CN113717233A - Aminopyridinyl Co (II) chloride compound for information storage material - Google Patents
Aminopyridinyl Co (II) chloride compound for information storage material Download PDFInfo
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- CN113717233A CN113717233A CN202111171426.XA CN202111171426A CN113717233A CN 113717233 A CN113717233 A CN 113717233A CN 202111171426 A CN202111171426 A CN 202111171426A CN 113717233 A CN113717233 A CN 113717233A
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- -1 Aminopyridinyl Chemical group 0.000 title claims abstract description 25
- 239000011232 storage material Substances 0.000 title claims abstract description 15
- 150000001805 chlorine compounds Chemical class 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 24
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000010409 thin film Substances 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 238000004377 microelectronic Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007810 chemical reaction solvent Substances 0.000 claims description 14
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- MEQBJJUWDCYIAB-UHFFFAOYSA-N 2-chloropyridin-3-amine Chemical compound NC1=CC=CN=C1Cl MEQBJJUWDCYIAB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 description 18
- 230000008021 deposition Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- JGHDSVGMTKVPGI-UHFFFAOYSA-L [Co](Cl)Cl.ClCCl Chemical compound [Co](Cl)Cl.ClCCl JGHDSVGMTKVPGI-UHFFFAOYSA-L 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- PPMDMZCZTBHTAC-UHFFFAOYSA-N C[Si](C)(C)C1=NC=CC=C1N Chemical compound C[Si](C)(C)C1=NC=CC=C1N PPMDMZCZTBHTAC-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- UUMQKWWKCDCMJS-UHFFFAOYSA-N n-cyclohexylpyridin-2-amine Chemical compound C1CCCCC1NC1=CC=CC=N1 UUMQKWWKCDCMJS-UHFFFAOYSA-N 0.000 description 3
- JQPJCPJUEYREHV-UHFFFAOYSA-N n-propan-2-ylpyridin-2-amine Chemical compound CC(C)NC1=CC=CC=N1 JQPJCPJUEYREHV-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZDZZPLGHBXACDA-UHFFFAOYSA-N [B].[Fe].[Co] Chemical compound [B].[Fe].[Co] ZDZZPLGHBXACDA-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention discloses an aminopyridyl chlorinated Co (II) compound for an information storage material, belonging to the technical field of microelectronic materials. The invention provides a novel aminopyridinyl chlorinated Co (II) compound for an information storage material, which has the advantages of simple synthesis method and mild synthesis conditions. The aminopyridyl Co (II) chloride compound has good air moisture resistance stability, good volatility and thermal stability and good film forming performance. The invention takes aminopyridinyl Co (II) chloride compound as a precursor of CVD/ALD, prepares Co-based thin films such as Co metal thin films and the like by a Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) process, and greatly reduces the cost of precursor materials; the precursor material has good air moisture resistance and stability, so that the operability, transportation and processing of the precursor material become simple and easy to operate.
Description
Technical Field
The invention relates to an aminopyridinyl Co (II) chloride compound for an information storage material, belonging to the technical field of microelectronic materials.
Background
With the development of the internet, the internet of things and big data, information storage technology is continuously facing new requirements and challenges. The core of the development of information storage technology lies in information storage materials, and great research and development forces are put into the information storage materials by various countries and companies all over the world. Among them, magnetic metal cobalt and its alloy nano-film have been widely studied in recent years as information storage materials. For example, in addition to the fact that Co metal nano-film material can be used as the base material for preparing the magnetic random access memory, some alloys thereof, such as cobalt-iron-boron (Co-Fe-B), aluminum-nickel-cobalt (Al-Ni-Co), cobalt oxide (CoO), etc., are considered to be strong competitors of the next generation information storage material due to their superior properties. (ACS Nano,2019,13(12): 14468; Nanoscale,2020,12(11): 6378; Journal of Materials Engineering and Performance,2015,24(4): 1522; Journal of Applied Physics,2010,108(11): 113918/1).
With the continuous reduction of the feature size of microelectronic devices and the continuous increase of the aspect ratio of device structures, the material filling is difficult greatly, the conventional deposition method such as Physical Vapor Deposition (PVD) technology cannot meet the requirement (the method deposits material at the opening of the trench faster and the bottom of the trench slower, which may result in poor step coverage at the bottom of the trench and cause device failure), and the Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) technologies have advantages in terms of good conformality and good uniformity, and the like. In CVD/ALD process technology, the properties of the precursor are of critical importance, requiring that the precursor has excellent volatility, thermal stability and reactivity, and furthermore, needs to have high purity, easy storage, non-toxic, easy synthesis, low cost and as high a stability against water and oxygen as possible for ease of handling and storage and transportation.
At present, some precursors for CVD/ALD Co have been reported to be roughly classified into carbonyl groups, β -diketo groups, cyclopentadienyl groups, amine groups, α -diimine groups, amidino groups, etc., depending on the ligand to which the cobalt center is attached. However, although these precursors have been reported to be applicable to CVD/ALD techniques for the preparation of metallic cobalt and related thin films, they still suffer from some problems. For example, although carbonyl complexes have very good volatility and can be used for thin film deposition at relatively low deposition temperatures, such complexes are pyrophoric and highly toxic, which increases the risk of use, and in addition, are susceptible to decomposition and cannot be stored for long periods; beta-diketo complexes, although less toxic and less expensive and readily available, are relatively less volatile and likewise cannot be stored for long periods of time, and in addition the corresponding partial CVD/ALD processes have higher deposition temperatures; the cyclopentadienyl complex has excellent volatility, and can be used for film deposition at moderate deposition temperature, but the prepared film has high carbon content easily and is only suitable for deposition of a part of film materials; the complex such as amido, alpha-diimine, etc. also has the defects of low thermal stability, high content of film-forming impurities, etc. (Journal of Vacuum Science & Technology, A,2018,36(6): 061505/1; Sensors and actors, B: Chemical,2019,298: 126868; electrochemical Acta,2005,50(23): 4592; Journal of Vacuum Science & Technology, A,2014,32: 020606; Organometallics,2011,30: 5010; Inorganic Chemistry,2003,42 (7924): 45951) furthermore, most of the precursors reported so far have low stability against water and oxygen, and are extremely inconvenient for synthesis and operation. Meanwhile, different precursors can directly influence the components and the performance of finally prepared film materials due to the self structure, process parameters and other reasons, and the types and the number of the currently developed precursors are relatively small and are not enough to meet the huge requirements of people on the preparation of different types and performance materials. Therefore, in the context of the continuous generation of related art, it becomes critical to explore the synthesis of more types of CVD/ALD Co precursors to meet the increasing demands.
Disclosure of Invention
In order to solve at least one of the above problems, the present invention aims to provide a novel aminopyridinyl co (ii) chloride compound for information storage materials, which has a simple synthesis method and mild synthesis conditions, and the precursor compound of the present invention has good air moisture resistance stability, good volatility and thermal stability, and good film-forming properties.
The first object of the present invention is to provide an aminopyridinylchloride co (ii) compound having a structure represented by general formula (I):
wherein R is a hydrogen atom, C1-C6Alkyl radical, C2-C5Alkenyl radical, C2-C5Cycloalkyl radical, C6-C10Aryl radicalsor-Si (R)1)3，R1Is C1-C6An alkyl group.
In one embodiment of the present invention, the structure of the aminopyridinyl co (ii) chloride compound specifically includes:
a second object of the present invention is to provide a process for the preparation of the above aminopyridinylchloride co (ii) compounds, comprising in particular the steps of:
(1) dissolving a 2-aminopyridine substrate shown in a formula (II) in a reaction solvent to obtain a substrate reaction solution;
(2) dispersing a cobalt dichloride solution in a reaction solvent to obtain a cobalt dichloride solution;
(3) dropwise adding the substrate reaction solution obtained in the step (1) into a cobalt dichloride solution for reaction;
(4) after the reaction is finished, removing volatile matters under reduced pressure, then adding hexane, toluene or ether solution for washing for multiple times, filtering and collecting solids; and adding dichloromethane for dissolving, and recrystallizing at-20-30 ℃ to obtain the aminopyridyl Co (II) chloride compound.
In one embodiment of the present invention, in the step (1), the mass ratio of the 2-aminopyridine-based substrate to the reaction solvent is 1:10 to 1: 20.
In one embodiment of the present invention, in step (1), the reaction solvent is dichloromethane.
In one embodiment of the present invention, in the step (2), the molar ratio of the 2-aminopyridine substrate to the cobalt dichloride is 2: 0.8-1.2. Specifically, 2:1 can be selected.
In one embodiment of the invention, in the step (2), the mass ratio of the cobalt dichloride to the reaction solvent is 1:10 to 1: 20.
In one embodiment of the present invention, in step (2), the reaction solvent is dichloromethane.
In one embodiment of the present invention, in step (3), the reaction temperature is room temperature (20-30 ℃); the reaction time is 15-25 h.
The third purpose of the invention is to provide the application of the aminopyridinyl Co (II) chloride compound in the field of microelectronic material preparation.
In one embodiment of the invention, the use is for the preparation of an information storage material.
In an embodiment of the invention, the application is to prepare a metal or metal alloy thin film by a chemical vapor deposition process or an atomic layer deposition process with the aminopyridinyl co (ii) chloride compound as a precursor.
The invention has the beneficial effects that:
the aminopyridinyl chlorinated Co (II) compound obtained by the invention can be used as a precursor of CVD/ALD to prepare a Co-based thin film such as metallic Co through a Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) process. The aminopyridinyl Co (II) chloride compound has the following advantages: (1) the synthesis method is simple and convenient, the conditions are mild, and the synthesis cost of the precursor material is greatly reduced; (2) the preparation method has good air moisture resistance stability, so that the operability, transportation and processing of the precursor become simple and easy to operate; (3) has good volatility and thermal stability, and T of the precursor of the isopropylaminopyridine cobalt chloride under normal pressure50At 202 ℃ with a minimum residual mass of 5.45%; (4) has good film-forming property, and the precursor of the isopropyl aminopyridine cobalt chloride is N2As carrier gas, nitrogen-hydrogen mixed gas (hydrogen content is 10%) is used as reducing gas, under the condition of 400 deg.C it can form good CVD Co film.
Drawings
FIG. 1 is a structural diagram of a 2-isopropylaminopyridyl cobalt dichloride precursor single crystal;
FIG. 2 is a TG map of a 2-isopropylaminopyridyldicobalt dichloride precursor, with the abscissa being temperature and the ordinate being weight loss rate in units;
FIG. 3 is an SEM image of a CVD thin film material obtained using a 2-isopropylaminopyridyldicobalt dichloride precursor.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given for detailed description, which are only for the purpose of better understanding the contents of the present invention and not for the purpose of limiting the scope of the present invention.
The preparation method of the 2-isopropylaminopyridyl cobalt dichloride compound is carried out according to the reaction of a formula (I):
example 1
A preparation method of aminopyridinyl chloride Co (II) compound for information storage material comprises the following steps: the method comprises the following steps:
(1) dissolving 2-isopropylaminopyridine (20.3g) in a dichloromethane solvent, wherein the mass ratio of the 2-isopropylaminopyridine to the dichloromethane solvent is 1:15, and uniformly mixing to obtain a reaction solution;
(2) weighing cobalt dichloride according to the molar ratio of 2-isopropylaminopyridine to cobalt dichloride of 2:1, adding dichloromethane according to the mass ratio of 1:15 of cobalt dichloride to dichloromethane, and uniformly mixing to obtain a cobalt dichloride dichloromethane solution;
(3) dropwise adding the reaction liquid obtained in the step (1) into a cobalt dichloride dichloromethane solution at room temperature, stirring and reacting for 20 hours to obtain a reaction mixture;
(4) and (4) decompressing the reaction mixture obtained in the step (3) to remove volatile matters, then adding hexane for washing for multiple times, filtering, collecting a filter cake, adding dichloromethane for dissolving, and repeatedly recrystallizing at-30 ℃ to obtain the target product.
The structural formula of the target product is as follows:
yield: 93%, melting point: 115-119.4 ℃, elemental analysis: c, 47.70; h, 6.13; n,13.99; cl, 17.58; co, 14.60; theoretical elemental analysis value is C, 47.78; h, 6.01; n, 13.93; cl, 17.63; co, 14.65. The structure of the target product (2-isopropylaminopyridyldicobalt dichloride precursor) is analyzed by single crystal X-ray diffraction, and the specific structural formula is shown in figure 1.
The synthesized precursor has good air moisture resistance and stability, and can be stored for more than 60 days in an atmospheric environment without deterioration, so that the operability, transportation and processing processes of the precursor become simple and easy to operate.
Testing the thermal property of the precursor by a Thermogravimetric (TG) method, wherein the T of the 2-isopropylaminopyridyl cobalt dichloride precursor is measured at normal pressure50At 202 c, the minimum residual mass was 5.45%, the results are shown in fig. 2, with good volatility and thermal stability.
CVD deposition of film:
the target product obtained was used as precursor, and the growth parameters used in the CVD deposition process were: total pressure 3.5torr, N2Flow rate: 100mL/min, nitrogen-hydrogen mixed gas (hydrogen content 10%): 50mL/min, deposition time: 60min, deposition temperature: the film forming rate is as follows at 400℃: 7.2nm/min, SEM image of the resulting deposited film is shown in FIG. 3.
Example 2
A preparation method of aminopyridinyl chloride Co (II) compound for information storage material comprises the following steps: the method comprises the following steps:
(1) dissolving 2-trimethylsilyl aminopyridine (28.7g) in a dichloromethane solvent, wherein the mass ratio of the 2-trimethylsilyl aminopyridine to the reaction solvent is 1: 10;
(2) weighing a certain amount of cobalt dichloride according to the molar ratio of 2:1 of 2-trimethylsilyl aminopyridine to the cobalt dichloride, and adding a dichloromethane solution according to the mass ratio of 1:10 of the cobalt dichloride;
(3) dropwise adding the reaction liquid obtained in the step (1) into a cobalt dichloride dichloromethane solution at room temperature, and stirring for reaction for 25 hours;
(4) and (4) decompressing the reaction mixture obtained in the step (3) to remove volatile matters, then adding hexane for washing for multiple times, filtering, collecting a filter cake, adding dichloromethane for dissolving, and repeatedly recrystallizing at-30 ℃ to obtain the target product.
The structural formula of the target product is as follows:
yield: 87%, melting point: 123-126.1 ℃, elemental analysis: c, 41.41; h, 6.23; n,12.22, Si, 12.10; cl, 15.39; co, 12.65; theoretical elemental analysis value is C, 41.56; h, 6.10; n, 12.12; si, 12.15; cl, 15.33; co, 12.74.
The synthesized precursor has good air moisture resistance and stability, and can be stored for more than 60 days in an atmospheric environment without deterioration, so that the operability, transportation and processing processes of the precursor become simple and easy to operate.
Testing the thermal property of the precursor by a Thermogravimetric (TG) method, wherein the T of the 2-trimethylsilyl amino pyridyl cobalt dichloride precursor is measured under normal pressure50At 218 deg.c and a minimum residual mass of 4.77%, and has good volatility and heat stability.
CVD deposition of film:
using this target product as a deposition precursor, the growth parameters used during CVD deposition were: total pressure 3.5torr, N2Flow rate: 100mL/min, nitrogen-hydrogen mixed gas (hydrogen content 10%): 50mL/min, deposition time: 60min, deposition temperature: the film forming rate is as follows at 400℃: 5.3 nm/min.
Example 3
A preparation method of aminopyridinyl chloride Co (II) compound for information storage material comprises the following steps: the method comprises the following steps:
(1) dissolving 2-cyclohexylaminopyridine (10.1g) in a dichloromethane solvent, wherein the mass ratio of the 2-cyclohexylaminopyridine to the reaction solvent is 1: 20;
(2) weighing a certain amount of cobalt dichloride according to the molar ratio of 2-cyclohexylaminopyridine to cobalt dichloride of 2:1, and adding a dichloromethane solution according to the mass ratio of the cobalt dichloride of 1: 20;
(3) dropwise adding the reaction liquid obtained in the step (1) into a cobalt dichloride dichloromethane solution at room temperature, and stirring for reaction for 15 hours;
(4) and (4) decompressing the reaction mixture obtained in the step (3) to remove volatile matters, then adding hexane for washing for multiple times, filtering, collecting a filter cake, adding dichloromethane for dissolving, and repeatedly recrystallizing at-29 ℃ to obtain the target product.
The structural formula of the target product is as follows:
yield: 85%, melting point: 137-139.4 ℃, element analysis: c, 54.69; h, 6.81; n, 11.54; cl, 14.63; co, 12.33; theoretical elemental analysis value is C, 54.78; h, 6.69; n, 11.62; cl, 14.70; co, 12.21.
The synthesized precursor has good air moisture resistance and stability, and can be stored for more than 60 days in an atmospheric environment without deterioration, so that the operability, transportation and processing processes of the precursor become simple and easy to operate.
Testing the thermal property of the precursor by a Thermogravimetric (TG) method, wherein T of the 2-cyclohexylaminopyridyl cobalt dichloride precursor is measured under normal pressure50231 ℃ and a minimum residual mass of 6.23 percent, and has good volatility and thermal stability.
CVD deposition of film:
using this target product as a precursor, the growth parameters used during CVD deposition were: total pressure 3.5torr, N2Flow rate: 100mL/min, nitrogen-hydrogen mixed gas (hydrogen content 10%): 50mL/min, deposition time: 60min, deposition temperature: the film forming rate is as follows at 400℃: 4.5 nm/min.
Comparative example 1
The most widely used cobalt amidinate complexes in the Co precursors reported so far were used as precursors for CVD deposited films, and compared with the precursors in example 1. The cobalt amidinate complex has the following structure:
the precursor has poor stability of resisting air moisture, is deteriorated after being exposed for 2s in the atmospheric environment, and generates a large amount of heat, thereby increasing the difficulty in operation, transportation and processing of the precursor. Meanwhile, due to the low air moisture resistance stability of the precursor and the need of using reagents such as lithium alkyl and the like in the synthesis process, the synthesis cost and the synthesis difficulty of the precursor are increased, and the industrial application is not facilitated.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. Aminopyridinylchloride Co (II) compounds having the structure shown in formula (I):
wherein R is a hydrogen atom, C1-C6Alkyl radical, C2-C5Alkenyl radical, C2-C5Cycloalkyl radical, C6-C10Aryl or-Si (R)1)3，R1Is C1-C6An alkyl group.
2. A process for the preparation of aminopyridinylchloride co (ii) compounds according to claim 1, characterized in that it comprises the following steps:
(1) dissolving a 2-aminopyridine substrate shown in a formula (II) in a reaction solvent to obtain a substrate reaction solution;
(2) dispersing a cobalt dichloride solution in a reaction solvent to obtain a cobalt dichloride solution;
(3) dropwise adding the substrate reaction solution obtained in the step (1) into a cobalt dichloride solution for reaction;
(4) after the reaction is finished, removing volatile matters under reduced pressure, then adding hexane, toluene or ether solution for washing for multiple times, filtering and collecting solids; and adding dichloromethane for dissolving, and recrystallizing at-20-30 ℃ to obtain the aminopyridyl Co (II) chloride compound.
3. The method according to claim 2, wherein in the step (1), the mass ratio of the 2-aminopyridine substrate to the reaction solvent is 1:10 to 1: 20.
4. The method according to claim 2, wherein in the step (1), the reaction solvent is dichloromethane.
5. The method according to claim 2, wherein in the step (2), the molar ratio of the 2-aminopyridine substrate to the cobalt dichloride is 2: 0.8-1.2.
6. The method according to claim 2, wherein in the step (2), the mass ratio of the cobalt dichloride to the reaction solvent is 1: 10-1: 20.
7. The method according to claim 2, wherein in the step (2), the reaction solvent is dichloromethane.
8. The method according to any one of claims 2 to 7, wherein in the step (3), the temperature of the reaction is room temperature; the reaction time is 15-25 h.
9. Use of aminopyridinylchloride co (ii) compounds according to claim 1 in the field of microelectronic material preparation.
10. A method for producing an information storage material, characterized in that a metal or metal alloy thin film is produced by a chemical vapor deposition process or an atomic layer deposition process using the aminopyridinylchloride co (ii) compound according to claim 1 as a precursor.
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| CN114573642A (en) * | 2022-02-28 | 2022-06-03 | 许昌学院 | Amino pyridyl tetramethyl ethylene diamine Ni (II) adduct as precursor for information storage material |
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| CN114573642A (en) * | 2022-02-28 | 2022-06-03 | 许昌学院 | Amino pyridyl tetramethyl ethylene diamine Ni (II) adduct as precursor for information storage material |
| CN114573642B (en) * | 2022-02-28 | 2024-01-12 | 许昌学院 | Precursor aminopyridyl tetramethyl ethylenediamine Ni (II) adduct for information storage material |
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