CN114773403A - Synthesis method of tri (dialkylamino) cyclopentadienyl metal complex - Google Patents
Synthesis method of tri (dialkylamino) cyclopentadienyl metal complex Download PDFInfo
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- -1 cyclopentadienyl metal complex Chemical class 0.000 title claims abstract description 38
- 125000004663 dialkyl amino group Chemical group 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000007983 Tris buffer Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229940125782 compound 2 Drugs 0.000 claims abstract description 14
- 229940126214 compound 3 Drugs 0.000 claims abstract description 14
- 229940125904 compound 1 Drugs 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 20
- 230000002194 synthesizing effect Effects 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 11
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002243 precursor Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- STHAQIJXOMGURG-UHFFFAOYSA-N cyclopenta-1,3-diene;dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C=1C=C[CH-]C=1 STHAQIJXOMGURG-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- 238000000231 atomic layer deposition Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- DWCMDRNGBIZOQL-UHFFFAOYSA-N dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C DWCMDRNGBIZOQL-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DCPPOHMFYUOVGH-UHFFFAOYSA-N CN(C)[Zr](C1C=CC=C1)(N(C)C)N(C)C Chemical compound CN(C)[Zr](C1C=CC=C1)(N(C)C)N(C)C DCPPOHMFYUOVGH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 2
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 2
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 2
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- KBBKHMIEEMSXSM-JVXZTZIISA-N 6-{[(4R,5R)-4-(hydroxymethyl)thymin-5-yl]methyl}thymine Chemical compound N1C(=O)NC(=O)C(C)=C1C[C@@]1(C)C(=O)NC(=O)N[C@H]1CO KBBKHMIEEMSXSM-JVXZTZIISA-N 0.000 description 1
- PLPSXDNKVPYVEG-UHFFFAOYSA-N C(C)N(CC)[Zr](C1C=CC=C1)(N(CC)CC)N(CC)CC Chemical compound C(C)N(CC)[Zr](C1C=CC=C1)(N(CC)CC)N(CC)CC PLPSXDNKVPYVEG-UHFFFAOYSA-N 0.000 description 1
- JIGXARPLYFNBCG-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C Chemical compound C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C JIGXARPLYFNBCG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SJZKDQIEKKDKQA-UHFFFAOYSA-N hexane;n-methylmethanamine Chemical compound CNC.CCCCCC SJZKDQIEKKDKQA-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- BTGDVSGAIXBEDP-UHFFFAOYSA-N n-methyl-n-trimethylsilylethanamine Chemical compound CCN(C)[Si](C)(C)C BTGDVSGAIXBEDP-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of a tri (dialkylamino) cyclopentadienyl metal complex, which comprises the following steps: (1) reacting Compound 1 with MCl4Carrying out a reaction to prepare a compound 2; (2) reacting compound 2 with HNR1R2Carrying out a reaction to prepare a compound 3; (3) the tris (dialkylamino) cyclopentadienyl metal complex is prepared by reacting compound 3 with compound 4. According to the synthesis method, through reasonably setting each reaction step, the synthesis yield can be effectively improved, the raw materials are safe and easy to obtain, butyl lithium is avoided, the safety coefficient of the reaction is greatly improved, impurity metal is avoided from being introduced into the reaction, the purification of the product is facilitated, and the requirement of the semiconductor industry on the purity of the precursor source can be met. Meanwhile, the method is simple to operate, does not need to separate the intermediate, is environment-friendly in route, and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of a tri (dialkylamino) cyclopentadienyl metal complex.
Background
With the development of the very large scale integrated circuit industry, more stringent requirements are put on the properties of semiconductor materials and the preparation process thereof. According to moore's law, integrated circuit technology is continuously developed along with the reduction of the size of a single electronic device, and the thickness of a gate dielectric layer is one of the determining factors influencing the size of the electronic device. SiO is commonly used in the integrated circuit electronic industry at present2Gate as an electronic deviceDielectric materials, but as device feature sizes decrease, conventional SiO2The thickness of the gate dielectric material is close to the physical thickness of the material, so that the power consumption of the device is greatly increased, and the stability requirement of the device in the microelectronic industry is difficult to meet. Search for high dielectric constant material (high-K material) to replace traditional SiO2The gate dielectric layer reduces the tunneling effect by increasing the physical thickness of the dielectric layer, and is an effective technical means for improving the stability of the electronic device.
ZrO2The film has moderate dielectric constant (K-25), has excellent characteristics compatible with the traditional silicon-based integrated circuit process, and is regarded as a novel gate dielectric material with the greatest development prospect. Oxide films are typically obtained using CVD or ALD techniques by first introducing a precursor in the gas phase, followed by a chemical reaction of the precursor at the wafer surface. To be successfully used in production, the ideal precursor must have sufficient reactivity and stability to ensure safe operation, and suitable vapor pressure, while also being pure to ensure that the resulting film does not cause device problems (current leakage, threshold voltage drift, etc.).
The tris (dimethylamino) cyclopentadienyl zirconium is liquid at normal temperature, has better stability and higher vapor pressure, and shows quite high reactivity, so the physicochemical characteristics of the tris (dimethylamino) cyclopentadienyl zirconium can be used for preparing zirconium oxide films by CVD or ALD technology.
The traditional method for preparing tris (dimethylamino) cyclopentadienyl zirconium is as follows: butyl lithium and dimethylamine are firstly used for reaction to prepare dimethylamino lithium, then the dimethylamino lithium is reacted with zirconium tetrachloride to prepare tetra (dimethylamino) zirconium, and finally the tetra (dimethylamino) zirconium is reacted with cyclopentadiene to obtain the tri (dimethylamino) cyclopentadienyl zirconium. The yield of this process is low, only 74% at the maximum. In addition, the raw materials of the traditional method are fed by a one-pot method without separation of intermediates, and are directly desolventized without being filtered after the reaction is finished, and then products are distilled, so that the contact between the intermediate products and air is reduced, the post-treatment process is simplified, and the production efficiency is improved. But the yield of the method is greatly reduced by 35% compared with the traditional method, and simultaneously, the container is difficult to clean after the reaction is finished, and the labor cost is increased. In addition, another method relates to a method for producing pentamethylcyclopentadienyltris (dimethylamino) zirconium, which comprises reacting butyllithium with dimethylamine to produce dimethylaminolithium, and then reacting the dimethylaminolithium with pentamethylcyclopentadienyltris (dimethylamino) zirconium chloride to produce pentamethylcyclopentadienyltris (dimethylamino) zirconium. The yield of the preparation process was 83%.
In the method, highly flammable raw materials of butyl lithium are inevitably used, or flammable intermediates such as dimethyl amino lithium, tetra (dimethyl amino) zirconium and the like are needed, so that potential safety hazards exist, and butyl lithium products are generally diluted in alkane solvents, so that a large amount of waste liquid is generated in the using process, and the industrial production amplification of the tri (dimethyl amino) cyclopentadienyl zirconium is limited. Meanwhile, the yield of the preparation method needs to be further improved.
Disclosure of Invention
Based on the method, the synthesis method of the tris (dialkylamino) cyclopentadienyl metal complex is high in yield, high in production safety and environment-friendly.
The specific technical scheme is as follows:
a method for synthesizing a tri (dialkylamino) cyclopentadienyl metal complex comprises the following steps:
(1) reacting Compound 1 with MCl4Carrying out a reaction to prepare a compound 2;
(2) reacting compound 2 with HNR1R2Carrying out a reaction to prepare a compound 3;
(3) reacting a compound 3 with a compound 4 to prepare the tris (dialkylamino) cyclopentadienyl metal complex;
wherein, the structural formula of the compound 1 is as follows:
the structural formula of compound 2 is as follows:
the structural formula of compound 3 is as follows:
the structural formula of compound 4 is as follows:
m is Zr or Hf;
R1、R2each independently selected from: C1-C5 alkyl;
R3each occurrence is independently selected from: h or C1-C5 alkyl; n is 0, 1, 2, 3, 4 or 5.
In one embodiment, R3Is H or methyl.
In one embodiment, R1、R2Each independently selected from: methyl or ethyl.
In one embodiment, MCl4The molar ratio of the compound to the compound 1 is 1 (1-4).
In one embodiment, MCl4With HNR1R2The molar ratio of (1) to (6).
In one embodiment, MCl4The molar ratio of the compound to the compound 4 is 1 (1-3).
In one embodiment, in the step (1), the reaction temperature is room temperature, and the reaction time is 10-15 h.
In one embodiment, in step (2), the step of reacting comprises:
adding HNR into the compound 2 at the temperature of-10 ℃ to 0 DEG C1R2And after the addition is finished, reacting for 2-5 h under the reflux condition.
In one embodiment, in step (3), the step of reacting comprises:
adding the compound 4 into the compound 3 at the temperature of-10-0 ℃, and reacting for 10-15 h at room temperature after the addition is finished.
In one embodiment, the reaction solution obtained by the reaction in the step (1) is directly subjected to the step (2) without post-treatment; and/or the presence of a catalyst in the reaction mixture,
concentrating the reaction liquid obtained in the step (2) under reduced pressure, and directly performing the step (3); and/or the like, and/or,
and (4) filtering the reaction liquid obtained in the step (3), concentrating and distilling under reduced pressure to prepare the tri (dialkylamino) cyclopentadienyl metal complex.
According to the method for synthesizing the tri (dialkylamino) cyclopentadienyl metal complex, the reaction steps are reasonably arranged, the synthesis yield can be effectively improved, the raw materials are safe and easy to obtain, butyl lithium is avoided, the safety coefficient of the reaction is greatly improved, impurity metal is avoided being introduced in the reaction, the product is convenient to purify, and the requirement of the semiconductor industry on the purity of the precursor source can be met. Meanwhile, the method is simple to operate, does not need to separate the intermediate, is green and environment-friendly in route, and is suitable for industrial large-scale production.
Detailed Description
The method for synthesizing the tris (dialkylamino) cyclopentadienyl metal complex of the present invention will be described in further detail with reference to the following specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or", "and/or" includes any and all combinations of two or more of the associated listed items, including any two or any more of the associated listed items, or all of the associated listed items.
In the present invention, the technical features described in the open type include a closed technical solution including the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the added component in the system after the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The room temperature in the present invention is generally 4 ℃ to 30 ℃, preferably 20. + -. 5 ℃.
The invention provides a method for synthesizing a tri (dialkylamino) cyclopentadienyl metal complex, which comprises the following steps:
(1) reacting Compound 1 with MCl4Carrying out a reaction to prepare a compound 2;
(2) reacting compound 2 with HNR1R2Carrying out a reaction to prepare a compound 3;
(3) reacting compound 3 with compound 4 to prepare the tris (dialkylamino) cyclopentadienyl metal complex;
wherein, the structural formula of the compound 1 is as follows:
the structural formula of compound 2 is as follows:
the structural formula of compound 3 is as follows:
the structural formula of compound 4 is as follows:
m is Zr or Hf;
R1、R2each independently selected from: C1-C5 alkyl;
R3each occurrence is independently selected from: h or C1-C5 alkyl; n is 0, 1, 2, 3, 4 or 5.
In one specific example, R3H or C1-C2 alkyl. Further, R3Is H or methyl.
In one specific example, R1、R2Each independently selected from: C1-C3 alkyl. Further, R1、R2Each independently selected from: methyl or ethyl.
In one specific example, HNR1R2Selected from the group consisting of: dimethylamine, diethylamine or methylethylamine.
In one particular example, compound 1 is selected from: trimethylsilyl dimethylamine, trimethylsilyl diethylamine or trimethylsilyl methylethylamine.
In one specific example, MCl4The molar ratio of the compound to the compound 1 is 1 (1-4). Specifically, MCl4The molar ratio to compound 1 includes, but is not limited to: 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4.
In one specific example, MCl4With HNR1R2The molar ratio of (1) to (6) is 1 (3). Specifically, MCl4With HNR1R2Including but not limited to: 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1: 6.
In one specific example, MCl4The molar ratio of the compound to the compound 4 is 1 (1-3). Specifically, MCl4The molar ratio to compound 4 includes, but is not limited to: 1:1, 1:1.5, 1:2, 1:2.5, 1:3.
In one specific example, in the step (1), the reaction temperature is room temperature, and the reaction time is 10-15 h. Specifically, in step (1), the reaction time includes, but is not limited to: 10h, 11h, 12h, 13h, 14h and 15 h.
In one specific example, in the step (1), the solvent used for the reaction is an alkane solvent. Further, in the step (1), the solvent adopted in the reaction is n-hexane. Further, in the step (1), the solvent adopted by the reaction is anhydrous n-hexane.
In one specific example, in the step (2), the reacting step includes:
adding HNR into the compound 2 at the temperature of-10 ℃ to 0 DEG C1R2And after the addition is finished, reacting for 2-5 h under the reflux condition.
Specifically, in step (2), the reaction temperature includes, but is not limited to: -10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, and-1 ℃.
Specifically, in step (2), the reaction time includes, but is not limited to: 2h, 3h, 4h and 5 h.
In one specific example, in step (3), the step of reacting comprises:
adding the compound 4 into the compound 3 at the temperature of-10-0 ℃, and reacting for 10-15 h at room temperature after the addition is finished.
Specifically, in step (3), the reaction temperature includes, but is not limited to: -10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, and-1 ℃.
Specifically, in step (3), the reaction time includes, but is not limited to: 10h, 11h, 12h, 13h, 14h and 15 h.
In one specific example, step (1), step (2) and step (3) are performed in an inert gas atmosphere, and the inert gas used is high-purity nitrogen or high-purity argon.
In one specific example, the reaction solution obtained by the reaction in step (1) is directly subjected to step (2) without being subjected to post-treatment.
In one specific example, the reaction solution obtained by the reaction in the step (2) is concentrated under reduced pressure and then directly subjected to the step (3).
In one specific example, the reaction solution obtained by the reaction in step (3) is filtered, concentrated and distilled under reduced pressure to prepare the tris (dialkylamino) cyclopentadienyl metal complex. Furthermore, the filtration refers to anhydrous anaerobic filtration by using a sand core.
In one specific example, the vacuum distillation is followed by a rectification step.
The following are specific examples, and the starting materials used in the examples are all commercially available products unless otherwise specified.
The route of the synthetic method of the tris (dialkylamino) cyclopentadienyl metal complex in the examples is as follows:
in the embodiment, cyclopentadiene is freshly depolymerized cyclopentadiene, and the depolymerization method is to carry out atmospheric distillation depolymerization on dicyclopentadiene under the protection of nitrogen and collect cyclopentadiene monomers at 41-42 ℃.
Example 1:
this embodiment is a method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex, comprising the following steps:
under the nitrogen atmosphere, 27.9 g of zirconium tetrachloride, 28.2 g of N, N-dimethyl trimethyl silicane and 400 ml of N-hexane are added into a 1000 ml Schlenk bottle, stirred at room temperature for 12 hours, cooled to-10 ℃, added with 81 g of dimethylamine N-hexane solution with the mass concentration of 20%, slowly returned to room temperature and refluxed for 3 hours, decompressed and concentrated to remove half volume of solvent, the system is cooled to-10 ℃, 7.9 g of cyclopentadiene which is just depolymerized is slowly added under the protection of nitrogen, returned to room temperature, continuously stirred for 12 hours, and subjected to anhydrous and anaerobic filtration by a sand core, filtrate is concentrated and drained of the solvent, and residues are decompressed and distilled to obtain 30.1 g of tris (dimethylamino) cyclopentadienyl zirconium with the yield of 87%.
1HNMR(C6D6):6.06(s,5H),2.92(s,18H)。
Elemental analysis and detection are carried out on the final product, and the theoretical value is as follows: 45.79 for C, 8.03 for H and 14.56 for N. Measurement values: 45.62 percent of C, 7.97 percent of H and 14.02 percent of N.
Example 2:
this example is a method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex, which has the same steps as example 1, except that: the amount of the dimethylamine-n-hexane solution in example 1 was changed to 108 g.
Under the nitrogen atmosphere, 27.9 g of zirconium tetrachloride, 28.2 g of N, N-dimethyl trimethyl silicane and 400 ml of N-hexane are added into a 1000 ml Schlenk bottle, stirred at room temperature for 12 hours, cooled to-10 ℃, 108 g of dimethylamine N-hexane solution with the mass concentration of 20% is added, the room temperature is slowly recovered and refluxed for 3 hours, half volume of the solvent is removed through reduced pressure concentration, the system is cooled to-10 ℃, 7.9 g of cyclopentadiene which is just depolymerized is slowly added under the protection of nitrogen, the mixture is recovered to the room temperature, stirring is continued for 12 hours, anhydrous and anaerobic filtration is carried out through a sand core, the solvent is extracted through filtrate concentration, the residue is distilled under reduced pressure, 31.5 g of tris (dimethylamino) cyclopentadienyl zirconium is obtained, and the yield is 91%.
Example 3:
this example is a method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex, which has the same steps as example 2, except that: the amount of cyclopentadiene in example 2 was changed to 11.9 g.
Under the atmosphere of nitrogen, 27.9 g of zirconium tetrachloride, 28.2 g of N, N-dimethyl-trimethyl-silicane and 400 ml of N-hexane are added into a 1000 ml Schlenk bottle, stirred at room temperature for 12 hours, cooled to-10 ℃, 108 g of dimethylamine N-hexane solution with the mass concentration of 20% is added, the room temperature is slowly recovered and refluxed for 3 hours, after half volume of the solvent is removed through decompression and concentration, the system is cooled to-10 ℃, 11.9 g of cyclopentadiene which is just depolymerized is slowly added under the protection of nitrogen, the mixture is recovered to the room temperature, the stirring is continued for 12 hours, anhydrous and anaerobic filtration is carried out through a sand core, the filtrate is concentrated and the solvent is pumped, the residue is distilled under reduced pressure, 33.6 g of tris (dimethylamino) cyclopentadienyl zirconium is obtained, and the yield is 97%.
And (3) rectifying the final product by using a 25 cm-high spine-type column in a thousand-level clean room, and analyzing the purity of the obtained pure product by using an inductively coupled plasma mass spectrometer (ICP-MS), wherein the result shows that the metal purity of the product is 5N.
Example 4:
this example is a method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex, which has the same steps as example 3, except that: the cyclopentadiene in example 3 was changed to an equivalent amount of pentamethylcyclopentadiene.
Under the nitrogen atmosphere, 27.9 g of zirconium tetrachloride, 28.2 g of N, N-dimethyl trimethyl silicane and 400 ml of N-hexane are added into a 1000 ml Schlenk bottle, stirred at room temperature for 12 hours, cooled to-10 ℃, 108 g of dimethylamine N-hexane solution with the mass concentration of 20% is added, the room temperature is slowly recovered and refluxed for 3 hours, half volume of the solvent is removed through reduced pressure concentration, the system is cooled to-10 ℃, 24.5 g of pentamethylcyclopentadiene is slowly added under the protection of nitrogen, the temperature is recovered to the room temperature, stirring is continued for 12 hours, anhydrous and anaerobic filtration is carried out through a sand core, the solvent is extracted through filtrate concentration, the residue is distilled under reduced pressure, 40 g of pentamethylcyclopentadienyl tri (dimethylamino) zirconium is obtained, and the yield is 93%.
1HNMR(C6D6):2.93(s,18H),1.98(s,15H)。
Elemental analysis and detection are carried out on the final product, and the theoretical value is as follows: 53.58 parts of C, 9.27 parts of H and 11.72 parts of N. Measurement values: 53.44 percent of C, 9.21 percent of H and 12.03 percent of N.
Example 5:
this example is a method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex, which has the same steps as example 3, except that: the zirconium tetrachloride in example 3 was changed to an equivalent amount of hafnium tetrachloride.
Under the atmosphere of nitrogen, 38.4 g of hafnium tetrachloride, 28.2 g of N, N-dimethyl-trimethyl-silicane and 400 ml of N-hexane are added into a 1000 ml Schlenk bottle, stirred at room temperature for 12 hours, cooled to-10 ℃, 108 g of dimethylamine N-hexane solution with the mass concentration of 20% is added, the room temperature is slowly recovered and refluxed for 3 hours, after half volume of the solvent is removed by decompression and concentration, the system is cooled to-10 ℃, 11.9 g of cyclopentadiene which is just depolymerized is slowly added under the protection of nitrogen, the mixture is recovered to the room temperature and is continuously stirred for 12 hours, anhydrous and anaerobic filtration is carried out through a sand core, the solvent is pumped out by concentrating the filtrate, the residue is distilled under reduced pressure, 41.5 g of tris (dimethylamino) cyclopentadienyl hafnium is obtained, and the yield is 92%.
1HNMR(C6D6):6.04(s,5H),2.96(s,18H)。
Elemental analysis and detection are carried out on the final product, and the theoretical value is as follows: 35.16 for C, 6.17 for H and 11.18 for N. Measurement values: 35.02 percent of C, 5.99 percent of H and 11.33 percent of N.
Example 6:
this example is a method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex, which has the same steps as example 3, except that: the N, N-dimethyltrimethylsilylamine in example 3 was changed to an equivalent amount of N, N-diethyltrimethylsilylamine, and a 20% dimethylamine in-hexane solution was changed to an equivalent amount of diethylamine in-hexane solution.
Under the atmosphere of nitrogen, 27.9 g of zirconium tetrachloride, 34.9 g of N, N-diethyl-trimethyl-silicane and 400 ml of N-hexane are added into a 1000 ml Schlenk bottle, stirred at room temperature for 12 hours, cooled to-10 ℃, added with 175.5 g of diethylamine N-hexane solution with the mass concentration of 20%, slowly returned to room temperature and refluxed for 3 hours, after half volume of solvent is removed by decompression concentration, the system is cooled to-10 ℃, 11.9 g of cyclopentadiene which is just depolymerized is slowly added under the protection of nitrogen, returned to room temperature, continuously stirred for 12 hours, and subjected to anhydrous and anaerobic filtration by a sand core, filtrate is concentrated and drained of the solvent, and residues are distilled under reduced pressure to obtain 41.6 g of tris (diethylamino) cyclopentadienyl zirconium with the yield of 93%.
1HNMR(C6D6):6.10(s,5H),3.29(q,12H),1.04(t,18H)。
Elemental analysis and detection are carried out on the final product, and the theoretical value is as follows: 54.78 parts of C, 9.47 parts of H and 11.27 parts of N. Measurement values: 54.52 for C, 9.11 for H and 11.43 for N.
Comparative example 1:
this comparative example is a method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex, the procedure is the same as in example 3, except that: the cyclopentadiene in example 3 was changed to an equivalent amount of cyclopentadienyl lithium.
Under the nitrogen atmosphere, 27.9 g of zirconium tetrachloride, 28.2 g of N, N-dimethyl-trimethyl-silicane and 400 ml of N-hexane are added into a 1000 ml Schlenk bottle, stirred at room temperature for 12 hours, cooled to-10 ℃, 108 g of dimethylamine N-hexane solution with the mass concentration of 20% is added, the room temperature is slowly recovered and refluxed for 3 hours, half volume of the solvent is reduced and concentrated, the system is cooled to-10 ℃, 13.0 g of cyclopentadienyl lithium is slowly added under the protection of nitrogen, the temperature is recovered to room temperature, stirring is continued for 12 hours, anhydrous and oxygen-free filtration is carried out through a sand core, the solvent is pumped out by concentrating the filtrate, the residue is distilled under reduced pressure, 31.2 g of tris (dimethylamino) cyclopentadienyl zirconium is obtained, and the yield is 90%.
The final product was rectified in a thousand-stage clean room using a 25 cm high barbed column, and the purity of the pure product was analyzed by an inductively coupled plasma mass spectrometer (ICP-MS), which indicated that the product contained 52ppm lithium and the metal purity was 4N.
Test example:
sequentially using acetone, absolute ethyl alcohol, deionized water, RCA solution, deionized water and absolute ethyl alcohol on a non-doped silicon chip substrateUltrasonically cleaning, drying by using nitrogen, and putting into an atomic layer deposition chamber after drying; adjusting the room temperature of the atomic layer deposition cavity to 260 ℃, and vacuumizing; heating the tris (dimethylamino) cyclopentadienyl zirconium liquid source obtained in the embodiment 3 to 150 ℃, sending the evaporated tris (dimethylamino) cyclopentadienyl zirconium molecules into an atomic layer deposition chamber by using high-purity argon, and continuously introducing argon for 10s after the tris (dimethylamino) cyclopentadienyl zirconium molecules are introduced so as to clean the residual Zr source and reaction byproducts; using argon to remove H2The O pulse enters an atomic layer deposition chamber and waits for a pulse H2After the introduction of O molecules is finished, argon is continuously introduced for 10s so as to clean residual H2O molecules and reaction by-products; repeating the process, obtaining the zirconium dioxide film through 200 cycles, and detecting the thickness of the film through an ellipsometer. Part of the test data is shown in the following table 1:
TABLE 1
As can be seen from Table 1, tris (dimethylamino) cyclopentadienyl zirconium prepared by the inventive example has different pulse time, purge time, H2Under the conditions of O pulse time and purging time, the preparation of the zirconium dioxide film with good uniformity can be realized, and the requirement of the semiconductor industry on the purity of the precursor source can be met.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present patent should be subject to the content of the appended claims, and the description can be used to interpret the content of the claims.
Claims (10)
1. A method for synthesizing a tri (dialkylamino) cyclopentadienyl metal complex is characterized by comprising the following steps:
(1) reacting Compound 1 with MCl4Carrying out a reaction to prepare a compound 2;
(2) reacting compound 2 with HNR1R2Carrying out a reaction to prepare a compound 3;
(3) reacting a compound 3 with a compound 4 to prepare the tris (dialkylamino) cyclopentadienyl metal complex;
wherein, the structural formula of the compound 1 is as follows:
the structural formula of compound 2 is as follows:
the structural formula of compound 3 is as follows:
the structural formula of compound 4 is as follows:
m is Zr or Hf;
R1、R2each independently selected from: C1-C5 alkyl;
R3each occurrence is independently selected from: h or C1-C5 alkyl; n is 0, 1, 2, 3, 4 or 5.
2. The method of synthesizing a tris (dialkylamino) cyclopentadienyl metal complex as recited in claim 1, wherein R is3Is H or methyl.
3. The method of synthesizing a tris (dialkylamino) cyclopentadienyl metal complex according to claim 1, wherein R is1、R2Each independently selected from: methyl or ethyl.
4. A process for the synthesis of a tris (dialkylamino) cyclopentadienyl metal complex according to any one of claims 1 to 3, wherein MCl is MCl4The molar ratio of the compound to the compound 1 is 1 (1-4).
5. A process for the synthesis of a tris (dialkylamino) cyclopentadienyl metal complex according to any one of claims 1 to 3, wherein MCl is MCl4With HNR1R2The molar ratio of (1) to (6).
6. A process for the synthesis of a tris (dialkylamino) cyclopentadienyl metal complex according to any one of claims 1 to 3, wherein MCl is MCl4The molar ratio of the compound to the compound 4 is 1 (1-3).
7. A method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex according to any one of claims 1 to 3, wherein in the step (1), the reaction temperature is room temperature, and the reaction time is 10 to 15 hours.
8. A method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex according to any one of claims 1 to 3, wherein in the step (2), the step of reacting comprises:
adding HNR into the compound 2 at the temperature of-10 ℃ to 0 DEG C1R2And after the addition is finished, reacting for 2-5 h under the reflux condition.
9. A method of synthesising a tris (dialkylamino) cyclopentadienyl metal complex as claimed in any one of claims 1 to 3 wherein in step (3) the step of reacting comprises:
adding the compound 4 into the compound 3 at the temperature of-10-0 ℃, and reacting for 10-15 h at room temperature after the addition is finished.
10. A method for synthesizing a tris (dialkylamino) cyclopentadienyl metal complex according to any one of claims 1 to 3, wherein the reaction solution obtained by the reaction in the step (1) is directly subjected to the step (2) without being subjected to post-treatment; and/or the presence of a catalyst in the reaction mixture,
concentrating the reaction liquid obtained in the step (2) under reduced pressure, and directly performing the step (3); and/or the like, and/or,
and (4) filtering the reaction liquid obtained in the step (3), concentrating and distilling under reduced pressure to prepare the tri (dialkylamino) cyclopentadienyl metal complex.
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