CN114957014A - Preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation - Google Patents
Preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation Download PDFInfo
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Abstract
The invention provides a preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation, belonging to the technical field of chemical synthesis. Firstly, the TaCl is introduced into the reactor 5 Reaction with 5 times dimethylamine in organic solvent to introduce 2-NMe atoms on tantalum metal atom 2 And reacting the bis (dimethylamino) tantalum trichloride with 3 times of dimethylaminolithium to obtain the pentakis (dimethylamino) tantalum. The preparation method reduces the consumption of n-butyllithium and the manufacturing cost; and the product and the by-products are separated by a centrifugal process under the protection of nitrogen, so that the problem of difficult separation is solved, the dosage of the solvent is reduced, the contact frequency of the product with air and water vapor caused by multiple times of washing is reduced, the production cost is reduced, and the product purity is improved.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation.
Background
The micro-electronic chip tantalum nitride (TaN) film has a series of excellent performances such as low resistivity, high melting point, high activation energy of crystal lattice and grain boundary diffusion, high thermal stability and the like, for example, in a standard copper interconnection technology of a CMOS (complementary metal oxide semiconductor) later stage, the tantalum nitride film is often used as a diffusion barrier layer of copper, and the tantalum nitride and a high-dielectric constant gate medium have good high-temperature chemical stability, so the tantalum nitride film is used as a metal gate material; in the extreme ultraviolet lithography process, the tantalum nitride can also serve as an absorber layer.
Tantalum pentoxide (Ta) 2 O 5 ) The film has high dielectric constant (25-35), high refractive index and good chemical stability, and can be used as a key material of a dynamic random access memory, an antireflection film, high-temperature impedance, a gas sensor and a capacitor. Particularly, the tantalum pentoxide is used as a high dielectric constant material, which is much higher than that of the traditional silicon dioxide material, so that the tantalum pentoxide can have larger physical thickness under the same capacitance density, thereby effectively reducing the leakage current density of the device, improving the reliability of the device and prolonging the service life of the device. At present, tantalum pentoxide has been well applied in the fields of dynamic random access memories, radio frequency integrated circuit passive capacitors and the like.
High purity pentakis (dimethylamino) tantalum (C) 10 H 30 N 5 Ta) is a precursor for preparing a microelectronic chip tantalum nitride film with the thickness of less than 45nm and is also a raw material for preparing a tantalum pentoxide film. Tantalum pentakis (dimethylamino) is a key reactant source for growing tantalum nitride or tantalum pentoxide by Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) processes.
At present, reports about a pentakis (dimethylamino) tantalum synthesis method are only limited to laboratory synthesis, and the operation process is not suitable for stable control, so that the reaction yield is low and the purity is low. The main synthesis method comprises the following steps: (1) reacting dimethylamine with butyl lithium to obtain lithium dimethylamide; (2) after the lithium dimethylamide salt reacts with the tantalum pentachloride, the solvent is removed by filtration; (3) transferring the separated crude product to a sublimator, and sublimating to obtain the crude product.
In the prior art, Can j. chem., 40, 1962, 1355, a method for synthesizing pentakis (dimethylamino) tantalum is disclosed, PDMAT [ pentakis (dimethylamino) tantalum ] is prepared by reacting tantalum pentachloride with five equivalents of dimethylaminolithium, which is prepared from dimethylamine and n-butyllithium in an alkane solution (usually n-hexane, n-heptane, methylcyclohexane). The pentakis (dimethylamino) tantalum prepared by the method has low yield, high metal lithium atom content and purity which cannot reach the deposition of an integrated circuit chip.
Chinese patent CN106916072A discloses a method for synthesizing pentakis (dimethylamino) tantalum, which is prepared by reacting TaCl 5 Mixing with excessive dimethylamine at low temperature by using alkane as a solvent, and adding excessive n-butyllithium hexane solution to react to prepare PDMAT, wherein dimethylamine is firstly added into TaCl 5 To the solid alkane mixture, the target product PDMAT is prepared by subsequently adding n-butyllithium, using excess dimethylamine and excess n-butyllithium, which increases the manufacturing cost.
However, the methods disclosed in the above prior arts and patents have the following disadvantages: (1) the reaction uses more than 5 times of expensive n-butyllithium solution, and the manufacturing cost is high. (2) Because excessive butyl lithium generates a large amount of byproduct lithium dimethylamide fine particles, the precipitation separation is poor, the solid-liquid separation by a filtration method is difficult, and blockage is easy to form. (3) A large amount of solvent is needed to be repeatedly washed, filtered and collected to obtain a product solution, so that product loss is easily caused, the synthesis yield is reduced, the solvent consumption is increased, a large amount of hazardous wastes are caused, the manufacturing time is prolonged, and the cost is increased. Meanwhile, the contact probability of the product and air water vapor is increased by multiple times of solution washing, so that the product is decomposed. (4) TaCl 5 Adding excessive n-butyl lithium solution into the mixed solution of the dimethyl amine to directly react the butyl lithium with the TaCl 5 The reaction produces by-products, resulting in low product purity.
Therefore, it is an object of the present invention to provide a method for producing pentakis (dimethylamino) tantalum, which is low in cost, easy to separate, and high in product purity, and can be used for film formation of an IC chip.
Disclosure of Invention
In view of the above, the invention provides a preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation, which reduces the usage amount of n-butyllithium, reduces the manufacturing cost, solves the problem of filtration and separation, reduces the contact frequency of the product with air and water vapor caused by multiple times of washing, reduces the production cost, and improves the product purity.
The invention relates to a preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation, which comprises the following steps:
(1)[(CH 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]the preparation of (1):
adding TaCl 5 Adding the mixed solution into an organic solvent, stirring to form a mixed solution, controlling the temperature of the mixed solution to be 8-12 ℃, and adding dimethylamine into the mixed solution under a stirring state to form a red suspension; then stirring for 4-5 hours, standing for 2-2.5 hours, filtering to remove solid residues to obtain red clear [ (CH) 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]A solution;
(2) lithium dimethylamide LiN (CH) 3 ) 2 The preparation of (1):
adding the n-butyllithium hexane solution into n-hexane, stirring and diluting to obtain a diluted n-butyllithium hexane solution, slowly adding dimethylamine into the diluted n-butyllithium hexane solution at room temperature, and continuously stirring for 1-1.5 hours at room temperature after the dimethylamine is added to form a dimethylaminolithium suspension;
(3) pentakis (dimethylamino) tantalum Ta (N (CH) 3 ) 2 ) 5 The preparation of (1):
cooling the dimethyl amino lithium suspension prepared in the step (2) to 8-12 ℃, and stirring [ (CH) prepared in the step (1) 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]Slowly adding the solution into the dimethyl amino lithium suspension to obtain a mixed solution, wherein the color of the mixed solution gradually changes into light yellow; then heating to 70-80 ℃, and continuously stirring for reaction for 4.5-5.5 hours;
(4) separation and purification:
after the reaction in the step (3) is finished, cooling to room temperature, and performing centrifugal separation under the protection of nitrogen to obtain yellow clear liquid; the solvent was evaporated under reduced pressure to give a yellow solid; the yellow solid was sublimed under reduced pressure to give Ta (N (CH) as a pale orange crystalline solid 3 ) 2 ) 5 。
Preferably, the TaCl of step (1) 5 The mass-to-volume ratio of the organic solvent to the organic solvent is 25-30: 500 g/mL.
Preferably, the organic solvent in step (1) is formed by mixing toluene and n-hexane according to a volume ratio of 4: 1.
Preferably, the dimethylamine of step (1) is reacted with TaCl 5 In a molar ratio of 1: 5.
preferably, the concentration of the n-butyllithium hexane solution in the step (2) is 1-2.5M, and the volume ratio of the n-butyllithium hexane solution to n-hexane is 90-100: 200.
Preferably, the molar ratio of n-butyllithium to dimethylamine in step (2) is 1: 1.
preferably, [ (CH) in the mixed solution of step (3) 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]The molar ratio to lithium dimethylamide is 1: 3.
Preferably, the rotation speed of the centrifugal separation in the step (4) is 3000-5000 rpm.
The method comprises the following steps of firstly preparing bis (dimethylamino) tantalum trichloride from tantalum pentachloride and dimethylamine in an organic solvent, wherein the reaction formula is as shown in formula (I):
TaCl 5 +5HN(CH 3 ) 2 →(HN(CH 3 ) 2 )Ta(N(CH 3 ) 2 )Cl 3 +2[Cl][H 2 N(CH 3 ) 2 )] (I)
the compounds formed during the reaction are soluble, and [ Me ] 2 NH 2 ][Cl]The salt is insoluble and therefore solid salts can be removed by filtration or centrifugation.
Then, bis (dimethylamino) tantalum trichloride is reacted with 3 times of dimethylamino lithium to prepare a target compound pentakis (dimethylamino) tantalum, wherein the reaction formula is shown as the formula (II):
compared with the prior art, the invention has the following beneficial effects:
the application provides a preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation, which is to prepare TaCl 5 Reaction with 5 times dimethylamine in organic solvent to introduce 2-NMe atoms on tantalum metal atom 2 And reacting the bis (dimethylamino) tantalum trichloride with 3 times of dimethyl lithium amide to obtain the pentakis (dimethylamino) tantalum. The preparation method reduces the consumption of n-butyllithium and the manufacturing cost; and the product and the by-products are separated by a centrifugal process under the protection of nitrogen, so that the problem of difficult separation is solved, the dosage of the solvent is reduced, the preparation working hour is reduced, the contact frequency of the product with air and water vapor caused by multiple times of washing is reduced, the chance of decomposition is reduced, and the product yield is improved.
Drawings
FIG. 1 is a nuclear magnetic spectrum of high purity pentakis (dimethylamino) tantalum for use in the formation of a chip prepared in example 1 of the present application.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation comprises the following steps:
(1)[(CH 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]the preparation of (1):
to a 1L round bottom glass bottle was added 29g of TaCl 5 (0.08mol) and an organic solvent consisting of 400ml of toluene and 100ml of n-hexane, stirring to form a yellow suspension mixed solution, controlling the temperature of the mixed solution to be 10 ℃, and adding 18g (0.4mol) of dimethylamine into the mixed solution under the stirring state to form a red suspension; stirring for 4 hr, standing for 2 hr, filtering to remove solid residue to obtain red clear[(CH 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]A solution;
(2) lithium dimethylamide LiN (CH) 3 ) 2 The preparation of (1):
adding 96ml (2.5M, 0.24mol) of n-butyllithium hexane solution and 200ml of n-hexane into a 2L round-bottom flask, stirring to obtain a diluted n-butyllithium hexane solution, slowly adding 11g (0.24mol) of dimethylamine into the n-butyllithium solution at room temperature, and continuing to stir at room temperature for 1 hour after the dimethylamine is added to form a dimethylaminolithium suspension;
(3) pentakis (dimethylamino) tantalum Ta (N (CH) 3 ) 2 ) 5 The preparation of (1):
cooling the lithium dimethylamide suspension prepared in step (2) to 10 ℃, and stirring [ (CH) prepared in step (1) 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]Slowly adding the solution into the dimethyl amino lithium suspension to obtain a mixed solution, wherein the color of the mixed solution gradually changes into light yellow; then heating to 70 ℃, and continuing stirring for 5 hours;
(4) separation and purification
Cooling the mixed solution in the step (3) to room temperature, and separating solid from liquid by using a centrifugal machine under the protection of nitrogen, wherein the rotating speed of the centrifugal machine is 4000rpm, so as to obtain yellow clarified liquid; the solvent was evaporated under reduced pressure to give a yellow solid; the yellow solid was sublimed under reduced pressure to obtain Ta (N (CH) 3 ) 2 ) 5 Ta (N (CH) 3 ) 2 ) 5 The purity of (D) was 99.999% (calculated as metal content).
The nuclear magnetic spectrum of the high purity pentakis (dimethylamino) tantalum film formed on the chip prepared in example 1 is shown in fig. 1. Description of the peak value of the spectrogram: delta (ppm)3.25N (CH) 3 ) 2 (ii) a 7.16ppm is the deuterated benzene reference peak.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation is characterized by comprising the following steps:
(1)[(CH 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]the preparation of (1):
adding TaCl 5 Adding the mixed solution into an organic solvent, stirring to form a mixed solution, controlling the temperature of the mixed solution to be 8-12 ℃, and adding dimethylamine into the mixed solution under a stirring state to form a red suspension; then stirring for 4-5 hours, standing for 2-2.5 hours, filtering to remove solid residues to obtain red clear [ (CH) 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]A solution;
(2) lithium dimethylamide LiN (CH) 3 ) 2 The preparation of (1):
adding the n-butyllithium hexane solution into n-hexane, stirring and diluting to obtain a diluted n-butyllithium hexane solution, slowly adding dimethylamine into the diluted n-butyllithium hexane solution at room temperature, and continuously stirring for 1-1.5 hours at room temperature after the dimethylamine is added to form a dimethylaminolithium suspension;
(3) pentakis (dimethylamino) tantalum Ta (N (CH) 3 ) 2 ) 5 The preparation of (1):
cooling the dimethyl amino lithium suspension prepared in the step (2) to 8-12 ℃, and stirring [ (CH) prepared in the step (1) 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]Slowly adding the solution into the dimethyl amino lithium suspension to obtain a mixed solution, wherein the color of the mixed solution gradually changes into light yellow; then heating to 70-80 ℃, and continuously stirring for reaction for 4.5-5.5 hours;
(4) separation and purification:
after the reaction in the step (3) is finished, cooling to room temperature, and performing centrifugal separation under the protection of nitrogen to obtain yellow clear liquid; the solvent was evaporated under reduced pressure to give a yellow solid; the yellow solid was sublimed under reduced pressure to obtain Ta (N (CH) 3 ) 2 ) 5 。
2. The method for preparing high purity pentakis (dimethylamino) tantalum for use in on-chip film formation according to claim 1, wherein the TaCl of step (1) 5 The mass volume ratio of the organic solvent to the organic solvent is 25-30: 500 g/mL.
3. The method for preparing high-purity pentakis (dimethylamino) tantalum for chip film formation according to claim 2, wherein the organic solvent in the step (1) is a mixture of toluene and n-hexane at a volume ratio of 4: 1.
4. The method for producing highly pure pentakis (dimethylamino) tantalum for use in on-chip film formation according to claim 1, wherein the dimethylamine and TaCl in step (1) 5 In a molar ratio of 1: 5.
5. the method for preparing high-purity pentakis (dimethylamino) tantalum for chip film formation according to claim 1, wherein the n-butyllithium hexane solution in the step (2) has a concentration of 1-2.5M, and the volume ratio of the n-butyllithium hexane solution to n-hexane is 90-100: 200.
6. The method for preparing highly pure pentakis (dimethylamino) tantalum for use in die-coating according to claim 1, wherein the molar ratio of n-butyllithium to dimethylamine in step (2) is 1: 1.
7. the method for preparing high-purity pentakis (dimethylamino) tantalum for use in on-chip film formation according to claim 1, wherein [ (CH) is present in the mixed solution in the step (3) 3 ) 2 NH][Ta(N(CH 3 ) 2 ) 2 Cl 3 ]The molar ratio to lithium dimethylamide is 1: 3.
8. The method for preparing high-purity pentakis (dimethylamino) tantalum for chip film formation according to claim 1, wherein the rotation speed of the centrifugal separation in the step (4) is 3000-5000 rpm.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106916072A (en) * | 2015-12-24 | 2017-07-04 | 苏州复纳电子科技有限公司 | A kind of five（Dimethylamino）Tantalum synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916072A (en) * | 2015-12-24 | 2017-07-04 | 苏州复纳电子科技有限公司 | A kind of five（Dimethylamino）Tantalum synthetic method |
Non-Patent Citations (3)
| Title |
|---|
| CHEN, SHU-JIAN等: "Crystal Structure of TaCl(NMe2)4 and Its Reactions with Lithium Amides and Water. Indirect Observation of an Equilibrium among TaCl(NMe2)4, Ta(NMe2)5 and Ta2(μ-Cl)2(NMe2)6Cl2", ORGANOMETALLICS, vol. 28, no. 1, pages 167 - 171 * |
| MALCOLM H.: "Chloro(dimethylamido) Compounds of Tantalum(V): Preparations, Properties, and Structures of [Ta(NMe2)3Cl2]2, TaCl3(NMe2)2(HNMe2), Ta(NMe2)3Cl2(HNMe2), and [TaCl2(NMe2)2(HNMe2)]20", INORG. CHEM., pages 1859 - 1866 * |
| SCHWEIGER, SCOTT W.等: "The isolation and chemistry of niobium and tantalum dimethylamides containing mono- and di-aryloxide ancillary ligands", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS, vol. 2001, no. 16, pages 2401 - 2408 * |
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