
under the protection atmosphere, cooling the solution containing platinum halide to-10-0 ℃, then adding the solution containing cyclopentadienyl alkali metal salt, and continuing to react for 30min to 120min at the temperature.
In a specific example, the solution containing platinum halide and the solution containing cyclopentadienyl alkali metal salt are tetrahydrofuran solutions. It is understood that the solution containing platinum halide and the solution containing cyclopentadienyl alkali metal salt are not limited to the tetrahydrofuran solution.
Step S120: reacting cyclopentadienyl platinum halide with a methylating agent to produce trimethylcyclopentadienyl platinum.
In some embodiments, the methylating agentSelected from methyllithium (CH) 3 Li) and trimethylaluminum (Al (CH) 3 ) 3 ) At least one of (a). Experiments prove that in the methylation reagent: methyl magnesium bromide is less reactive than methyl lithium and trimethylaluminum. The yield and appearance of the product prepared from the trimethylaluminum are better than those of the methyllithium. Therefore, in the present embodiment, the methylating agent is preferably trimethylaluminum.
In some embodiments, the molar ratio of the cyclopentadienyl platinum halide to the methyl group in the methylating agent is 1 (3.3 to 3.6). In a particular example, the molar ratio of cyclopentadienyl platinum halide to methyl in the methylating agent is in the range of 1.
In some embodiments, the step of reacting the cyclopentadienyl platinum halide with a methylating agent comprises: firstly, adding a methylating agent into cyclopentadienyl platinum halide at 0-25 ℃, and then reacting for 12h-24h at 10-30 ℃. In a specific example, during the addition of the methylating agent to the cyclopentadienyl platinum halide, the methylating agent is dissolved in an organic solvent such as diethyl ether and toluene, and added dropwise.
Further, in some embodiments, the step of reacting the cyclopentadienyl platinum halide with a methylating agent is followed by a purification step. Specifically, the purification step comprises:
adding a quenching agent into the system after the reaction, then removing the solvent to obtain a mixture of the trimethyl cyclopentadienyl platinum and the halide, and then removing the halide to obtain the trimethyl cyclopentadienyl platinum.
In one particular example, the quenching agent is water.
In one specific example, during the halide removal, an organic solvent such as methylene chloride is added to the mixture, and then a layer of diatomaceous earth is filtered to remove the halide.
Specifically, the chemical formula of trimethylcyclopentadienylplatinum is CpPtMe 3 Me is methyl, the structural formula is
Figure 884466DEST_PATH_IMAGE002
. Reacting cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum according to the reaction formula: cpPtX 3 +3CH 3 Li→CpPtMe 3 +3LiX; alternatively, cpPtX 3 +Al(CH 3 ) 3 →CpPtMe 3 +AlX 3 . X is halogen.
Step S130: in the presence of Lewis acid, performing Friedel-crafts reaction on trimethylcyclopentadienyl platinum and alkyl halide to prepare a platinum precursor.
Specifically, the alkyl halide is methyl halide. In a specific example, the alkyl halide is at least one selected from methyl bromide and methyl iodide. The platinum precursor is trimethyl (methylcyclopentadienyl) platinum (IV). Experiments have shown that methyl iodide and methyl bromide have little effect in the preparation of trimethyl (methylcyclopentadienyl) platinum (IV), but methyl iodide is more toxic, and therefore methyl bromide is preferred as the alkyl halide in this embodiment.
In some embodiments, the lewis acid is selected from at least one of aluminum trichloride, iron trichloride, tin tetrachloride, and zinc chloride.
In some embodiments, the molar ratio of trimethylcyclopentadienylplatinum to the Lewis acid and the alkyl halide is 1 (0.1 to 0.5) to (1.5 to 2).
In some embodiments, the step of friedel-crafts reacting trimethylcyclopentadienylplatinum with an alkyl halide comprises: adding trimethyl cyclopentadienyl platinum into a mixed system of Lewis acid and alkyl halide at the temperature of 0-30 ℃, and then reacting for 12h-24h at the temperature of 10-30 ℃. In a specific example, during the process of adding trimethylcyclopentadienyl platinum to the mixture system of lewis acid and alkyl halide, the trimethylcyclopentadienyl platinum is dissolved in an organic solvent such as dichloromethane, tetrahydrofuran, etc. and is added dropwise.
Further, in some embodiments, the friedel-crafts reaction of trimethylcyclopentadienylplatinum with an alkyl halide further comprises:
adding a quenching agent into the system after the Friedel-crafts reaction, and then passing through a silica gel column, removing a solvent, and purifying by sublimation.
In one particular example, the quenching agent is water.
In a specific example, the pressure during sublimation purification is 10Pa and the temperature is 35 ℃.
In the preparation process of the platinum precursor, a section of silica gel column is added during purification, which is beneficial to removing large-polarity impurities and some inorganic salts, and is beneficial to improving the product quality and the yield.
Specifically, the platinum precursor has the formula RCpPtMe 3 Structural formula is
Figure 167811DEST_PATH_IMAGE003
. Performing Friedel-crafts reaction on trimethylcyclopentadienyl platinum and alkyl halide to prepare a platinum precursor according to the following reaction formula: cpPtMe 3 +RX→RCpPtMe 3 + HX, R is alkyl and X is halogen.
In one specific example, RX is MeX and the platinum precursor is mecppptme 3 Structural formula is
Figure 897870DEST_PATH_IMAGE004
。
The preparation method of the platinum precursor has at least the following advantages:
(1) The preparation method of the platinum precursor takes platinum halide as a raw material, and the platinum halide reacts with cyclopentadienyl alkali metal salt under a protective atmosphere to obtain cyclopentadienyl platinum halide; then reacting with a methylating agent to generate trimethyl cyclopentadienyl platinum; finally, under the action of Lewis acid, the platinum precursor is subjected to Friedel-crafts reaction with alkyl halide to prepare a platinum precursor, and when the alkyl halide is methyl halide, a target product trimethyl (methyl cyclopentadienyl) platinum (IV) can be obtained. The method has simple process, high material activity in each step of reaction, no need of large excess of methylating reagent, and the method also reduces various complex dangerous operations generated by preparing trimethyl platinum iodide, improves the safety coefficient of the reaction and provides possibility for industrial production.
(2) The preparation method of the platinum precursor reduces the problem of a large amount of three wastes generated by preparing trimethyl platinum iodide, and simultaneously saves the cost.
(3) According to the preparation method of the platinum precursor, the trimethyl cyclopentadienyl platinum is prepared firstly, and then trimethyl (methyl cyclopentadienyl) platinum (IV) is prepared on the basis of the trimethyl cyclopentadienyl platinum, so that the operation is simple, the obtained product has high purity, and the trimethyl cyclopentadienyl platinum can be co-produced.
(4) The preparation method of the platinum precursor removes most of the impurity metals by using the adsorption silica gel, and then carries out sublimation purification, so that the purification efficiency is high and the impurity content is low.
(5) The preparation method of the platinum precursor has high yield which is more than 70 percent and even up to 90 percent.
The present invention also provides a method for preparing a metal thin film according to an embodiment, including the steps of:
step S210: and preparing a platinum precursor.
Specifically, the platinum precursor is prepared by the method for preparing a platinum precursor according to the above embodiment, which is not described herein again.
Step S220: the platinum precursor is decomposed to form a film on the substrate.
Specifically, the platinum precursor may be decomposed by thermal, chemical, photochemical or plasma-activated means.
In order to make the objects and advantages of the present invention more apparent, the following detailed description of the method for preparing a platinum precursor and the effects thereof is given in conjunction with the following specific examples, it being understood that the specific examples described herein are only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention. The following examples are not specifically described, and other components except inevitable impurities are not included. The examples, which are not specifically illustrated, employ drugs and equipment, all of which are conventional in the art. The experimental procedures, in which specific conditions are not indicated in the examples, were carried out according to conventional conditions, such as those described in the literature, in books, or as recommended by the manufacturer.
Example 1
The embodiment provides a preparation method of a platinum precursor, which includes the following steps:
(1) Under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is raised to 0 ℃, 206mL of 1.6M methyl lithium ether solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and decompressing and distilling off the solvent to obtain the trimethylcyclopentadienyl platinum and the by-product lithium chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove lithium chloride, and a dark brown solution was obtained as a solution of trimethylcyclopentadienylplatinum in dichloromethane.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is washed, the solvent is evaporated by decompression, the obtained brown crude product is transferred to a 250mL sublimator, an oil pump is arranged at 10Pa, the temperature is 35 ℃, and light yellow crystals, namely trimethyl (methyl cyclopentadienyl) platinum in the embodiment, are sublimed. The mass of the obtained pale yellow crystals was 23.0g, and the yield was 72%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 1 and FIG. 2, respectively, and the deuterated reagent is CDCl 3 。
Example 2
The embodiment provides a preparation method of a platinum precursor, which includes the following steps:
(1) Under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl sodium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is raised to 0 ℃, 206mL of 1.6M methyl lithium ether solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and decompressing and distilling off the solvent to obtain the trimethylcyclopentadienyl platinum and a by-product sodium chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove the sodium chloride and a dark brown solution was obtained as a solution of trimethylcyclopentadienylplatinum in dichloromethane.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is flushed, the solvent is evaporated by reduced pressure, the obtained dark brown crude product is transferred to a 250mL sublimer, an oil pump is arranged at 10Pa, the temperature is 35 ℃, and yellow crystals, namely trimethyl (methyl cyclopentadienyl) platinum of the embodiment, are sublimed. The mass of the resulting yellow crystals was 23.8g, and the yield was 74.5%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 3 and FIG. 4, respectively, and the deuterated reagent is CDCl 3 。
Example 3
The embodiment provides a preparation method of a platinum precursor, which includes the following steps:
(1) Under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran are added to a 2L three-necked flask, the mixture is cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl potassium in tetrahydrofuran is added dropwise, the mixture is gradually dissolved in the reddish brown turbid solution, and the reaction is continued for 30min at the temperature.
(2) The temperature is raised to 0 ℃, 206mL of 1.6M methyl lithium ether solution is added dropwise, the reaction solution becomes brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water, quenching, and evaporating the solvent under reduced pressure to obtain the trimethylcyclopentadienyl platinum and the byproduct potassium chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove the potassium chloride and a dark brown solution was obtained as a solution of trimethylcyclopentadienylplatinum in dichloromethane.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is flushed, the solvent is evaporated by reduced pressure, the obtained dark brown crude product is transferred to a 250mL sublimer, an oil pump is arranged at 10Pa, the temperature is 35 ℃, and yellow crystals, namely trimethyl (methyl cyclopentadienyl) platinum of the embodiment, are sublimed. The mass of the obtained yellow crystals was 23.6g, and the yield was 73.9%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 5 and FIG. 6, respectively, and the deuterated reagent is CDCl 3 。
Example 4
The embodiment provides a preparation method of a platinum precursor, which comprises the following steps:
(1) Under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran are added to a 2L three-necked flask, the mixture is cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran is added dropwise, the mixture is gradually dissolved in the reddish brown turbid liquid, and the reaction is continued for 30min at the temperature.
(2) The temperature is raised to 0 ℃, 120mL of 1.0M trimethylaluminum in toluene solution is added dropwise, the reaction solution becomes brown turbid liquid, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and decompressing and distilling off the solvent to obtain the trimethylcyclopentadienyl platinum and the byproduct aluminum chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove aluminum chloride, and a brown-yellow solution, i.e., a solution of trimethylcyclopentadienylplatinum in dichloromethane, was obtained.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is washed, the solvent is evaporated by decompression, the obtained brown crude product is transferred to a 250mL sublimer, an oil pump is used for 10Pa, the temperature is 35 ℃, and white crystals, namely trimethyl (methyl cyclopentadienyl) platinum in the embodiment, are sublimed. The obtained white crystals had a mass of 28.8g and a yield of 90.3%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 7 and FIG. 8, respectively, and the deuterated reagent used is CDCl 3 。
Example 5
The embodiment provides a preparation method of a platinum precursor, which comprises the following steps:
(1) Under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran are added to a 2L three-necked flask, the mixture is cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran is added dropwise, the mixture is gradually dissolved in the reddish brown turbid liquid, and the reaction is continued for 30min at the temperature.
(2) The temperature is increased to 0 ℃, 120mL of 1.0M trimethylaluminum toluene solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and decompressing and distilling off the solvent to obtain the trimethylcyclopentadienyl platinum and the byproduct aluminum chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove aluminum chloride, and a tan solution, i.e., a dichloromethane solution of trimethylcyclopentadienyl platinum, was obtained.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 21.3g of methyl iodide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is flushed, the solvent is evaporated by reduced pressure, the obtained brown crude product is transferred to a 250mL sublimer, and white crystals, namely trimethyl (methylcyclopentadienyl) platinum in the embodiment, are sublimated at the temperature of 35 ℃ under the oil pump 10 Pa. The mass of the obtained white crystals was 27.6g, and the yield was 86.5%.
Trimethyl (methylcyclopentadiene) prepared in this exampleBased) on platinum 1 HNMR and 13 CNMR is shown in FIG. 9 and FIG. 10, respectively, and the deuterated reagent used is CDCl 3 。
As can be seen from a comparison of example 4 and example 5, methyl iodide is less effective than methyl bromide in the preparation of trimethyl (methylcyclopentadienyl) platinum (IV), but methyl iodide is more toxic, so methyl bromide is preferred.
Example 6
The embodiment provides a preparation method of a platinum precursor, which includes the following steps:
(1) Under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran are added to a 2L three-necked flask, the mixture is cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran is added dropwise, the mixture is gradually dissolved in the reddish brown turbid liquid, and the reaction is continued for 30min at the temperature.
(2) The temperature is increased to 0 ℃, 120mL of 1.0M trimethylaluminum toluene solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water, quenching, and evaporating the solvent under reduced pressure to obtain trimethylcyclopentadienyl platinum and a byproduct aluminum chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove aluminum chloride, and a brown-yellow solution, i.e., a solution of trimethylcyclopentadienylplatinum in dichloromethane, was obtained.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-necked bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Quenching by dropping 50mL of water, separating, drying the organic phase with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, transferring the obtained brown crude product to a 250mL sublimator, pumping 10Pa oil, sublimating at 35 ℃ to obtain brown crystals, namely trimethyl (methylcyclopentadienyl) platinum of the embodiment. The mass of the resulting brown crystals was 26.2g, and the yield was 82.2%.
As can be seen from the comparison between example 4 and example 6, in the preparation process of trimethyl (methylcyclopentadienyl) platinum (IV), a silica gel column is flushed during purification, which is helpful for removing the large polar impurities and some inorganic salts, and is beneficial for improving the product quality and increasing the yield.
Comparative example 1
Comparative example 1 provides a method for preparing a platinum precursor, comprising the steps of:
under the condition of argon, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran are added into a 2L three-necked bottle, the mixture is cooled to-10 ℃, 110mL of 1.5M tetrahydrofuran solution of cyclopentadienyl trimethyl silicon is dropwise added, and no obvious phenomenon change is found in the red-brown turbid liquid after 2h. Presumably, the cyclopentadienyl trimethylsilane was not sufficiently active and further dosing was abandoned.
As can be seen from a comparison of examples 1 to 3 with comparative example 1, in the preparation of cyclopentadienylplatinum chloride, lithium cyclopentadienyl, sodium cyclopentadienyl and potassium cyclopentadienyl were almost as good from the viewpoint of yield, while cyclopentadienyl trimethylsilane was not sufficiently reactive. The cyclopentadienyl sodium and the cyclopentadienyl potassium have strong alkalinity, so that the final product has dark color. In addition, in view of ease of preparation, cyclopentadienyl lithium is preferably selected.
Comparative example 2
Comparative example 2 provides a method for preparing a platinum precursor, comprising the steps of:
(1) Under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) Heating to 0 ℃, dropwise adding 120mL of 3.0M methyl magnesium bromide ether solution, changing the reaction solution into brown turbid solution, and reacting at room temperature for 12h. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and decompressing and distilling off the solvent to obtain the trimethylcyclopentadienyl platinum and a by-product magnesium chloride. To the resulting product was added 200mL of dichloromethane, and a layer of celite was filtered to remove the magnesium chloride, yielding a pale yellow solution, i.e., a dichloromethane solution of trimethylcyclopentadienylplatinum.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-necked bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Quenching by dripping 50mL of water, separating liquid, drying the organic phase with anhydrous sodium sulfate, washing a section of silica gel column with the thickness of 3cm, evaporating the solvent under reduced pressure, transferring the obtained brown viscous substance to a 250mL sublimator, setting an oil pump at 10Pa, and heating to 50 ℃ at 35 ℃ without sublimating the product.
As can be seen from a comparison of example 1, example 4 and comparative example 2, methyl magnesium bromide is less active than the methyl lithium reagent and the trimethyl aluminum reagent in the preparation of trimethyl cyclopentadienyl platinum. The yield and appearance of the product prepared from trimethylaluminum are relatively good.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims (10)

1. A preparation method of a platinum precursor is characterized by comprising the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt in a protective atmosphere to prepare cyclopentadienyl platinum halide;
reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum; and
carrying out Friedel-crafts reaction on the trimethylcyclopentadienyl platinum and alkyl halide in the presence of Lewis acid to prepare a platinum precursor;
the platinum halide is platinum tetrachloride, the cyclopentadienyl alkali metal salt is selected from at least one of cyclopentadienyl lithium, cyclopentadienyl sodium and cyclopentadienyl potassium, the methylating agent is selected from at least one of methyl lithium and trimethyl aluminum, and the alkyl halide is selected from at least one of methyl bromide and methyl iodide.
2. The method for producing a platinum precursor according to claim 1, wherein the molar ratio of the platinum halide to the cyclopentadienyl alkali metal salt is 1 (1.1 to 1.5).
3. The method for producing a platinum precursor according to claim 1, wherein the molar ratio of the cyclopentadienyl platinum halide to the methyl group in the methylating agent is 1 (3.3 to 3.6).
4. The method for preparing the platinum precursor according to claim 1, wherein the molar ratio of the trimethylcyclopentadienylplatinum to the Lewis acid and the alkyl halide is 1 (0.1 to 0.5) to (1.5 to 2).
5. The method for producing a platinum precursor according to claim 1, further comprising, after the step of subjecting the trimethylcyclopentadienylplatinum to a friedel-crafts reaction with an alkyl halide:
adding a quenching agent into the system after the Friedel-crafts reaction to quench the reaction, and then passing through a silica gel column, removing the solvent, and sublimating and purifying.
6. The method for producing a platinum precursor according to any one of claims 1 to 5, wherein in the step of reacting the platinum halide with the cyclopentadienyl alkali metal salt, the reaction temperature is-10 ℃ to 0 ℃ and the reaction time is 30min to 120min.
7. The method for producing a platinum precursor according to any one of claims 1 to 5, wherein the step of reacting the cyclopentadienyl platinum halide with a methylating agent comprises: the methylation reagent is added into the cyclopentadienyl platinum halide at 0-25 ℃, and then the reaction is carried out for 12h-24h at 10-30 ℃.
8. The method for preparing a platinum precursor according to any one of claims 1 to 5, wherein the step of carrying out a Friedel-crafts reaction on the trimethylcyclopentadienyl platinum and the alkyl halide comprises the following steps: adding the trimethylcyclopentadienyl platinum into the mixture system of the Lewis acid and the alkyl halide at the temperature of 0-30 ℃, and then reacting for 12h-24h at the temperature of 10-30 ℃; and/or the presence of a catalyst in the reaction mixture,
the Lewis acid is at least one selected from aluminum trichloride, ferric trichloride, stannic chloride and zinc chloride.
9. A preparation method of trimethyl cyclopentadienyl platinum is characterized by comprising the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt in a protective atmosphere to prepare cyclopentadienyl platinum halide; and
reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum;
wherein the platinum halide is platinum tetrachloride, the cyclopentadienyl alkali metal salt is selected from at least one of cyclopentadienyl lithium, cyclopentadienyl sodium and cyclopentadienyl potassium, and the methylating agent is selected from at least one of methyl lithium and trimethyl aluminum.
10. The preparation method of the metal film is characterized by comprising the following steps:
preparing a platinum precursor by the preparation method according to any one of claims 1 to 8; and
the platinum precursor is decomposed to form a film on the substrate.
CN202210830414.1A 2022-07-15 2022-07-15 Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum Active CN114989226B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210830414.1A CN114989226B (en) 2022-07-15 2022-07-15 Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210830414.1A CN114989226B (en) 2022-07-15 2022-07-15 Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum

Publications (2)

Publication Number Publication Date
CN114989226A CN114989226A (en) 2022-09-02
CN114989226B true CN114989226B (en) 2022-11-04

Family

ID=83022826

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210830414.1A Active CN114989226B (en) 2022-07-15 2022-07-15 Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum

Country Status (1)

Country Link
CN (1) CN114989226B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040010158A1 (en) * 2002-06-12 2004-01-15 Meiere Scott Houston Method for producing organometallic compounds
CN101925608A (en) * 2008-01-25 2010-12-22 瓦克化学股份公司 Hydrosilylation reactions activated through radiation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040010158A1 (en) * 2002-06-12 2004-01-15 Meiere Scott Houston Method for producing organometallic compounds
CN101925608A (en) * 2008-01-25 2010-12-22 瓦克化学股份公司 Hydrosilylation reactions activated through radiation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
195Pt NMR Study of (η5-Cyclopentadienyl) trialkylplatinum(IV) Cornplexes;Larry D. Boardman等;《MAGNETIC RESONANCE IN CHEMISTRY》;19921231;第30卷;第481-489页 *
Chemical vapor deposition (CVD) of iridium and platinum films and gas-phase chemical etching of iridium thin films;Xu, Chongying等;《Mat. Res. Soc. Symp. Proc.》;19991231;第541卷;第129-139页 *
Preparation of some cyclopentadienyl platinum (IV) complexes;ALAN SHAVER;《Canadian Journal of Chemistry》;19781231;第56卷(第17期);第2281-2285页 *

Also Published As

Publication number Publication date
CN114989226A (en) 2022-09-02

Similar Documents

Publication Publication Date Title
JP5460501B2 (en) Organometallic compounds
US10106425B2 (en) Synthesis methods for halosilanes
JP6340470B2 (en) Molybdenum and tungsten-containing precursors for thin film deposition
TWI660958B (en) Molybdenum silylcyclopentadienyl and silylallyl complexes and use thereof in thin film deposition
WO2013065806A1 (en) Tris (dialkylamide) aluminum compound, and method for producing aluminum-containing thin film using same
US6420582B1 (en) Organometallic compounds for chemical vapor deposition and their preparing processes, and processes for chemical vapor deposition of precious-metal films and precious-metal compound films
WO2019238469A1 (en) Process for the generation of metal or semimetal-containing films
CN114989226B (en) Preparation method and application of platinum precursor and trimethylcyclopentadienyl platinum
CN112125931A (en) Synthesis method of bis (tert-butylamine) bis (dimethylamine) tungsten (VI)
US6663706B2 (en) Raw material compounds for use in CVD, and chemical vapor deposition for producing iridium or iridium compound thin films
KR20000013302A (en) Glass copper precursor for chemical vapor deposition
KR100298125B1 (en) Organocuprous precursors for chemical deposition of copper
TW200526802A (en) Metal complex having BETA-diketonato ligand and method for producing metal-containing thin film
US4841082A (en) Preparation of dimethylzinc
KR102355133B1 (en) Precursor For Forming A Thin Film, Method For Preparing Thereof, Method For Preparing The Thin Film, and The Thin Film
KR20120120182A (en) Ruthenium complex mixture, method for producing same, composition for forming film, ruthenium-containing film and method for producing same
WO2010032673A1 (en) Nickel-containing film‑formation material, and nickel-containing film‑fabrication method
KR100704464B1 (en) Copper aminoalkoxide complexes, preparation method thereof and process for the formation of copper thin film using the same
WO2017030150A1 (en) Method for producing aluminum oxide film, material for producing aluminum oxide film and aluminum compound
US9738971B2 (en) Vapor deposition methods to form group 8-containing films
WO2010032679A1 (en) Material used for forming nickel-containing film and method for manufacturing the nickel-containing film
JP2002220397A (en) Manufacturing method for bis(cyclopentadienyl) ruthenium derivative, bis(cyclopentadienyl)ruthenium derivative manufactured by the method, and manufacturing method for ruthenium film or ruthenium compound film
JP2022536116A (en) Method for producing metal- or metalloid-containing films
CN116947916A (en) Preparation method of metal complex
KR20210031492A (en) Method for producing a metal or semimetal-containing film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant