Copper alcohol amine compound as well as preparation method and application thereof

Abstract

The invention discloses a copper alcohol amine compound and a preparation method and application thereof, and belongs to the technical field of organic metal synthesis. The structural formula of the copper alcohol amine compound is as follows: the copper alcohol amine compound comprises the following raw materials: CuX2 and ROM in a molar ratio of (1-3): (1-5): (1-5); the preparation method specifically comprises the following steps: (1) dispersing CuX2 in a solvent, adding ROM, heating and stirring; (2) adding, heating, refluxing and stirring; and (3) filtering to remove the solvent. The invention develops a synthesis process for preparing a series of copper precursors by a series one-pot method, the feeding process is simplified, the treatment process is optimized, the synthesis time and cost are greatly shortened, a qualified copper precursor product is obtained by fewer purification steps, and the process is more convenient.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organometallic synthesis, and more particularly to a copper alcohol amine compound, a preparation method and application thereof. BACKGROUND

[0002] Atomic layer deposition (ALD) technology has become a key process in the fields of semiconductor, catalysis and energy due to its high precision, excellent conformality and controllability. Copper (Cu) is an ideal interconnection metal material due to its lower resistivity, higher thermal conductivity and stronger anti-electromigration ability compared with aluminum. As a seed layer for interconnection application, copper thin film needs to have continuous surface morphology and high purity.

[0003] Compared with other copper precursors, the most commonly used chemical vapor deposition (CVD) precursor, monovalent copper complex Cu(hfac)(tmvs) (hexafluoroacetylacetone trimethylvinylsilane copper), cannot be used for atomic layer deposition (ALD) due to the lack of self-limiting property of disproportionation reaction and poor thermal stability. Divalent copper β-diketone complexes such as Cu(thd)2 and Cu(acac)2 have the defects of low vapor pressure and slow volatilization rate. Fluorinated divalent copper β-diketone molecules (such as Cu(hfac)2) have a relatively high vapor pressure, but require a very high decomposition temperature, and the fluorine atoms in the precursor will result in poor adhesion of ALD copper film to barrier metals. Copper β-ketimine compounds have the problem of insufficient volatility.

[0004] In comparison, the new copper alcohol amine compound precursor exhibits significant advantages: excellent thermal stability (activation energy 113 kJ / mol), room temperature liquid state (traditional divalent copper precursors are all solid), high vapor pressure (0.9 Torr at 75℃) and low-temperature deposition capability (deposition on polymer materials). More importantly, the ligand does not contain fluorine elements, avoiding the problem of fluorine residues.

[0005] Currently, the synthesis methods of the new copper alcohol amine compound precursor mainly include the following two methods:

[0006] 1. The new copper alcohol amine compound precursor is synthesized by reacting copper alcohol with the corresponding alcohol amine compound. The reaction equation is as follows:

[0007]

[0008] 2. The new copper alcohol amine compound precursor is synthesized by reacting copper halide with the corresponding deprotonated alcohol amine salt. The reaction equation is as follows:

[0009]

[0010] However, the existing synthesis process has high cost, complex route, and complicated process, and needs multiple steps.

[0011] Therefore, how to quickly and simply prepare a copper alcohol amine compound is a problem to be solved by those skilled in the art. SUMMARY

[0012] Therefore, the purpose of the present application is to provide a copper alcohol amine compound, a preparation method thereof and an application thereof, so as to solve the problems in the prior art.

[0013] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0014] A copper alcohol amine compound, the structural formula of which is:

[0015] wherein R 1 , R 2 , R 3 , R 4 are the same or different alkyl substituents with carbon number 0-5; n=0-3 (all are integers).

[0016] The copper alcohol amine compound includes the following raw materials: CuX2, ROM and The molar ratio is (1-3):(1-5):(1-5).

[0017] wherein X is halogen, preferably Cl, Br or I, more preferably Cl; R is alkyl substituent with carbon number 1-5, preferably methyl or ethyl; M is Li, Na, K, Mg or Ca, preferably K; R 1 , R 2 , R 3 , R 4 are the same or different alkyl substituents with carbon number 0-5; n=0-3 (all are integers).

[0018] Further, the CuX2 is copper bromide; the ROM is potassium ethoxide or sodium ethoxide; and the R is 3-dimethylamino-2-butanol or 3-dimethylamino-2-propanol.

[0019] The preparation method of the copper alcohol amine compound specifically includes the following steps:

[0020] (1) dispersing CuX2 in a solvent, adding ROM, warming, stirring, and obtaining a Cu(OR)2 solution;

[0021] (2) adding to the Cu(OR)2 solution, warming, refluxing, and stirring to obtain a copper alcohol amine solution;

[0022] The reaction equation is as follows:

[0023]

[0024] (3) filtering the copper alcohol amine solution to remove the solvent, thereby obtaining the copper alcohol amine compound.

[0025] Further, in the step (1), the solvent is at least one of dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methanol, ethanol, tert-butanol, tetrahydrofuran, toluene, xylene, n-heptane and n-hexane, preferably dichloromethane.

[0026] Further, in the step (1), the temperature is raised to room temperature.

[0027] Further, in the step (1), the stirring time is 1-24h.

[0028] Further, in the step (2), the temperature is raised to room temperature.

[0029] Further, in the step (2), the reflux time is 1-24h.

[0030] Further, in the step (2), the stirring time is 1-24h.

[0031] The application also claims a use of the above-mentioned copper alcohol amine compound in atomic layer deposition.

[0032] According to the above technical solution, compared with the prior art, the application has the following beneficial effects:

[0033] 1. The process route is greatly shortened, and the process is convenient and efficient;

[0034] 2. The material cost is greatly reduced, and the raw materials used are all cheap and easily available drugs;

[0035] 3. The separation is simple, and the purification is convenient.

[0036] In summary, the application develops a synthesis process for preparing a series of copper precursors by a series one-pot method, simplifies the feeding process, optimizes the processing technology, greatly shortens the synthesis time and cost, and obtains qualified copper precursor products with fewer purification steps, and the process is more convenient. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0038] Example 1

[0039] A method for preparing a copper alcohol amine compound having the structural formula: The method comprises the following steps:

[0040] (1) Copper bromide (314 g, 2.19 mol) was dispersed in dichloromethane (1 L), and a solution of sodium ethoxide (347 g, 5.11 mol) in ethanol (800 mL) was slowly added. After the addition was completed, the temperature was raised to room temperature, and the mixture was stirred for 1 h to obtain a copper ethoxide solution;

[0041] (2) 3-Dimethylamino-2-propanol (4.95 mol) was added dropwise to the copper ethoxide solution, and 3 L of n-heptane was added. After the addition was completed, the temperature was raised to room temperature, and the mixture was refluxed for 5 h and then stirred at room temperature for 2 h to obtain a copper alcohol amine solution;

[0042] (3) The copper alcohol amine solution was filtered, and the solvent was removed to obtain a purple solid product (517 g) with a yield of 87.8%, which was the copper alcohol amine compound. The product was distilled at 80 °C (10 -14 Torr) to obtain a product with a GC purity of 99.902% and a decomposition temperature of 184-185 °C.

[0043] Example 2

[0044] A method for preparing a copper alcohol amine compound having the structural formula: The method comprises the following steps:

[0045] (1) Copper bromide (314 g, 2.19 mol) was dispersed in dichloromethane (1 L), and a solution of sodium ethoxide (347 g, 5.11 mol) in ethanol (800 mL) was slowly added. After the addition was completed, the temperature was raised to room temperature, and the mixture was stirred for 1 h to obtain a copper ethoxide solution;

[0046] (2) 3-Dimethylamino-2-propanol (4.95 mol) was added dropwise to the copper ethoxide solution, and 3 L of n-heptane was added. After the addition was completed, the temperature was raised to room temperature, and the mixture was refluxed for 5 h and then stirred at room temperature for 2 h to obtain a copper alcohol amine solution;

[0047] (3) The copper alcohol amine solution was filtered, and the solvent was removed to obtain a purple solid product (517 g) with a yield of 87.8%, which was the copper alcohol amine compound. The product was distilled at 80 °C (10 -3 Torr) to obtain a product with a GC purity of 99.902% and a decomposition temperature of 184-185 °C.

[0048] The foregoing description of the disclosed embodiments enables a person skilled in the art to make or use the application. Modifications of these embodiments will occur to persons of skill in the art, and that the appended claims are intended to cover all such modifications that do not depart from the true spirit and scope of the application. Therefore, the application is not limited to the embodiments shown but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A copper alcohol amine compound, characterized in that The structural formula is: Among them, R 1 、R 2 、R 3 、R 4 are the same or different alkyl substituents having 0 to 5 carbon atoms; n=0-3.

2. A copper alcohol amine compound according to claim 1, characterized in that, Including the following raw materials: CuX2, ROM and The molar ratio is (1-3):(1-5):(1-5); Wherein, X is a halogen; R is an alkyl substituent having 1 to 5 carbon atoms; M is Li, Na, K, Mg or Ca; R 1 、R 2 、R 3 、R 4 are the same or different alkyl substituents having 0 to 5 carbon atoms; n=0-3.

3. A method for preparing the copper alcoholamine compound according to claim 1 or 2, characterized in that: The specific steps include: (1) Dispersing CuX2 in a solvent, adding ROM, heating, and stirring to obtain a Cu(OR)2 solution; (2) Add to Cu(OR)2 solution, heat, reflux, stir to obtain copper alcoholamine solution; (3) filtering the copper alcohol amine solution and removing the solvent to obtain the copper alcohol amine compound.

4. The method for preparing a copper alcohol amine compound according to claim 3, wherein In step (1), the solvent is at least one of dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methanol, ethanol, tert-butanol, tetrahydrofuran, toluene, xylene, n-heptane and n-hexane.

5. The method for preparing a copper alcoholamine compound according to claim 3, wherein: In step (1), the temperature is raised to room temperature.

6. The method for preparing a copper alcoholamine compound according to claim 3, wherein: In step (1), the stirring time is 1-24h.

7. The method for preparing a copper alcoholamine compound according to claim 3, wherein: In step (2), the temperature is raised to room temperature.

8. The method for preparing a copper alcohol amine compound according to claim 3, wherein: In step (2), the reflux time is 1-24h.

9. The method for preparing a copper alcoholamine compound according to claim 3, wherein: In step (2), the stirring time is 1-24h.

10. Use of the copper alkoxide amine compound according to claim 1 or 2 or the copper alkoxide amine compound according to any one of claims 3 to 9 in atomic layer deposition.

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