A method for preparing a metal complex

Abstract

The present invention relates to the technical field of metal organic source synthesis, and specifically discloses a method for preparing a metal complex. The general structural formula of the metal complex to be prepared is R1C5H4M(NR2R3)3, wherein R1 is i Pr, n Pr, Me or Et; R2 and R3 are Me or Et; M is Ti, Zr or Hf; this case provides a method for synthesizing a high-purity metal complex precursor, which not only has good chemical stability, a mild reaction process and high safety, but also is simple to operate and the subsequent separation and purification are relatively simple, and the operation is relatively safe; the prepared compound will be dedicated to uniformly depositing a film or thin film containing Group III, IV and V metal elements on the entire surface of a substrate with uneven or porous characteristics, thereby significantly improving the uniformity and overall performance of the film.

Description

Technical Field

[0001] The present invention relates to the technical field of metal organic source synthesis, and in particular to a method for preparing a metal complex. Background Art

[0002] Chip manufacturing is a highly sophisticated process, centered on the precise transfer of designed circuit patterns onto thin films. The key to this process lies in the thin film deposition process. The performance of the thin film not only directly determines the quality and performance of the chip, but also largely depends on the technological sophistication of the deposition process. However, the technical barriers to thin film deposition processes and equipment remain high. This stems from the diverse performance requirements of thin film deposition for different modules in chip integration, as well as the continuous emergence of new materials and device structures, which necessitate new processes and equipment. In chip manufacturing, as transistor dimensions continue to decrease, the gate oxide thickness must be continuously reduced to maintain sufficient gate capacitance and gate control capability. However, when the physical thickness of the gate oxide is reduced to a certain level, device leakage current increases significantly, severely impacting chip performance and stability. Therefore, replacing traditional SiO2 with high-k dielectric materials has become an effective solution. High-k materials maintain a relatively large gate dielectric thickness while the equivalent gate oxide thickness continues to decrease, effectively reducing gate dielectric leakage current and improving chip performance and stability.

[0003] Currently, commonly used high-k materials include oxides of elements such as Ti, Hf, Zr, and Ta, as well as materials such as titanates doped with alkaline earth metals. For example, lead titanate-based materials, such as PbZrxTi1-xO3, have very large bulk dielectric constants, typically ranging from several hundred to several thousand, and are used as capacitor dielectrics in dynamic random access memory (DRAM). Barium titanate-based materials, such as BaxSr1-xTiO3, also have high dielectric constants and are suitable for similar electronic devices. Hafnium-based oxide materials, such as HfO2 / HfSiO / HfSiON, also have very high dielectric constants and are among the most commonly used high-k materials. These materials are typically deposited using advanced deposition techniques, such as atomic layer deposition (ALD) or chemical vapor deposition (CVD), to achieve high-quality, high-precision thin films. High-quality precursor materials are crucial for achieving high-k thin film deposition and are crucial for improving chip performance and stability. Therefore, the technical level of thin film deposition processes and equipment, as well as the selection of high-quality precursor materials, are crucial in chip manufacturing.

[0004] Conventional source materials used to form thin films containing Group IV metal elements using chemical vapor deposition (CVD) or atomic layer deposition (ALD) techniques include tetrakis(dimethylamino)hafnium, tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, tetrakis(methylethylamino)hafnium, and cyclopentadienyltris(dimethylamino)zirconium. Although thin films containing Group III, IV, and V metal elements have been produced, the uniformity of these films still needs to be improved, especially when processing substrates with concave-convex structures (such as grooves) or porous structures.

[0005] Therefore, in order to meet the above requirements, it is urgent to develop compounds of group III, IV and V metal elements as precursors, which must have the ability to form uniform thin films on complex substrate surfaces. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing a metal complex to solve the above-mentioned deficiencies in the prior art.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] A method for preparing a metal complex, wherein the general structural formula of the metal complex is R1C5H4M(NR2R3)3, wherein R1 is i Pr, n Pr, Me or Et; R2 and R3 are Me or Et; M is Ti, Zr or Hf.

[0009] The steps are as follows:

[0010] S1: Under inert gas protection, add potassium tert-butoxide and tetrahydrofuran solvent to a reaction cylinder, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly add the substituted cyclopentadiene monomer dropwise, and continue stirring for 2 hours after the addition is completed to obtain a substituted cyclopentadiene potassium solution;

[0011] S2: Add metal chloride MCl4 and tetrahydrofuran solvent to another reaction tube, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly add the substituted cyclopentadienyl potassium solution dropwise, and after the addition is completed, slowly raise the temperature to 30~40℃ and stir for 8h;

[0012] S3: Re-control the temperature at -20~0℃, then slowly add the amino compound. After the addition is complete, slowly raise the temperature to 30~40℃ and stir to react for 8 hours. After the reaction is completed, filter and rinse with tetrahydrofuran to obtain a filtrate, and finally separate by distillation to obtain a substituted cyclopentadienyl tris(dialkylamino) metal complex.

[0013] Furthermore, steps S1, S2 and S3 are all carried out under the protection of an inert gas, and the water and oxygen content of the inert gas is less than 1 ppm.

[0014] Furthermore, in step S1, the molar ratio of potassium tert-butoxide to the substituted cyclopentadiene monomer is 1.05:1 to 1.2:1.

[0015] Furthermore, in step S2, the molar ratio of the Group IVB metal chloride to the substituted cyclopentadiene is 1.02:1 to 1.1:1.

[0016] Furthermore, the molar ratio of the amino compound in step S3 to the substituted cyclopentadiene in step S1 is 6.3:1 to 7.8:1.

[0017] Furthermore, the target product in step S3 is sampled and analyzed: the product is subjected to nuclear magnetic resonance testing and ICP testing.

[0018] In the above technical solution, the preparation method of the metal complex provided by the present invention has the beneficial effects of:

[0019] This case provides a method for synthesizing high-purity metal complex precursors, which not only has good chemical stability, a mild reaction process, and high safety, but also is simple to operate and subsequent separation and purification are relatively simple, and the operation is relatively safe; the prepared compound will be able to uniformly deposit a film or thin film containing Group III, IV, and V metal elements on the entire surface of an uneven or porous substrate, thereby significantly improving the uniformity and overall performance of the film.

[0020] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.

[0021] This application document provides an overview of various implementations or examples of the technology described in this disclosure, and is not a comprehensive disclosure of the full scope or all features of the disclosed technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments described in the present invention. For ordinary technicians in this field, other drawings can also be obtained based on these drawings.

[0023] Figure 1 This is the nuclear magnetic resonance detection result of n-propylcyclopentadienyltris(dimethylamino)zirconium in Example 3 of the present invention.

[0024] Figure 2 This is the ICP detection data diagram of n-propylcyclopentadienyltris(dimethylamino)zirconium in Example 3 of the present invention.

[0025] Description of reference numerals:

[0026] IPZ-235, n-propylcyclopentadienyl tris(dimethylamino)zirconium. DETAILED DESCRIPTION

[0027] To make the purpose, technical solutions, and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below in conjunction with the accompanying drawings of the embodiments of the present disclosure. Obviously, the described embodiments are part of the embodiments of the present disclosure, not all of the embodiments. Based on the described embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present disclosure.

[0028] Please see the attached Figure 1-2 The present invention provides a method for preparing a metal complex, wherein the general structural formula of the metal complex is R1C5H4M(NR2R3)3, wherein R1 is i Pr, n Pr, Me or Et; R2 and R3 are Me or Et; M is Ti, Zr or Hf; wherein the Ti-containing compound is [ i PrCpTi(NMe2)3]、[ i PrCpTi(NEt2)3 ]、[ i PrCpTi(NEtMe)3]、[ n PrCpTi(NMe2)3]、[ n PrCpTi(NEt2)3 ]、[ n PrCpTi(NEtMe)3], [MeCpTi(NMe2)3], [MeCpTi(NEt2)3], [MeCpTi(NEtMe)3], [EtCpTi(NMe2)3], [EtCpTi(NEt2)3], [EtCpTi(NEtMe)3];

[0029] The Zr-containing compound is [ i PrCpZr(NMe2)3]、[ i PrCpZr(NEt2)3 ]、[ i PrCpZr(NEtMe)3]、[ n PrCpZr(NMe2)3]、[ n PrCpZr(NEt2)3 ]、[ n PrCpZr(NEtMe)3], [MeCpZr(NMe2)3], [MeCpZr(NEt2)3], [MeCpZr(NEtMe)3], [EtCpZr(NMe2)3], [EtCpZr(NEt2)3], [EtCpZr(NEtMe)3];

[0030] wherein the Hf-containing compound is [ i PrCpHf(NMe2)3]、[ i PrCpHf(NEt2)3]、[ i PrCpHf(NEtMe)3]、[ n PrCpHf(NMe2)3]、[ n PrCpHf(NEt2)3]、[ n PrCpHf(NEtMe)3], [MeCpHf(NMe2)3], [MeCpHf(NEt2)3], [MeCpHf(NEtMe)3], [EtCpHf(NMe2)3], [EtCpHf(NEt2)3], [EtCpHf(NEtMe)3];

[0031] The reaction principle is as follows:

[0032] R1C5H5+(CH3)3COK→R1C5H4K+(CH3)3COH

[0033] R1C5H4K+MCl4→R1C5H4MCl3+KCl

[0034] R1C5H4MCl3+6R2R3NH→R1C5H4M(NR2R3)3+3R2R3NH2Cl;

[0035] Example 1. The purpose of this example is to synthesize isopropylcyclopentadienyl tris(diethylamino)titanium [ i PrCpTi(NEt2)3].

[0036] 1. Under inert gas protection, add 117.8g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, and slowly add 108g of isopropylcyclopentadiene monomer dropwise. After the addition is completed, continue stirring for 2h to obtain a potassium isopropylcyclopentadiene solution;

[0037] 2. Add 193.5g of titanium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, slowly add potassium isopropylcyclopentadienyl solution dropwise, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed;

[0038] 3. Re-control the temperature at -20~0°C, then slowly add 460.5g of diethylamine dropwise. After the addition is complete, slowly raise the temperature to 30~40°C and stir to react for 8h. After the reaction is complete, filter and rinse with tetrahydrofuran to obtain the filtrate, and finally separate by distillation to obtain 305.3g of the target product;

[0039] In this case, the synthesis yield of isopropylcyclopentadienyltris(diethylamino)titanium was 82.3%.

[0040] Example 2, the purpose of this example is to synthesize n-propylcyclopentadienyl tris (dimethylamino) zirconium [ n PrCpZr(NMe2)3].

[0041] 1. Under inert gas protection, add 123.4g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, and slowly add 108g of n-propylcyclopentadiene monomer dropwise. After the addition is completed, continue stirring for 2h to obtain a potassium n-propylcyclopentadiene solution;

[0042] 2. Add 244.6g of zirconium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, slowly add potassium n-propylcyclopentadienyl solution dropwise, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed;

[0043] 3. Re-control the temperature at -20~0°C, then slowly introduce 297g of dimethylamine. After the addition is complete, slowly raise the temperature to 30~40°C and stir to react for 8h. After the reaction is completed, filter and rinse with tetrahydrofuran to obtain the filtrate, and finally separate by distillation to obtain 293.4g of the target product;

[0044] In this case, the synthesis yield of n-propylcyclopentadienyltris(dimethylamino)zirconium was 88.9%, and the product was confirmed to be the target product by a JNM-ECZ400S nuclear magnetic resonance spectrometer.

[0045] Example 3, the purpose of this example is to synthesize n-propylcyclopentadienyl tris (dimethylamino) zirconium [ n PrCpZr(NMe2)3].

[0046] 1. Under inert gas protection, add 134.6g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, and slowly add 108g of n-propylcyclopentadiene monomer dropwise. After the addition is completed, continue stirring for 2h to obtain a potassium n-propylcyclopentadiene solution;

[0047] 2. Add 256.3g of zirconium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, slowly add potassium n-propylcyclopentadienyl solution dropwise, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed;

[0048] 3. Re-control the temperature at -20~0°C, then slowly introduce 324g of dimethylamine. After the addition is complete, slowly raise the temperature to 30~40°C and stir to react for 8h. After the reaction is completed, filter and rinse with tetrahydrofuran to obtain the filtrate, and finally separate by distillation to obtain 294g of the target product;

[0049] In this case, the synthesis yield of n-propylcyclopentadienyltris(dimethylamino)zirconium was 89%, and the product was confirmed to be the target product by JNM-ECZ400S nuclear magnetic resonance spectrometer.

[0050] Figure 2 Among them, IPZ-235 is n-propylcyclopentadienyl tris(dimethylamino)zirconium in this embodiment.

[0051] Example 4. The purpose of this example is to synthesize n-propylcyclopentadienyltris(dimethylamino)hafnium[ n PrCpTi(NMe2)3].

[0052] 1. Under inert gas protection, add 134.6g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, and slowly add 108g of n-propylcyclopentadiene monomer dropwise. After the addition is completed, continue stirring for 2h to obtain a potassium n-propylcyclopentadiene solution;

[0053] 2. Add 352.3g of hafnium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, slowly add potassium n-propylcyclopentadienyl solution dropwise, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed;

[0054] 3. Re-control the temperature at -20~0°C, then slowly introduce 297g of dimethylamine. After the addition is complete, slowly raise the temperature to 30~40°C and stir to react for 8h. After the reaction is completed, filter and rinse with tetrahydrofuran to obtain the filtrate, and finally separate by distillation to obtain 361.8g of the target product;

[0055] In this case, the synthesis yield of n-propylcyclopentadienyltris(dimethylamino)hafnium was 86.6%.

[0056] Example 5. The purpose of this example is to synthesize n-propylcyclopentadienyltri(methylethylamine)hafnium[ n PrCpHf(NMeEt)3].

[0057] 1. Under inert gas protection, add 123.4g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, and slowly add 108g of n-propylcyclopentadiene monomer dropwise. After the addition is completed, continue stirring for 2h to obtain a potassium n-propylcyclopentadiene solution;

[0058] 2. Add 336.3g of hafnium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked flask, start stirring, control the temperature of the reaction flask at -20~0℃, slowly add potassium n-propylcyclopentadienyl solution dropwise, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed;

[0059] 3. Re-control the temperature at -20~0℃, then slowly introduce 371.7g of methylethylamine. After the addition is complete, slowly raise the temperature to 30~40℃ and stir to react for 8h. After the reaction is completed, filter and rinse with tetrahydrofuran to obtain the filtrate, and finally separate by distillation to obtain 391.8g of the target product;

[0060] In this case, the synthesis yield of n-propylcyclopentadienyltri(methylethylamine)hafnium was 84.7%.

[0061] The above description is merely illustrative of certain exemplary embodiments of the present invention. It goes without saying that those skilled in the art will be able to modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and description are illustrative in nature and should not be construed as limiting the scope of protection of the claims.

Claims

1. A method for preparing a metal complex, characterized in that: The general structural formula of the metal complex to be prepared is R1C5H4M(NR2R3)3, where R1 is i Pr, n Pr, Me or Et; R2 and R3 are Me or Et; M is Ti, Zr or Hf; The steps are as follows: S1: Under inert gas protection, add potassium tert-butoxide and tetrahydrofuran solvent to a reaction cylinder, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly add the substituted cyclopentadiene monomer dropwise, and continue stirring for 2 hours after the addition is completed to obtain a substituted cyclopentadiene potassium solution; S2: Add metal chloride MCl4 and tetrahydrofuran solvent to another reaction tube, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly add the substituted cyclopentadienyl potassium solution dropwise, and after the addition is completed, slowly raise the temperature to 30~40℃ and stir for 8h; S3: Re-control the temperature at -20~0°C, then slowly add the amino compound. After the addition is complete, slowly raise the temperature to 30~40°C, stir and react for 8 hours. After the reaction is complete, filter and rinse with tetrahydrofuran to obtain a filtrate, and finally separate by distillation to obtain a substituted cyclopentadienyl tris(dialkylamino) metal complex; In step S1, the molar ratio of potassium tert-butoxide to the substituted cyclopentadiene monomer is 1.05:1 to 1.2:1; In step S2, the molar ratio of metal chloride MCl4 to substituted cyclopentadiene is 1.02:1 to 1.1:1; The molar ratio of the amino compound in step S3 to the substituted cyclopentadiene in step S1 is 6.3:1 to 7.8:

1.

2. The method for preparing a metal complex according to claim 1, wherein Steps S1, S2 and S3 are all carried out under the protection of an inert gas, and the water and oxygen content of the inert gas is less than 1 ppm.

3. The method for preparing a metal complex according to claim 2, wherein: The target product in step S3 is sampled and analyzed: the product is subjected to nuclear magnetic resonance testing and ICP testing.

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