CN113717233B - Aminopyridyl chloride Co (II) compound for information storage material - Google Patents
Aminopyridyl chloride Co (II) compound for information storage material Download PDFInfo
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- 239000011232 storage material Substances 0.000 title claims abstract description 14
- MEQBJJUWDCYIAB-UHFFFAOYSA-N 2-chloropyridin-3-amine Chemical compound NC1=CC=CN=C1Cl MEQBJJUWDCYIAB-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 24
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 150000003927 aminopyridines Chemical class 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- -1 aminopyridyl Chemical group 0.000 claims description 21
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 239000000758 substrate Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000000231 atomic layer deposition Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 5
- 238000004377 microelectronic Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 description 17
- 230000008021 deposition Effects 0.000 description 16
- 239000010408 film Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010409 thin film 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
- 230000006866 deterioration Effects 0.000 description 4
- 239000000203 mixture Substances 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
- 238000005137 deposition process Methods 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 description 1
- 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
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 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
- 230000015654 memory Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000004580 weight loss Effects 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- 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
-
- 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
-
- 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]
-
- 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
Abstract
The invention discloses an aminopyridyl chloride Co (II) compound for an information storage material, and belongs to the technical field of microelectronic materials. The invention provides a novel aminopyridine-based Co (II) chloride compound for an information storage material, which has the advantages of simple synthesis method and mild synthesis condition. The aminopyridyl chloride Co (II) compound has good air moisture resistance stability, good volatility and thermal stability and good film forming performance. The aminopyridine-based Co (II) chloride compound is used as a precursor of CVD/ALD, and a Co-based film such as a Co metal film and the like is prepared through a Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) process, so that the cost of a precursor material is greatly reduced; the precursor material has good air-moisture resistance and stability, so that the precursor material has simple operability, transportation, conveying and processing processes.
Description
Technical Field
The invention relates to an aminopyridyl chloride Co (II) 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, the information storage technology is also facing new requirements and challenges. The core of the development of information storage technology is information storage materials, and large nations and companies all around the world have put great research and development efforts on the materials. Among them, magnetic metallic cobalt and its alloy nano-films have been widely studied in recent years as information storage materials. For example, in addition to the fact that Co metal nano-film materials themselves can be used as the base material for preparing magnetic random access memories, some of its alloys such as cobalt-iron-boron (Co-Fe-B), aluminum-nickel-cobalt (Al-Ni-Co), cobalt oxide (CoO) and the like are considered to be powerful competitors for next-generation information storage materials due to their superior properties. (ACS Nano,2019,13 (12): 14468; nanoscales 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 decrease of the feature size of microelectronic devices and the continuous increase of the aspect ratio of device structures, the filling of materials faces great difficulties, the conventional deposition methods such as Physical Vapor Deposition (PVD) technology cannot meet the requirements (the method is faster to deposit materials at the openings of the trenches, and the slower bottom of the trenches can cause poor step coverage at the bottom of the trenches to cause device failure), and the Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) technologies become new device manufacturing technologies due to their advantages in terms of good conformality, good uniformity and the like. In CVD/ALD process technology, the nature of the precursor is critical, and the precursor is required to have excellent volatility, thermal stability and reactivity, and in addition, to have high purity, easy storage, non-toxicity, easy synthesis, low cost and as high resistance to water and oxygen as possible, so as to facilitate handling, use, storage and transportation.
Currently, some CVD/ALD Co precursors have been reported to be broadly classified as carbonyl, β -diketonate, cyclopentadienyl, amine, α -diimine, amidinate, and the like, depending on the ligand attached to the cobalt center. However, while these precursors have been reported to be applicable to CVD/ALD techniques for producing metallic cobalt and related thin films, they still present some problems. For example, carbonyl complexes, while having very good volatility and being capable of thin film deposition at lower deposition temperatures, are prone to spontaneous combustion and have high toxicity, which increases their use risks, and in addition are prone to decomposition and cannot be stored for long periods; beta-diketo complexes, while low in toxicity and inexpensive and readily available, are relatively poorly volatile and likewise cannot be stored for long periods of time, and moreover the deposition temperatures of the corresponding partial CVD/ALD processes are relatively high; the metallocene-based complex has excellent volatility, and can be used for film deposition at moderate deposition temperature, but the prepared film has high carbon content and can be only suitable for deposition of a part of film materials; complexes such as amino, alpha-diimine and the like have the defects of low thermal stability, high content of film-forming impurities and the like. (Journal of Vacuum Science & Technology, A,2018,36 (6): 061505/1;Sensors and Actuators,B:Chemical,2019,298:126868;Electrochimica Acta,2005,50 (23): 4592;Journal of Vacuum Science&Technology,A,2014,32:020606;Organometallics,2011,30:5010;Inorganic Chemistry,2003,42 (24): 7951) furthermore, most of the precursors reported to date have low stability to water and oxygen and are extremely inconvenient to prepare, synthesize and handle. Meanwhile, the components and the performances of the finally prepared film material can be directly influenced by different precursors due to the self structure, the process parameters and the like, and the types and the quantity of the precursors developed at present are relatively less and are not enough to meet the great demands of people for the preparation of different types and performance materials. Therefore, in the great background of the continual updating of the related art, it is becoming critical to explore the synthesis of more types of CVD/ALD Co precursors to meet the increasing/rising demands.
Disclosure of Invention
In order to solve at least one of the problems, the invention aims to provide a novel aminopyridine-based Co (II) chloride compound for information storage materials, which has the advantages of simple synthesis method, mild synthesis conditions, good air moisture resistance stability, good volatility and thermal stability and good film forming property.
The first object of the present invention is to provide an aminopyridyl Co (II) chloride compound having a structure represented by the general formula (I):
wherein R is a hydrogen atom, C 1 -C 6 Alkyl, C 2 -C 5 Alkenyl, C 2 -C 5 Cycloalkyl, C 6 -C 10 Aryl or-Si (R) 1 ) 3 ，R 1 Is C 1 -C 6 An alkyl group.
In one embodiment of the present invention, the aminopyridyl Co (II) chloride compound has a structure specifically comprising:
a second object of the present invention is to provide a process for preparing the aminopyridyl Co (II) chloride compound described above, which comprises 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 cobalt dichloride solution in a reaction solvent to obtain cobalt dichloride solution;
(3) Dropwise adding the substrate reaction solution obtained in the step (1) into cobalt dichloride solution for reaction;
(4) After the reaction is finished, removing volatile matters under reduced pressure, adding hexane, toluene or diethyl ether solution for washing for a plurality of times, and collecting solids after filtration; and adding dichloromethane for dissolution, and recrystallizing at the temperature of-20 to 30 ℃ to obtain the aminopyridyl chloride Co (II) compound.
In one embodiment of the present invention, in step (1), the mass ratio of the 2-aminopyridine 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 methylene chloride.
In one embodiment of the present invention, in step (2), the molar ratio of the 2-aminopyridine substrate to cobalt dichloride is from 2:0.8 to 1.2. Specifically, the ratio is 2:1.
In one embodiment of the present invention, in the step (2), the mass ratio of 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 methylene chloride.
In one embodiment of the present invention, in step (3), the temperature of the reaction is room temperature (20-30 ℃); the reaction time is 15-25 h.
A third object of the present invention is to provide the use of the aminopyridyl Co (II) chloride compounds described above in the field of microelectronic material preparation.
In one embodiment of the invention, the use is for the preparation of information storage materials.
In one embodiment of the present invention, the application is to prepare a metal or metal alloy film by chemical vapor deposition or atomic layer deposition using the aminopyridyl Co (II) chloride compound as a precursor.
The invention has the beneficial effects that:
the aminopyridyl Co (II) chloride compound obtained by the present invention can be used as a precursor for CVD/ALD to prepare Co-based thin films such as metal Co by Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) processes. The aminopyridyl chloride Co (II) compound disclosed by the invention has the following advantages: (1) The synthesis method is simple and convenient, the condition is mild, and the synthesis cost of the precursor material is greatly reduced; (2) The air-moisture resistance stability is good, so that the precursor operability, transportation and conveying processes become simple and easy to operate; (3) Has good volatility and thermal stability, and the T of the isopropyl aminopyridine cobalt chloride precursor under normal pressure 50 202 ℃ and a minimum residual mass of 5.45%; (4) Has good film forming performance, and the isopropyl aminopyridine cobalt chloride precursor is prepared by N 2 As a carrier gas, a good CVD Co film can be formed by using a nitrogen-hydrogen mixed gas (hydrogen content 10%) as a reducing gas at 400 ℃.
Drawings
FIG. 1 is a diagram of the structure of a single crystal of a 2-isopropylaminopyridyl cobalt dichloride precursor;
FIG. 2 is a graph of TG pattern of a 2-isopropylaminopyridyl cobalt dichloride precursor with temperature in degrees Celsius on the abscissa and weight loss on the ordinate;
FIG. 3 is an SEM image of a CVD film material obtained using a 2-isopropylaminopyridyl cobalt dichloride precursor.
Detailed Description
In order that the technical content of the present invention may be more clearly understood, the following examples are given in detail only for the purpose of better understanding the content of the present invention and are not to be construed as limiting the scope of the present invention.
The preparation method of the 2-isopropyl aminopyridyl cobalt dichloride compound is carried out according to the reaction of a formula (I):
example 1
A preparation method of aminopyridyl chloride Co (II) compound for information storage material comprises the following steps: the method comprises the following steps:
(1) 2-isopropylaminopyridine (20.3 g) is dissolved in a dichloromethane solvent, the mass ratio of the 2-isopropylaminopyridine to the dichloromethane solvent is 1:15, and the mixture is uniformly mixed to obtain a reaction solution;
(2) Weighing cobalt dichloride according to the proportion of 2:1 of the mol ratio of the 2-isopropyl aminopyridine to the cobalt dichloride, adding dichloromethane according to the proportion of the cobalt dichloride to the dichloromethane of which the mass ratio is 1:15, and uniformly mixing to obtain a cobalt dichloride dichloromethane solution;
(3) Dropwise adding the reaction solution obtained in the step (1) into cobalt dichloride dichloromethane solution at room temperature, stirring and reacting for 20 hours, and obtaining a reaction mixture after finishing the reaction;
(4) And (3) decompressing the reaction mixture obtained in the step (3) to remove volatile matters, adding hexane for washing for multiple times, filtering, collecting a filter cake, adding dichloromethane for dissolving, and repeatedly recrystallizing at the temperature of minus 30 ℃ to obtain a 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; theoretically, the 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-isopropyl aminopyridine cobalt 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 stability, and can be stored for more than 60 days in an atmospheric environment without deterioration, so that the precursor has simple operability, transportation, conveying and processing processes.
Thermal properties of the precursor were tested by Thermogravimetric (TG) method, T of 2-isopropylaminopyridyl cobalt dichloride precursor at atmospheric pressure 50 The minimum residual mass was 5.45% at 202℃and the results are shown in FIG. 2, with good volatility and thermal stability.
CVD deposition of thin films:
the obtained target product is used as a precursor, and the growth parameters used in the CVD deposition process are as follows: total pressure 3.5torr, N 2 Flow rate: 100mL/min, nitrogen-hydrogen mixture (hydrogen content 10%): 50mL/min, deposition time: 60min, deposition temperature: the film forming rate is 400 ℃: SEM of the resulting deposited film at 7.2nm/min is shown in FIG. 3.
Example 2
A preparation method of aminopyridyl chloride Co (II) compound for information storage material comprises the following steps: the method comprises the following steps:
(1) 2-trimethylsilyl aminopyridine (28.7 g) was dissolved in dichloromethane solvent at a mass ratio of 2-trimethylsilyl aminopyridine to reaction solvent of 1:10;
(2) In addition, weighing a certain amount of cobalt dichloride according to the proportion of 2:1 of the molar ratio of the 2-trimethylsilyl aminopyridine to the cobalt dichloride, and adding a dichloromethane solution according to the proportion of 1:10 of the mass ratio of the cobalt dichloride;
(3) Dropwise adding the reaction liquid obtained in the step (1) into cobalt dichloride dichloromethane solution at room temperature, and stirring for reaction for 25 hours;
(4) And (3) decompressing the reaction mixture obtained in the step (3) to remove volatile matters, adding hexane for washing for multiple times, filtering, collecting a filter cake, adding dichloromethane for dissolving, and repeatedly recrystallizing at the temperature of minus 30 ℃ to obtain a 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; theoretically, the elemental analysis value is C,41.56; h,6.10; n,12.12; 12.15 parts of Si; cl,15.33; co,12.74.
The synthesized precursor has good air-moisture resistance stability, and can be stored for more than 60 days in an atmospheric environment without deterioration, so that the precursor has simple operability, transportation, conveying and processing processes.
Thermal properties of the precursor were tested by Thermogravimetric (TG) method, T of 2-trimethylsilyl aminopyridyl cobalt dichloride precursor at atmospheric pressure 50 The minimum residual mass is 4.77% at 218 ℃, and the product has good volatility and thermal stability.
CVD deposition of thin films:
the target product is used as a deposition precursor, and the growth parameters used in the CVD deposition process are as follows: total pressure 3.5torr, N 2 Flow rate: 100mL/min, nitrogen-hydrogen mixture (hydrogen content 10%): 50mL/min, deposition time: 60min, deposition temperature: the film forming rate is 400 ℃:5.3nm/min.
Example 3
A preparation method of aminopyridyl chloride Co (II) compound for information storage material comprises the following steps: the method comprises the following steps:
(1) 2-cyclohexylaminopyridine (10.1 g) was dissolved in dichloromethane solvent at a mass ratio of 2-cyclohexylaminopyridine to reaction solvent of 1:20;
(2) In addition, weighing a certain amount of cobalt dichloride according to the proportion of 2-cyclohexylaminopyridine to 2:1 of cobalt dichloride molar ratio, and adding a dichloromethane solution according to the proportion of 1:20 of cobalt dichloride mass ratio;
(3) Dropwise adding the reaction liquid obtained in the step (1) into cobalt dichloride dichloromethane solution at room temperature, and stirring for reaction for 15 hours;
(4) And (3) decompressing the reaction mixture obtained in the step (3) to remove volatile matters, adding hexane for washing for multiple times, filtering, collecting a filter cake, adding dichloromethane for dissolving, and repeatedly recrystallizing at the temperature of-29 ℃ to obtain a target product.
The structural formula of the target product is as follows:yield: 85%, melting point: 137-139.4 ℃, elemental analysis: c,54.69; h,6.81; n,11.54; cl,14.63; co,12.33; theoretical elemental analysis valueC,54.78; h,6.69; n,11.62; cl,14.70; co,12.21.
The synthesized precursor has good air-moisture resistance stability, and can be stored for more than 60 days in an atmospheric environment without deterioration, so that the precursor has simple operability, transportation, conveying and processing processes.
Thermal properties of the precursor were tested by Thermogravimetric (TG) method, T of 2-cyclohexylaminopyridyl cobalt dichloride precursor at atmospheric pressure 50 The minimum residual mass is 6.23% at 231 ℃, and the product has good volatility and thermal stability.
CVD deposition of thin films:
the target product is used as a precursor, and the growth parameters used in the CVD deposition process are as follows: total pressure 3.5torr, N 2 Flow rate: 100mL/min, nitrogen-hydrogen mixture (hydrogen content 10%): 50mL/min, deposition time: 60min, deposition temperature: the film forming rate is 400 ℃:4.5nm/min.
Comparative example 1
The most widely used cobalt amidinate complexes of the Co precursors reported so far are used as precursors for CVD deposition films, compared to the precursor of example 1. The cobalt amidinate complex has the following structure:
the precursor has poor air-moisture resistance stability, and is subject to deterioration after being exposed for 2 seconds in an atmospheric environment, and generates a large amount of heat, so that the use difficulty of the precursor in the processes of operation, transportation, conveying and processing is increased. Meanwhile, due to the low air-moisture stability of the precursor and the need of using reagents such as alkyl lithium in the synthesis process, the synthesis cost and the synthesis difficulty of the precursor are increased, and the method is not beneficial to industrial application.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and 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 (8)
1. A method for preparing an information storage material is characterized in that aminopyridine-based Co (II) chloride compound with a structure shown in a general formula (I) is used as a precursor, and a metal film is prepared through a chemical vapor deposition process;
wherein R is a hydrogen atom, C 1 -C 6 Alkyl, C 2 -C 5 Cycloalkyl, or-Si (R) 1 ) 3 ，R 1 Is C 1 -C 6 An alkyl group.
2. The method according to claim 1, wherein the preparation of aminopyridyl Co (II) chloride compound comprises 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 cobalt dichloride solution in a reaction solvent to obtain cobalt dichloride solution;
(3) Dropwise adding the substrate reaction solution obtained in the step (1) into cobalt dichloride solution for reaction;
(4) After the reaction is finished, removing volatile matters under reduced pressure, adding hexane, toluene or diethyl ether solution for washing for a plurality of times, and collecting solids after filtration; and adding dichloromethane for dissolution, and recrystallizing at the temperature of-20 to 30 ℃ to obtain the aminopyridyl chloride Co (II) 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 process of claim 2, wherein in step (1), the reaction solvent is methylene chloride.
5. The process of claim 2, wherein in step (2), the molar ratio of the 2-aminopyridine substrate to cobalt dichloride is from 2:0.8 to 1.2.
6. The method according to claim 2, wherein in the step (2), the mass ratio of cobalt dichloride to the reaction solvent is 1:10 to 1:20.
7. The process of claim 2, wherein in step (2), the reaction solvent is methylene chloride.
8. The process according to any one of claims 2 to 7, wherein in step (3), the temperature of the reaction is room temperature; the reaction time is 15-25 h.
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| US4818898A (en) * | 1986-09-10 | 1989-04-04 | E. I. Du Pont De Nemours And Company | Optical nonlinearity in organic and organometallic molecules via lattice inclusion complexation |
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|---|---|---|---|---|
| US4513302A (en) * | 1982-06-24 | 1985-04-23 | Ciba-Geigy Corporation | Pressure-sensitive or heat-sensitive recording material |
| US4818898A (en) * | 1986-09-10 | 1989-04-04 | E. I. Du Pont De Nemours And Company | Optical nonlinearity in organic and organometallic molecules via lattice inclusion complexation |
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