Preparation method of metal complex

Abstract

The invention relates to the technical field of metal organic source synthesis, and particularly discloses a preparation method of a metal complex, the general structural formula of the metal complex to be prepared is R1C5H4M (NR2R3) 3, and R1 is iPr, nPr, Me or Et; r2 and R3 are Me or Et; m is Ti, Zr or Hf; according to the synthesis method of the high-purity metal complex precursor, the chemical stability is better, the reaction process is mild, the safety is high, the operation is simple, the subsequent separation and purification are simpler, and the operation is relatively safe; the prepared compound can be applied to the surface of a whole substrate with uneven or porous characteristics, and films or thin films containing III, IV and V group metal elements can be uniformly deposited, so that the uniformity and the overall performance of the thin films are remarkably improved.

Description

Technical Field

[0001] The 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 precise process, the core of which is to accurately transfer the designed circuit pattern to the thin film, and 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 depends to a large extent on the technical level of the deposition process. However, there are high technical barriers in the field of thin film deposition technology and equipment. This is due to the diverse performance requirements of thin film deposition for different modules of chip integration, and the continuous emergence of new materials and new device structures. The continuous demand for new processes and new equipment. In chip manufacturing, as the size of transistors continues to decrease, in order to maintain sufficient gate capacitance to ensure gate control capability, the thickness of the gate oxide layer needs to be continuously thinned. However, when the physical thickness of the gate oxide layer is thinned to a certain extent, the leakage current of the device will increase significantly, seriously affecting the performance and stability of the chip. Therefore, high dielectric constant (High-K) materials are used to replace traditional SiO 2 It has become an effective solution. High-K materials can keep the physical thickness of the gate dielectric relatively large while the equivalent gate oxide thickness continues to shrink, thereby effectively reducing the leakage current of the gate dielectric and improving the performance and stability of the chip.

[0003] At present, commonly used High-K materials include oxides of elements such as Ti, Hf, Zr, Ta, and materials such as titanates doped with alkaline earth metals. For example: lead titanate materials: such as PbZrxTi1-xO 3 Its bulk material has a very large dielectric constant, generally in the hundreds to thousands, and can be used as a capacitor medium for dynamic random access memory (DRAM); barium titanate-based materials BaxSr1-xTiO 3 , also has a high dielectric constant and is suitable for similar electronic devices; hafnium-based oxide materials, HfO 2 / HfSiO / HfSiON: It has a very high dielectric constant and is one of the commonly used high-K materials. These materials are usually deposited with high quality and high precision through advanced deposition techniques such as atomic layer deposition (ALD) or chemical vapor deposition (CVD). High-quality precursor materials are the key support for achieving High-K thin film deposition and are of great significance for improving the performance and stability of chips. Therefore, in chip manufacturing, the technical level of thin film deposition process and equipment and the selection of high-quality precursor materials are crucial.

[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, cyclopentadienyltri(dimethylamino)zirconium, etc. Although thin films containing Group III, IV and V metal elements have been prepared, 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, and these compounds must have the ability to form uniform thin films on the surfaces of complex substrates. 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: A method for preparing a metal complex, wherein the general structural formula of the metal complex is R 1 C 5 H 4 M(NR 2 R 3 ) 3 , where R 1 for i Pr, n Pr, Me or Et; R 2 and R 3 is Me or Et; M is Ti, Zr or Hf.

[0008] The steps are as follows: S1: Under the protection of inert gas, add potassium tert-butoxide and tetrahydrofuran solvent into the reaction cylinder, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly dropwise add the substituted cyclopentadiene monomer, and continue stirring for 2h after the dropwise addition to obtain a substituted cyclopentadiene potassium solution; S2: Add metal chloride MCl to another reaction tube. 4 and tetrahydrofuran solvent into the reaction cylinder, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly drop the substituted cyclopentadienyl potassium solution, and after the dropwise addition, slowly raise the temperature to 30~40℃ and stir for 8h; S3: Re-control the temperature at -20~0℃, then slowly add the amino compound. After the addition is completed, 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 the filtrate, and finally separate by distillation to obtain the substituted cyclopentadienyl tris(dialkylamino) metal complex.

[0009] 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.

[0010] Furthermore, in step S1, the molar ratio of potassium tert-butoxide to the substituted cyclopentadiene monomer is 1.05:1 to 1.2:1.

[0011] 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.

[0012] 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.

[0013] Furthermore, the target product in step S3 is sampled and analyzed: the product is subjected to nuclear magnetic resonance testing and ICP testing.

[0014] In the above technical scheme, the preparation method of the metal complex provided by the present invention has the beneficial effects of: 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 relatively safe to operate; the prepared compound will be committed to uniformly depositing a film or thin film containing metal elements of Groups III, IV and V on the entire surface of a substrate with uneven or porous characteristics, thereby significantly improving the uniformity and overall performance of the film.

[0015] 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.

[0016] This application document provides an overview of various implementations or examples of the technology described in the present disclosure, and is not a comprehensive disclosure of the entire scope or all features of the disclosed technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can also be obtained based on these drawings.

[0018] Figure 1 This is the nuclear magnetic resonance detection result of n-propylcyclopentadienyltri(dimethylamino)zirconium in Example 3 of the present invention.

[0019] Figure 2 This is an ICP detection data diagram of n-propylcyclopentadienyltri(dimethylamino)zirconium in Example 3 of the present invention.

[0020] Description of reference numerals: IPZ-235, n-propylcyclopentadienyltri(dimethylamino)zirconium. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solution and advantages of the embodiments of the present disclosure clearer, the technical solution of the embodiments of the present disclosure will be clearly and completely described below in conjunction with the 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.

[0022] Please see 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 R 1 C 5 H 4 M(NR 2 R 3 ) 3 , where R 1 for i Pr, n Pr, Me or Et; R 2 and R 3 is Me or Et; M is Ti, Zr or Hf; wherein the Ti-containing compound is [ i PrCpTi(NMe 2 ) 3 ]、[ i PrCpTi(NEt 2 ) 3 ]、[ i PrCpTi(NEtMe) 3 ]、[ n PrCpTi(NMe 2 ) 3 ]、[ n PrCpTi(NEt 2 ) 3 ]、[ n PrCpTi(NEtMe) 3 ]、[MeCpTi(NMe 2 ) 3 ]、[MeCpTi(NEt 2 ) 3 ]、[MeCpTi(NEtMe) 3 ]、[EtCpTi(NMe 2 ) 3 ]、[EtCpTi(NEt2 ) 3 ]、[EtCpTi(NEtMe) 3 ]; The Zr-containing compound is [ i PrCpZr(NMe 2 ) 3 ]、[ i PrCpZr(NEt 2 ) 3 ]、[ i PrCpZr(NEtMe) 3 ]、[ n PrCpZr(NMe 2 ) 3 ]、[ n PrCpZr(NEt 2 ) 3 ]、[ n PrCpZr(NEtMe) 3 ]、[MeCpZr(NMe 2 ) 3 ]、[MeCpZr(NEt 2 ) 3 ]、[MeCpZr(NEtMe) 3 ]、[EtCpZr(NMe 2 ) 3 ]、[EtCpZr(NEt 2 ) 3 ]、[EtCpZr(NEtMe) 3 ]; The Hf-containing compound is [ i PrCpHf(NMe 2 ) 3 ]、[ i PrCpHf(NEt 2 ) 3 ]、[ i PrCpHf(NEtMe) 3 ]、[ n PrCpHf(NMe 2 ) 3 ]、[ n PrCpHf(NEt 2 ) 3 ]、[ n PrCpHf(NEtMe) 3 ]、[MeCpHf(NMe 2 ) 3 ]、[MeCpHf(NEt 2 ) 3]、[MeCpHf(NEtMe) 3 ]、[EtCpHf(NMe 2 ) 3 ]、[EtCpHf(NEt 2 ) 3 ]、[EtCpHf(NEtMe) 3 ]; The reaction principle is as follows: R 1 C 5 H 5 +(CH 3 ) 3 COK → R 1 C 5 H 4 K+(CH 3 ) 3 COH R 1 C 5 H 4 K+MCl 4 →R 1 C 5 H 4 MCl 3 +KCl R 1 C 5 H 4 MCl 3 +6R 2 R 3 NH→R 1 C 5 H 4 M(NR 2 R 3 ) 3 +3R 2 R 3 NH 2 Cl; Example 1, the purpose of this example is to synthesize isopropylcyclopentadienyl tris (diethylamino) titanium [ i PrCpTi(NEt 2 ) 3 ].

[0023] 1. Under the protection of inert gas, add 117.8g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly drop 108g of isopropylcyclopentadiene monomer, and continue stirring for 2h after the addition to obtain a potassium isopropylcyclopentadiene solution; 2. Add 193.5g of titanium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly drop the isopropylcyclopentadienyl potassium solution, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed; 3. Re-control the temperature at -20~0℃, then slowly drop 460.5g of diethylamine, and after the dropwise addition is completed, 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 305.3g of the target product; In this case, the synthesis yield of isopropylcyclopentadienyltri(diethylamino)titanium is 82.3%.

[0024] Example 2, the purpose of this example is to synthesize n-propylcyclopentadienyl tris(dimethylamino)zirconium [ n PrCpZr(NMe 2 ) 3 ].

[0025] 1. Under the protection of inert gas, add 123.4g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly drop 108g of n-propylcyclopentadiene monomer, and continue stirring for 2h after the addition to obtain a potassium n-propylcyclopentadiene solution; 2. Add 244.6g zirconium tetrachloride and 0.5L tetrahydrofuran solvent to a 3L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly drop the potassium n-propylcyclopentadienyl solution, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed; 3. Re-control the temperature at -20~0℃, then slowly introduce 297g of dimethylamine. 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 293.4g of the target product; In this case, the synthesis yield of n-propylcyclopentadienyltris(dimethylamino)zirconium was 88.9%, and the product was confirmed as the target product by JNM-ECZ400S nuclear magnetic resonance spectrometer.

[0026] Example 3, the purpose of this example is to synthesize n-propylcyclopentadienyl tris(dimethylamino)zirconium [ n PrCpZr(NMe 2 ) 3 ].

[0027] 1. Under the protection of inert gas, add 134.6g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly drop 108g of n-propylcyclopentadiene monomer, and continue stirring for 2h after the addition to obtain a potassium n-propylcyclopentadiene solution; 2. Add 256.3g zirconium tetrachloride and 0.5L tetrahydrofuran solvent to a 3L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly drop the potassium n-propylcyclopentadienyl solution, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed; 3. Re-control the temperature at -20~0℃, then slowly introduce 324g of dimethylamine. 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 294g of the target product; In this case, the synthesis yield of n-propylcyclopentadienyltris(dimethylamino)zirconium was 89%, and the product was confirmed as the target product by JNM-ECZ400S nuclear magnetic resonance spectrometer.

[0028] Figure 2 In the example, IPZ-235 is n-propylcyclopentadienyltris(dimethylamino)zirconium of this embodiment.

[0029] Example 4, the purpose of this example is to synthesize n-propylcyclopentadienyltris(dimethylamino)hafnium[ n PrCpTi(NMe 2 ) 3 ].

[0030] 1. Under the protection of inert gas, add 134.6g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly drop 108g of n-propylcyclopentadiene monomer, and continue stirring for 2h after the addition to obtain a potassium n-propylcyclopentadiene solution; 2. Add 352.3g of hafnium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly drop the potassium n-propylcyclopentadienyl solution, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed; 3. Re-control the temperature at -20~0℃, then slowly introduce 297g of dimethylamine. 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 361.8g of the target product; In this case, the synthesis yield of n-propylcyclopentadienyltri(dimethylamino)hafnium was 86.6%.

[0031] Example 5. The purpose of this example is to synthesize n-propylcyclopentadienyltri(methylethylamine)hafnium[ n PrCpHf(NMeEt) 3 ].

[0032] 1. Under the protection of inert gas, add 123.4g of potassium tert-butoxide and 1L of tetrahydrofuran solvent to a 2L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly drop 108g of n-propylcyclopentadiene monomer, and continue stirring for 2h after the addition to obtain a potassium n-propylcyclopentadiene solution; 2. Add 336.3g of hafnium tetrachloride and 0.5L of tetrahydrofuran solvent to a 3L four-necked bottle, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly drop the potassium solution of n-propylcyclopentadienyl, and slowly raise the temperature to 30~40℃ and stir for 8h after the addition is completed; 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; In this case, the synthesis yield of n-propylcyclopentadienyltri(methylethylamine)hafnium is 84.7%.

[0033] The above description is only by way of illustration of certain exemplary embodiments of the present invention. It is undoubted that those skilled in the art can modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and descriptions are illustrative in nature and should not be construed as limiting the scope of protection of the claims of the present invention.

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 the protection of inert gas, add potassium tert-butoxide and tetrahydrofuran solvent into the reaction cylinder, start stirring, control the temperature of the reaction bottle at -20~0°C, slowly dropwise add the substituted cyclopentadiene monomer, and continue stirring for 2h after the dropwise addition to obtain a substituted cyclopentadiene potassium solution; S2: Add metal chloride MCl4 and tetrahydrofuran solvent to another reaction cylinder, start stirring, control the temperature of the reaction bottle at -20~0℃, slowly drop the substituted cyclopentadienyl potassium solution, 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℃, then slowly add the amino compound. After the addition is completed, 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 the filtrate, and finally separate by distillation to obtain the substituted cyclopentadienyl tris(dialkylamino) metal complex.

2. The method for preparing a metal complex according to claim 1, characterized in that: The 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, characterized in that: In the step S1, the molar ratio of potassium tert-butoxide to the substituted cyclopentadiene monomer is 1.05:1 to 1.2:

1.

4. The method for preparing a metal complex according to claim 3, characterized in that: In the step S2, the molar ratio of the metal chloride MCl4 to the substituted cyclopentadiene is 1.02:1 to 1.1:

1.

5. The method for preparing a metal complex according to claim 4, characterized in that: 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.

6. The method for preparing a metal complex according to claim 5, characterized in that: The target product sampling and analysis in step S3: the product is subjected to nuclear magnetic resonance testing and ICP testing.

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