Copper alcohol amine compound as well as convenient synthesis process and application thereof
The synthesis of copper alkanolamine compounds by reacting CuX2, ammonia, and alkanolamines simplifies the synthesis process of copper alkanolamine compounds, solves the problems of complex and high cost in the synthesis of copper alkanolamine compounds in the prior art, and realizes the production of copper alkanolamine compounds with low cost and high yield.
Patent Information
- Application Number
- CN202511058279.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-30
- Publication Date
- 2025-10-28
AI Technical Summary
The existing synthesis methods of copper alcohol amine compound precursors are complex and costly, and cannot meet the requirements of atomic layer deposition.
Copper alcoholamine compounds were synthesized by reacting CuX2, ammonia, and alcoholamines. The process was simplified by using dispersion, filtration, and reflux steps, and inexpensive and readily available solvents such as methanol or ethanol were used to optimize the reaction conditions.
This invention enables the production of copper alkanolamine compounds with a simple process, low cost, and high yield. It solves the technical problems existing in the synthesis process of copper alkanolamine compounds in the prior art, simplifies the process, reduces costs, and increases yield.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of organometallic synthesis technology, and more specifically to a copper alcoholamine compound and its convenient synthesis process and application. Background Technology
[0002] Atomic layer deposition (ALD) technology has become a key process in semiconductor, catalysis, and energy fields due to its high precision, excellent conformability, and controllability. Copper (Cu), as a high-performance conductive material, directly impacts film quality and device performance through the design and application of its ALD precursors. Compared to aluminum, copper has lower resistivity, higher thermal conductivity, and stronger resistance to electromigration, making it an ideal interconnect metal material. As a seed layer for interconnect applications, copper films require continuous surface morphology and high purity.
[0003] Compared to other copper precursors, the most commonly used chemical vapor deposition (CVD) precursor, the monovalent copper complex Cu(hfac)(tmvs) (copper hexafluoroacetylacetone trimethylvinylsilane), is unsuitable for atomic layer deposition (ALD) due to its lack of self-limiting disproportionation reaction and poor thermal stability. Divalent copper β-diketone complexes such as Cu(thd)₂ and Cu(acac)₂ suffer from low vapor pressure and slow volatilization rates. While fluorinated divalent copper β-diketone molecules (such as Cu(hfac)₂) have high vapor pressures, they require excessively high decomposition temperatures, and the fluorine atoms in the precursor lead to poor adhesion between the ALD copper film and the barrier metal. Copper β-ketoimine compounds, on the other hand, suffer from insufficient volatility.
[0004] In comparison, the novel copper alkanolamine precursor exhibits significant advantages: excellent thermal stability (activation energy 113 kJ / mol), room-temperature liquid properties (traditional divalent copper precursors are all solid), high vapor pressure (0.9 Torr at 75 °C), and low-temperature deposition capability (it can be deposited on polymer materials). More importantly, its ligands are fluorine-free, avoiding the problem of fluorine residue.
[0005] Currently, the main methods for synthesizing novel copper alcoholamine precursors are as follows:
[0006] 1. A novel copper alkanolamine precursor was synthesized by reacting copper alkoxide with the corresponding alkanolamine compound. The reaction equation is as follows:
[0007]
[0008] 2. A novel copper alkanolamine precursor was synthesized by reacting copper halides with their corresponding deprotonated alkanolamine salts. The reaction equation is as follows:
[0009]
[0010] However, the preparation process of copper precursors for alcoholamine ligands is currently relatively complex, time-consuming, and expensive.
[0011] Therefore, how to develop a novel synthetic process for preparing a series of copper precursors is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0012] In view of this, the purpose of the present invention is to provide a copper alcoholamine compound and its convenient synthesis process and application, so as to overcome the shortcomings of the prior art.
[0013] To achieve the above objectives, the present invention adopts the following technical solution:
[0014] A copper alcoholamine compound with the following structural formula:
[0015] Among them, R 1 R 2 R 3 R 4 These are the same or different alkyl substituents with 0-5 carbon atoms; n = 0-3 (all integers).
[0016] Furthermore, the structural formula of the above-mentioned copper alcoholamine compound is as follows:
[0017] Furthermore, the aforementioned copper alcoholamine compound comprises the following raw materials: CuX2, ammonia, and... The molar ratio is 1:(5-10):(1-4);
[0018] Where X is a halogen; R 1 R 2 R 3 R 4 These are the same or different alkyl substituents with 0-5 carbon atoms; n = 0-3 (all integers).
[0019] Furthermore, the CuX2 mentioned above is copper chloride.
[0020] Furthermore, the above It is 3-dimethylamino-2-butanol or 3-dimethylamino-2-propanol.
[0021] The convenient synthetic process for the above-mentioned copper alcoholamine compounds specifically includes the following steps:
[0022] (1) Disperse CuX2 in a solvent, add ammonia water, react, filter, and obtain Cu(NH3)6X2 solid;
[0023] (2) Add the solution to Cu(NH3)6X2 solid, add solvent, and heat to reflux to obtain a copper alcoholamine solution;
[0024] The reaction equation is:
[0025]
[0026] (3) Filter the copper alcoholamine solution to remove the solvent, and then obtain the copper alcoholamine compound.
[0027] Furthermore, in step (1) above, 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 methanol or ethanol.
[0028] Furthermore, in step (1) above, the reaction time is 1-24 hours.
[0029] Furthermore, in step (2) above, the heating and reflux time is 1-24 hours.
[0030] The present invention also claims protection for the use of the above-mentioned copper alcoholamine compound in atomic layer deposition.
[0031] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:
[0032] 1. The process is simple, convenient, efficient, and yields excellent output;
[0033] 2. Material costs have been significantly reduced, as all raw materials used are readily available and inexpensive pharmaceutical products;
[0034] 3. Simple separation and convenient purification.
[0035] In summary, this invention simplifies the feeding process, optimizes the processing technology, greatly shortens the reaction time, improves product yield, and makes the process more convenient and lower in cost. Detailed Implementation
[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0037] Example 1
[0038] A convenient synthetic process for copper alcoholamine compounds, with the following structural formula: Specifically, the following steps are included:
[0039] (1) Disperse copper chloride (295g, 2.2mol) in solvent ethanol (1L), and slowly add it to an aqueous solution of ammonia (575g, 16.43mol) (2.3L). After the addition is complete, react for 1h. After the reaction is complete, filter to obtain Cu(NH3)6Cl2 blue solid.
[0040] (2) 3-Dimethylamino-2-butanol ligand (4.5 mol) was slowly added to Cu(NH3)6Cl2 blue solid, and 3 L of n-heptane was added. After the addition was completed, the temperature was raised and refluxed for 2 h to obtain copper alcoholamine solution.
[0041] (3) After the reaction was completed, the copper alcoholamine solution was filtered to remove the solvent and 638g of purple liquid product (copper alcoholamine compound) was obtained, with a yield of 98%.
[0042] Example 2
[0043] A convenient synthetic process for copper alcoholamine compounds, with the following structural formula: Specifically, the following steps are included:
[0044] (1) Disperse copper chloride (295g, 2.2mol) in methanol (1L) solvent, and slowly add it to an aqueous solution of ammonia (539g, 15.4mol) (2.1L). After the addition is complete, react for 2 hours. After the reaction is complete, filter to obtain Cu(NH3)6Cl2 blue solid.
[0045] (2) 4.39 mol of 3-dimethylamino-2-methyl-2-propanol ligand was added dropwise to Cu(NH3)6Cl2 blue solid, and 3 L of toluene was added. After the addition was completed, the mixture was heated and refluxed for 2 h to obtain a copper alcoholamine solution.
[0046] (3) After the reaction was completed, the copper alcoholamine solution was filtered to remove the solvent and 569g of purple liquid product (copper alcoholamine compound) was obtained, with a yield of 96.9%.
[0047] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A copper alcoholamine compound, characterized in that, The structural formula is: Among them, R 1 R 2 R 3 R 4 These are the same or different alkyl substituents with 0-5 carbon atoms; n = 0-3.
2. The copper alcoholamine compound according to claim 1, characterized in that, The structural formula is:
3. A copper alcoholamine compound according to claim 1 or 2, characterized in that, Including the following raw materials: CuX2, ammonia water and The molar ratio is 1:(5-10):(1-4); Where X is a halogen; R 1 、R 2 、R 3 、R 4 These are the same or different alkyl substituents with 0-5 carbon atoms; n = 0-3.
4. The copper alcoholamine compound according to claim 3, characterized in that, The CuX2 is copper chloride.
5. A copper alcoholamine compound according to claim 3, characterized in that, The It is 3-dimethylamino-2-butanol or 3-dimethylamino-2-propanol.
6. A convenient synthetic process for the copper alcoholamine compound as described in any one of claims 1-5, characterized in that, Specifically, the following steps are included: (1) Disperse CuX2 in a solvent, add ammonia water, react, filter, and obtain Cu(NH3)6X2 solid; (2) Add the solution to Cu(NH3)6X2 solid, add solvent, and heat to reflux to obtain a copper alcoholamine solution; (3) The copper alcoholamine solution is filtered to remove the solvent, and the copper alcoholamine compound is obtained.
7. The convenient synthesis process of a copper alcoholamine compound according to claim 6, characterized in that, 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.
8. The convenient synthesis process of a copper alcoholamine compound according to claim 6, characterized in that, In step (1), the reaction time is 1-24 hours.
9. The convenient synthesis process of a copper alcoholamine compound according to claim 6, characterized in that, In step (2), the heating and reflux time is 1-24h.
10. The use of a copper alcoholamine compound as described in any one of claims 1-5 or as described in any one of claims 6-9 in atomic layer deposition.