CN106916072A - A kind of five（Dimethylamino）Tantalum synthetic method - Google Patents
A kind of five（Dimethylamino）Tantalum synthetic method Download PDFInfo
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- CN106916072A CN106916072A CN201510982447.8A CN201510982447A CN106916072A CN 106916072 A CN106916072 A CN 106916072A CN 201510982447 A CN201510982447 A CN 201510982447A CN 106916072 A CN106916072 A CN 106916072A
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Abstract
The invention discloses a kind of synthetic method of five (dimethylamino) tantalums, comprise the following steps：Tantalic chloride and alkane C are added in the reactor of inert atmosphere protectionnH2n+2(n >=6) mixture, adds dimethylamine to be reacted under conditions of stirring, and the temperature of reaction system is maintained at 0~-30 DEG C, after completion of dropping, is kept for 0~-30 DEG C react 8-12 hours.N-BuLi alkane C is added dropwisenH2n+2(n >=6) solution, is maintained at 0~-30 DEG C and reacts 4-20 hours, then maintain the reflux for reaction 4-12 hours.It is decompressed to 1000-7000Pa and steams alkane CnH2n+2(n >=6) solvent is transferred in sublimator to dry, is decompressed to 50-300Pa and is collected product five (dimethylamino) tantalum.Reagent selected by the inventive method is conventional reagent, inexpensive and be easy to get, and operating process is simple, without potential safety hazard；The application of snake type sandwich sublimation device, improves product purity and reaction yield；Solvent needed for reaction is reusable, discarded object is not produced, to environment without any pollution.
Description
Technical field
The present invention relates to material production field, more particularly to a kind of (dimethylamino) the tantalum C of used in electronic industry tantalum compound raw materials for production five10H30N5The synthetic method of Ta.
Background technology
Tantalum nitride (TaN) film has that resistivity is low, fusing point is high, the activation of lattice and grain boundary decision can a series of excellent performances such as high, heat endurance is high, therefore application in microelectronic chip and manufacturing process is than wide.For example, after the standard CMOS in the copper interconnection technology in road, tantalum nitride membrane is applied frequently as the diffusion impervious layer of copper；In below 45nm CMOS technologies, there is good stability at elevated temperature, therefore be used as metal gate material between tantalum nitride and high-dielectric-coefficient grid medium；In extreme ultraviolet carving technology, tantalum nitride is alternatively arranged as absorbed layer.
Tantalum pentoxide (Ta2O5) film has high-k (25~35), refractive index high and good chemical stability, can as dynamic RAM, antireflective film, high temperature impedance, gas sensor, capacitor critical material.Especially, tantalum pentoxide is used as high dielectric constant material, and it is more much higher than traditional earth silicon material, therefore can realize possessing bigger physical thickness under identical capacitance density, so as to be effectively reduced the leakage current density of device, the reliability and service life of device are improved.At present, in dynamic RAM, RF IC passive capacitive etc. has obtained good application to tantalum pentoxide in field.
As (dimethylamino) tantalum of critical materials-five C of tantalum nitride and tantalum pentoxide10H30N5Ta, structure is shown in Fig. 1, is the key reaction source of chemical vapor deposition (CVD) and ald (ALD) technique growth tantalum nitride or tantalum pentoxide.At present, the report about five (dimethylamino) tantalum synthetic methods is also limited only to laboratory synthesis, and the unsuitable stability contorting of operating process, and reaction yield is low, purity is low.Its primary synthetic methods is：(1) dimethylamine obtains dimethylamine lithium salts with butyl lithium reaction；(2) after dimethylamine lithium salts reacts with tantalic chloride, through filtering, solvent is extracted；(3) crude product will be separated out and is transferred to sublimator, distil to obtain crude product.But there are some shortcomings in the method：(1) because side product chlorinated lithium particle is thin and light specific gravity, so being difficult filtering during filtering, made troubles to practical operation；(2) solid by-product can wrap up a certain amount of product, cause product to lose, and reduce synthetic yield；(3) a large amount of solvents are needed to use in filter process constantly to clean, therefore reduces efficiency, improve production cost.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of five (dimethylamino) tantalums, to solve five (dimethylamino) tantalum synthetic operation cumbersomes, yield is low, and purity is low, high cost problem.
In order to solve the above problems, the invention provides a kind of five (dimethylamino) tantalum synthetic methods, comprise the following steps：Tantalic chloride and alkane C are added in the reactor of inert atmosphere protectionnH2n+2(n >=6) mixture, dropwise addition dimethylamine is reacted under conditions of stirring, and the temperature of reaction system is maintained at 0~-30 DEG C, after completion of dropping, keeps the temperature of reaction system to be reacted 8-12 hours at 0~-30 DEG C.N-BuLi alkane C is added dropwisenH2n+2(n >=6) solution, keeps system temperature to be reacted 4-20 hours at 0~-30 DEG C, then maintain the reflux for reaction 4-12 hours.Pressure in reactor is reduced to 1000-7000Pa, alkane C is then steamednH2n+2(n >=6) solvent, and product is transferred in sublimator, product five (dimethylamino) tantalum is collected under 50-300Pa low pressure.
The n-BuLi alkane CnH2n+2(n >=6) solution, n is selected from 6 or 7, and alkane is selected from n-hexane or normal heptane.
Maintenance system temperature is 0~-30 DEG C when the dimethylamine is added.
The dimethylamine is 5 with the mol ratio of tantalic chloride:1~10:1.
The n-BuLi alkane CnH2n+2Maintenance system temperature is advisable in 0~-30 DEG C of scopes during the addition of (n >=6) solution.
The tantalic chloride is 1 with butyl lithium mol ratio:5~1:8.
The alkane solvent rectification under vacuum pressure is 1000-7000Pa, and temperature is 30 DEG C~100 DEG C.
The product five (dimethylamino) tantalum Decompression Sublimation pressure is 50-300Pa, and temperature is 50 DEG C~100 DEG C.
The sublimator is snake type sandwich sublimation device.
The inert atmosphere is high pure nitrogen atmosphere or high-purity argon gas atmosphere.
The beneficial effects of the invention are as follows：1st, selected reagent is conventional reagent, is easily obtainable；2nd, course of reaction is more gentle, simple to operate controllable, does not have potential safety hazard；3rd, alkane CnH2n+2(n >=6) are reusable, do not have discarded object, environmentally safe；4th, the use of snake type sandwich sublimation device, improves the purity for preparing yield and product.
Brief description of the drawings
Fig. 1 five (dimethylamino) tantalum structural formula
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and the present embodiment is only used for explaining the present invention, is not intended to limit the scope of the present invention..
Embodiment 1
Under an argon atmosphere, 180 grams of tantalic chlorides and 500 milliliters of n-hexanes are added in a kettle., under agitation, to 135 grams of anhydrous dimethyl amine is added in reactor, -30 DEG C are maintained the temperature at during addition, add holding system thermotonus 10 hours, it is subsequently adding 1000 milliliters of n-BuLi n-hexane molten (2.5mol/L), adition process maintenance system temperature is -30 DEG C, adds and is reacted 16 hours at -30 DEG C, then back flow reaction 4 hours.Cooling is first decompressed to 7000Pa and steams solvent hexane, and temperature is 90 DEG C.Solid is transferred to sublimator by solvent after being evaporated, and 300Pa is finally decompressed to again and is distilled to obtain product five (dimethylamino) tantalum, and temperature is 90 DEG C, obtains 148.3 grams of product five (dimethylamino) tantalum, and yield is 74.2%.
Embodiment 2
In a nitrogen atmosphere, 180 grams of tantalic chlorides and 500 milliliters of normal heptanes are added in a kettle., under agitation, to 135 grams of anhydrous dimethyl amine is added in reactor, add speed to maintain the temperature at -10 DEG C, add holding system thermotonus 10 hours, it is subsequently adding 1100 milliliters of n-BuLi normal heptane molten (2.5mol/L), adition process maintenance system temperature is -10 DEG C, adds and is reacted 18 hours at -10 DEG C, then back flow reaction 4 hours.Cooling first reduces to 5000Pa and steams solvent n-heptane, and temperature is 70 DEG C.Solid is transferred to sublimator by solvent after being evaporated, and 250Pa is finally decompressed to again and is distilled to obtain product five (dimethylamino) tantalum, and temperature is 60 DEG C, obtains 166.5 grams of product five (dimethylamino) tantalum, and yield is 83.2%.
Embodiment 3
Under an argon atmosphere, 720 grams of tantalic chlorides and 2000 milliliters of normal heptanes are added in a kettle., under agitation, to 540 grams of anhydrous dimethyl amine is added in reactor, add speed to maintain the temperature at -20 DEG C, add holding system thermotonus 10 hours, it is subsequently adding 4400 milliliters of n-BuLi normal heptane molten (2.5mol/L), adition process maintenance system temperature is -20 DEG C, adds reaction 18 hours, then back flow reaction 4 hours.Cooling is first decompressed to 1000Pa and steams solvent n-heptane, and temperature is 50 DEG C.Solid is transferred to sublimator by solvent after being evaporated, and 50Pa is finally decompressed to again and is distilled to obtain product five (dimethylamino) tantalum, and temperature is 50-100 DEG C, obtains 698.4 grams of product five (dimethylamino) tantalum, and yield is 87.3%.
In invented technology, reaction and distillation condition are steady, it is easy to control, and stablize with materials safety, be readily obtained, cheap, reaction yield and the advantage such as production efficiency is high.Gross production rate can reach more than 90%.Alkane CnH2n+2(n >=6) are nontoxic, can reuse, will not produce any discarded object, are not only suitable for laboratory synthesis, are also suitable for certain scale and are combined to.
Claims (10)
1. one kind five (dimethylamino) tantalum synthetic method, it is characterised in that comprise the following steps：
(1) tantalic chloride and alkane C are added in the reactor of inert atmosphere protectionnH2n+2(n >=6) mixture,
Dimethylamine is added to be reacted under conditions of stirring, the temperature of reaction system is maintained at 0~-30
DEG C, after completion of dropping, kept for 0~-30 DEG C react 8-12 hours；
(2) n-BuLi alkane C is added dropwisenH2n+2(n >=6) solution, is maintained at 0~-30 DEG C and reacts 4-20 hours,
Reaction 4-12 hours is maintained the reflux for again；
(3) alkane C is steamed under 1000-7000Pa pressurenH2n+2, then be transferred to for product by (n >=6) solvent
In sublimator, product is collected under the reduced pressure of decompression 50-300Pa.
2. the method for claim 1, it is characterised in that the n-BuLi alkane CnH2n+2(n >=6) are molten
Liquid, n is selected from 6 or 7, and alkane is selected from n-hexane or normal heptane.
3. the method for claim 1, it is characterised in that maintenance system temperature is when the dimethylamine is added
0~-30 DEG C are advisable.
4. the method for claim 1, it is characterised in that the dimethylamine is with the mol ratio of tantalic chloride
The ︰ 1 of 5 ︰ 1~10.
5. the method for claim 1, it is characterised in that the n-BuLi alkane CnH2n+2(n >=6) are molten
Maintenance system temperature is advisable for 0~-30 DEG C when liquid is added.
6. the method for claim 1, it is characterised in that the tantalic chloride is 1 with butyl lithium mol ratio
The ︰ 8 of ︰ 5~1.
7. the method for claim 1, it is characterised in that the alkane solvent rectification under vacuum pressure is
1000-7000Pa, temperature is 30 DEG C~100 DEG C.
8. the method for claim 1, it is characterised in that the product Decompression Sublimation pressure is 50-300Pa,
Temperature is 50 DEG C~100 DEG C.
9. method according to claim 1, it is characterised in that the sublimator is snake type sandwich sublimation device.
10. the method for claim 1, it is characterised in that the inert atmosphere is high pure nitrogen atmosphere or height
Pure argon atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790671A (en) * | 2019-11-01 | 2020-02-14 | 浙江博瑞电子科技有限公司 | Method for refining pentakis (dimethylamino) tantalum |
| CN114957014A (en) * | 2022-06-21 | 2022-08-30 | 安徽博泰电子材料有限公司 | Preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790671A (en) * | 2019-11-01 | 2020-02-14 | 浙江博瑞电子科技有限公司 | Method for refining pentakis (dimethylamino) tantalum |
| CN110790671B (en) * | 2019-11-01 | 2022-05-20 | 浙江博瑞电子科技有限公司 | Method for refining pentakis (dimethylamino) tantalum |
| CN114957014A (en) * | 2022-06-21 | 2022-08-30 | 安徽博泰电子材料有限公司 | Preparation method of high-purity pentakis (dimethylamino) tantalum for chip film formation |
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