CN116180075B - Preparation method of low-stress strong-bonding high-temperature insulating coating - Google Patents
Preparation method of low-stress strong-bonding high-temperature insulating coating Download PDFInfo
- Publication number
- CN116180075B CN116180075B CN202310129637.XA CN202310129637A CN116180075B CN 116180075 B CN116180075 B CN 116180075B CN 202310129637 A CN202310129637 A CN 202310129637A CN 116180075 B CN116180075 B CN 116180075B
- Authority
- CN
- China
- Prior art keywords
- silicon nitride
- multilayer structure
- rich
- lean
- depositing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 90
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 168
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 168
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000151 deposition Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 23
- 238000005516 engineering process Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000004544 sputter deposition Methods 0.000 claims abstract description 9
- 238000007747 plating Methods 0.000 claims abstract description 8
- 238000005546 reactive sputtering Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 86
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 9
- -1 silicon nitrides Chemical group 0.000 abstract description 2
- 230000035882 stress Effects 0.000 description 42
- 239000010936 titanium Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000005433 ionosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005091 Si3N Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0042—Controlling partial pressure or flow rate of reactive or inert gases with feedback of measurements
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0073—Reactive sputtering by exposing the substrates to reactive gases intermittently
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
- C23C14/0652—Silicon nitride
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/548—Controlling the composition
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/44—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
Abstract
The invention discloses a preparation method of a low-stress strong-bonding high-temperature insulating coating, which is prepared by a magnetron sputtering technology in the prior art and comprises the following steps of sequentially performing pretreatment of plating, ar ion sputtering cleaning, bonding layer depositing and N-poor silicon nitride and N-rich silicon nitride alternating multilayer structure depositing, wherein the N-poor silicon nitride and N-rich silicon nitride alternating multilayer structure depositing is performed on the surface of the bonding layer depositing by the magnetron sputtering technology to obtain the N-poor silicon nitride and N-rich silicon nitride alternating multilayer structure, the silicon nitride is deposited by the magnetron sputtering technology through Si target and nitrogen reactive sputtering, and the nitrogen content in two adjacent silicon nitrides is regulated and controlled by periodically changing nitrogen flow in the magnetron sputtering process to obtain the multilayer structure consisting of the N-poor silicon nitride and the N-rich silicon nitride alternating multilayer structure, and the N-poor silicon nitride alternating multilayer structure can generate the micromechanics of alternating tensile stress and compressive stress.
Description
Technical Field
The invention discloses a preparation method of a low-stress strong-combination high-temperature insulating coating, and relates to the technical field of high-temperature insulating coatings.
Background
When the aircraft flies in the ionosphere, a large number of charged particles collide with the thermocouple, so that the thermoelectric potential generated by the thermocouple is changed, and the thermocouple is inaccurate in temperature measurement. A more effective solution to this problem is to apply an insulating coating to the thermocouple surface to shield the charged particles from interference. Meanwhile, the surface temperature of the high-speed aircraft is high under the influence of air resistance, so that the insulating coating needs to have high-temperature resistance besides insulating performance, and the silicon nitride and aluminum oxide coatings in the prior art have the performances and are used as common coating raw materials.
However, when the insulating coating made of the material is applied, the internal stress of the coating is higher, the binding force of the film base is insufficient, and the coating is easy to peel off due to the two reasons.
Disclosure of Invention
The invention aims to provide a preparation method of a low-stress strong-bonding high-temperature insulating coating, which solves the problem that the bonding performance or internal stress cannot be directly regulated through regulating key steps in the preparation process of the high-temperature insulating coating in the prior art.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
a preparation method of a low-stress strong-bonding high-temperature insulating coating comprises the following steps: the method comprises the following steps of sequentially performing a pre-plating treatment step, an Ar ion sputtering cleaning step, a bonding layer depositing step, an N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure depositing step, and an N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure depositing step.
Further, the step of depositing the N-lean silicon nitride and the N-rich silicon nitride alternating multilayer structure is to deposit silicon nitride on the surface of the deposited bonding layer by using a magnetron sputtering technology to obtain the N-lean silicon nitride and the N-rich silicon nitride alternating multilayer structure, wherein the silicon nitride is obtained by using the magnetron sputtering technology through reactive sputtering of a Si target and nitrogen.
Further, the nitrogen content in two adjacent layers of silicon nitride is regulated and controlled by periodically changing the nitrogen flow in the magnetron sputtering process, so that the N-lean silicon nitride and N-rich silicon nitride alternate multilayer structure is a multilayer structure formed by alternately lean silicon nitride and rich silicon nitride.
Further, the step of depositing the bonding layer is to deposit bonding metal on the surface of the base metal by a magnetron sputtering technology to obtain the deposited bonding layer, wherein the thickness of the deposited bonding layer is controlled by controlling the deposition time, the bonding metal is Ti (or Cr), and the deposition time of the bonding metal is 2-5min.
Further, each parameter of the magnetron sputtering is that the cavity is vacuumized to 1X 10 < -3 > Pa-5X 10 < -3 > Pa before the step of depositing the bonding layer is carried out;
in the Ar ion sputtering cleaning step, the Ar gas flow is 20-80 sccm, the Ar purity is more than 99.9%, and the air pressure is 0.2-2.0 Pa;
further, in the step of alternately forming a multilayer structure of the lean N silicon nitride and the rich N silicon nitride and the step of depositing the bonding layer, the current of the Si target and the Ti (or Cr) target is 1-5A, and the purity of the Ti (or Cr) and the Si target is more than 99%;
further, the negative bias voltage of the substrate is-50 to-100V.
Further, the nitrogen concentration in the step of carrying out the N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure is 99.999%, the time for depositing the silicon nitride is 100min, the periodic period is 20-30min, and the total steps are carried out for 3-5 periods.
Further, N in the one period 2 The flow rate is 0-5sccm for 5min, followed by N 2 The flow rate is 10-20sccm and kept for 20min, N 2 The partial pressure is kept between 0 and 0.15Pa.
Further, the step of depositing the N-lean silicon nitride/N-rich silicon nitride and metal bonding layer further comprises a step of preparing an alumina coating, wherein the alumina coating is prepared by coating a denser alumina layer on the N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure by using a sol-gel method.
Further, the sol-gel method comprises preparing aluminum sol which is mixed solution of aluminum nitrate and sodium carbonate;
further, the step of preparing the aluminum oxide coating comprises the steps of pulling the material deposited with the N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure in aluminum sol for 30-40 times by adopting a pulling method, and finally preserving heat in a high-temperature furnace;
further, the mass fraction of the aluminum nitrate is 30wt%, the mass fraction of the sodium carbonate mixed solution is 20-20wt%, and the heat preservation temperature is 900 ℃ and the duration time is 1-2 hours.
Further, the thickness of the deposited adhesive layer is 0.2-0.3 μm.
Further, the thickness of the N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure is 5-20 mu m.
Further, the thickness of the alumina layer is 0.6-1.0 μm.
The beneficial effects are that:
the insulating coating prepared by the method is applied to the process of preparing the coating by magnetron sputtering, a multilayer structure formed by alternately lean N silicon nitride and rich N silicon nitride is prepared by periodically changing the nitrogen flow, and the N content in the deposited silicon nitride can be adjusted by periodically changing the nitrogen flow, so that the deposited multilayer structure of alternately lean N silicon nitride and rich N silicon nitride can generate micromechanics of alternate tensile stress and compressive stress. The aforementioned micromechanical structure can effectively reduce internal stress of the coating by means of mutual stress cancellation.
Compared with the prior art, the invention changes the existing mode of reducing internal stress by selecting the expansion coefficient between the coating material and the matrix material, and creatively proposes to reduce the whole internal stress by mutually counteracting microscopic stresses among different layers in the multilayer structure of the coating material. In the preparation method, the mode of filling a certain amount of nitrogen in the magnetron sputtering process in the prior art is changed, and the mode of periodically controlling the flow of the nitrogen is selected to replace the nitrogen, so that the multilayer structure formed by alternately lean N silicon nitride and rich N silicon nitride is obtained.
The deposited bonding layer-deposited N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure-aluminum oxide layer structure prepared by the method can keep insulation at about 1MΩ in a high-temperature environment at 1000 ℃, and has more excellent high-temperature resistance compared with the prior art.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
Fig. 1 is a schematic view of a high temperature resistant insulating coating on the surface of a thermocouple wire according to this embodiment.
Fig. 2 is a profile of a coated k-type thermocouple wire according to this example.
Fig. 3 is a cross-sectional view of an alternate N-lean silicon nitride and N-rich silicon nitride multilayer structure and an EDS line scan profile of element N as described in this example.
Fig. 4 is a cross-sectional SEM topography of the titanium/single layer silicon nitride/aluminum oxide composite coating described in this example.
Detailed Description
In order to more clearly describe the technical scheme of the embodiment of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and the embodiment.
Examples
The high-temperature insulating coating and the metal matrix have larger difference in thermal expansion coefficient, so that the higher stress is one of the reasons why the coating is easy to peel off, in the prior art, the Shanghai aviation measurement and control technical institute of China aviation industry group company aims at accurately measuring the temperature of the turbine blade, and a coating structure with smaller internal attraction is designed in the process of designing a temperature sensor (patent CN 109338290A). The method utilizes an ion deposition technology to directly deposit a multi-layer film on the surface of a turbine blade, forms a gradient functional structure from an alumina film layer (a thermal growth layer) to a NiCrAlY alloy film layer (a transition layer) between a substrate and an insulating layer, releases thermal stress generated by mismatch of thermal expansion coefficients between a nickel-based alloy and the insulating layer, and achieves the purposes of improving the structural strength of a film thermocouple, prolonging the high-temperature service life of the film thermocouple and improving the working temperature of the film thermocouple.
The applicant tries to achieve the purpose of reducing the internal stress by the structural characteristics of the coating itself based on the way of matching the thermal expansion coefficients of the high-temperature insulating coating and the metal matrix to reduce the internal stress in the prior art, and in the process, the applicant finds that the insulating coating prepared by using silicon nitride can achieve the aforementioned functions, for example, the silicon nitride layer obtained by applying direct-current reactive sputtering in the patent (CN 108265272A) in the prior art has high hardness, the silicon nitride layer obtained by using radio-frequency sputtering has high toughness, and the advantages of the two are combined by alternating multilayer design, so that the thickness of the coating is increased and the internal stress of the coating is reduced.
Based on the foregoing, the applicant found that simply stacking a high hardness layer and a high toughness layer does not effectively reduce the internal stress of the coating, but greatly reduces the internal stress of the coating by changing the microscopic stress in the coating, so that the preparation method of the low stress and high temperature-bonded insulating coating described in this embodiment includes the following steps sequentially performed, performing a pre-plating treatment, performing Ar ion sputter cleaning, performing a step of depositing a bonding layer, obtaining a deposited bonding layer through the step of depositing a bonding layer, performing the step of depositing an N-lean silicon nitride and an N-rich silicon nitride alternating multilayer structure, and obtaining a deposited silicon/silicon oxide composite through the step of depositing an N-lean silicon nitride and an N-rich silicon nitride alternating multilayer structure.
The step of depositing the N-lean silicon nitride and the N-rich silicon nitride alternating multilayer structure is to deposit silicon nitride on the surface of a deposited bonding layer through a magnetron sputtering technology to obtain the deposited N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure, wherein the silicon nitride is obtained through reactive sputtering of a Si target and nitrogen by the magnetron sputtering technology.
The deposited N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure is actually a multilayer structure formed by alternately lean silicon nitride and rich silicon nitride, and the Si target and nitrogen can be deposited to obtain a silicon nitride layer when being subjected to reactive sputtering deposition.
The nitrogen content in two adjacent layers of silicon nitride is regulated and controlled by periodically changing the flow of nitrogen in the magnetron sputtering process, so that a multilayer structure formed by alternately lean N silicon nitride and rich N silicon nitride is obtained. It should be understood at first that the principle of the magnetron sputtering method for preparing the silicon nitride film is that silicon atoms sputtered from a silicon target and nitrogen ions ionized by nitrogen gas react on the surface of a substrate as follows: 3 Si(s) +2N.sub.2 (g). Fwdarw.Si3N.sub.4(s) to form a silicon nitride film. The ideal stoichiometric silicon nitride film has an Si to N atomic ratio of 3:4.
Applicants combine magnetron sputtering to form a thin film which is an unbalanced growth process, and depending on the concentration ratio of the reactants Si and N, a series of non-stoichiometric amorphous SiNx films are usually formed, if the reactant N concentration is insufficient, N-lean silicon nitride is obtained, and if N is excessive, N-rich silicon nitride is obtained. The invention in this example is to adjust the concentration of reactant N by periodically varying the flow of nitrogen to obtain silicon nitride films of different Si to N ratios. When the flow rate of the introduced nitrogen gas is 0, a pure silicon film should be obtained according to the foregoing theory, however, part of N atoms in the adjacent N-rich silicon nitride layer will diffuse into the silicon film through the interface, so that an N-lean silicon nitride layer is actually obtained.
In the multilayer structure of alternately composed of the N-lean silicon nitride and the N-rich silicon nitride obtained according to the foregoing, the N-lean silicon nitride layer exhibits a tensile stress state in which the thin film exhibits an attractive action between atoms due to the presence of N vacancies, whereas the N-rich silicon nitride layer exhibits a compressive stress state in which no vacancies are present and the structure is dense.
Compared with the mode of improving the binding force by controlling the difference of the thermal expansion coefficients of the high-temperature insulating coating and the metal matrix in the prior art, the invention provides an implementation mode of reducing the internal stress by adjusting the micromechanics relation between adjacent layers in the multilayer structure of the insulating coating; compared with the patent (CN 108265272A), the invention prepares the multilayer structure consisting of the N-lean silicon nitride and the N-rich silicon nitride alternately by controlling the nitrogen cycle flow, wherein the micromechanics generated by the N-lean silicon nitride layer are in a tensile stress state, the micromechanics generated by the N-rich silicon nitride layer are in a compressive stress state, and the structures of the internal stress in the adjacent N-lean layer and the internal stress in the N-rich layer counteract part of the internal stress, so that the internal stress of the whole coating is greatly reduced.
After solving the problem of higher internal stress, the problem of insufficient film-base binding force should be solved. The prior art patent (CN 104789964A) deposits a Ti metal layer on the superalloy substrate surface, the Ti metal layer being deposited to a thickness of 1 μm or more and preferably 1 to 100 μm. The invention improves the binding force by adjusting the thickness of the Ti metal layer.
The preparation is performed by applying the same principle (namely, the thickness of the deposited bonding layer is controlled to control the bonding force), the step of depositing bonding metal on the surface of the base metal by using a magnetron sputtering technology to obtain the deposited bonding layer, the thickness of the deposited bonding layer is controlled by controlling the deposition time, the bonding metal is Ti (or Cr), and the deposition time of the bonding metal is 2-5min. And taking the basic parameters as the basic parameters to carry out a series of subsequent specific implementation processes.
In order to prove that the multilayer structure formed by alternately lean N silicon nitride and rich N silicon nitride in the previous embodiment can effectively reduce the internal stress of the coating, specific embodiments are designed in the embodiment. In these embodiments, the applicant has chosen the materials according to the purpose of preparing the high temperature resistant insulating material and has limited some parameters with respect to the material properties required in the detailed field.
In order to meet the main application field of high-temperature insulating materials as far as possible, namely, the aircraft flies in the ionosphere, in the embodiment, flexible k-type or e-type thermocouple wires are selected as the base material, and the working condition is 1000 ℃.
The applicant considers that the thermal expansion coefficient of the nickel-base alloy is above 14 multiplied by 10 < -6 >/K, si and SiN are about 3 multiplied by 10 < -6 >/K, the thermal expansion coefficient of Ti is 9.4multiplied by 10 < -6 >/K, cr, and the thermal expansion coefficient is 6.5multiplied by 10 < -6 >/K. The adhesion metal is preferably Ti (or Cr) in order to improve the matching of the thermal expansion coefficient of the coating and the matrix. In some implementations, other materials can be selected according to the substrate by applying the key control method of the invention to achieve the coating thickness change.
The parameters of the magnetron sputtering are that the cavity is vacuumized to 1X 10 < -3 > Pa-5X 10 < -3 > Pa before the step of depositing the bonding layer is carried out, the Ar gas flow is 20-80 sccm in the Ar ion sputtering cleaning step, the Ar purity is over 99.9 percent, the gas pressure is 0.2-2.0 Pa, the currents of the Si target and the Ti (or Cr) target are 1-5A in the step of depositing the N-lean silicon nitride and the N-rich silicon nitride alternating multilayer structure and the step of depositing the bonding layer, the purity of the Ti (or Cr) and the Si target is over 99 percent, and the negative bias voltage of the matrix is-50 to-100V.
The purity of nitrogen in the step of depositing the N-lean silicon nitride and the N-rich silicon nitride alternating multilayer structure is 99.999%, the time for depositing the nitrogen or the silicon nitride is 100min, the periodic period is 20-30min, and the steps are performed for 3-5 periods in total.
N in said one period 2 The flow rate is 0-5sccm for 5min, followed by N 2 The flow rate is 10-20sccm and kept for 20min, N 2 The partial pressure is kept between 0 and 0.15Pa.
In order to avoid the influence of the experimental effect on the surface structure of the coating (the coarse columnar structure of the surface of the silicon nitride can reduce the compactness of the coating and further reduce the insulating property of the coating), the applicant can seal the defect of the silicon nitride by preparing a denser aluminum oxide layer on the surface of the silicon nitride by adopting a sol-gel method.
Therefore, in this embodiment, the step of depositing the silicon/silicon oxide and metal bonding layer further includes a step of preparing an alumina coating, where the step of preparing an alumina coating is to apply a sol-gel method to cover a denser alumina layer on the deposited N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure. The sol-gel method comprises the steps of preparing aluminum sol which is mixed liquid of aluminum nitrate and sodium carbonate, wherein the step of preparing an aluminum oxide coating comprises the steps of pulling a material deposited with the deposited N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure in the aluminum sol for 30-40 times by adopting a pulling method, and finally preserving heat in a high-temperature furnace.
The mass fraction of the aluminum nitrate is 30wt%, the mass fraction of the sodium carbonate mixed solution is 20-20wt%, and the heat preservation temperature is 900 ℃ and the duration time is 1-2 hours.
In one embodiment, the preparation method is specifically as follows:
a pre-plating treatment step of the alloy,
sequentially performing ultrasonic treatment on the thermocouple wire in acetone and alcohol for 15min, removing impurities, and cleaning the surface;
an Ar ion sputtering cleaning step is carried out,
pre-pumping background vacuum to 2.00×10 -3 Pa; then, introducing high-purity Ar gas with the purity of 99.999 percent into the cavity, applying negative bias to the matrix, ionizing Ar gas near the sample under negative bias of-1500V to obtain Ar+, bombarding the thermocouple wire, and continuously bombarding for 20min to remove a natural oxide layer on the surface of the thermocouple wire;
a step of depositing a bonding layer,
maintaining the Ar gas flow at 40sccm, applying 2A current to the Ti target, applying-50V bias to the substrate, and depositing the Ti bonding layer for 2min; the Ar gas flow is kept unchanged, then N2 with the purity of 99.999% is introduced into the cavity as reaction gas, and the current of the Si target is set to be 2A.
A step of depositing an alternating multilayer structure of lean N silicon nitride and rich N silicon nitride,
applying a bias voltage of-50V to the substrate, and depositing a silicon nitride coating on the surface of the thermocouple wire for 100min. Periodically varying N during silicon nitride deposition 2 Flow, 1 cycle at 25min, where N 2 The flow rate was maintained at 0sccm for 5min, followed by N 2 The flow is kept at 20sccm for 20min, and 4 periods are repeated, so that the nitrogen-lean/nitrogen-rich multilayer silicon nitride coating with the nitrogen element content being alternately changed can be obtained. And after the coating is deposited, cooling to below 50 ℃ in a vacuum environment, deflating to atmospheric pressure, and obtaining the metal Ti bonding layer and the multilayer silicon nitride coating on the surface of the substrate.
A step of preparing an alumina coating layer,
preparing aluminum sol with the mass fractions of 40wt% and 30wt% of aluminum nitrate and sodium carbonate respectively, pulling the aluminum sol on the surface of a thermocouple wire deposited with silicon nitride by adopting a pulling method, drying the thermocouple wire by using an oven after each pulling, repeatedly pulling for 50 times, and finally preserving the temperature in a high-temperature furnace at 800 ℃ for 4 hours to obtain an aluminum oxide layer on the surface.
In one embodiment, the preparation method is substantially the same as the previous one, but the following parameter adjustments are made:
in the step of depositing the bonding layer, a Ti bonding layer is deposited for 5min. The periodic nitrogen flow control technology is not applied any more, and the silicon nitride layer is directly deposited in a constant nitrogen environment.
The parameters detected in the two embodiments are respectively:
in the former embodiment, the adhesive layer thickness is 0.2 μm; in the latter embodiment, the adhesive layer thickness is 0.3 μm.
The internal stress of the SiN multilayer coating prepared on the silicon substrate is measured by using a cantilever beam method, wherein the internal stress of the SiN layer in the former embodiment is 40MPa, and the internal stress of the SiN layer in the latter embodiment is 800MPa, so that the internal stress of the coating can be effectively reduced by the multilayer structure formed by alternately lean N silicon nitride and rich N silicon nitride.
The applicant devised a control group to observe the effect of the deposited tie layer on internal stress, so in one embodiment the preparation method is specifically as follows:
the pre-plating treatment step, the Ar ion sputtering cleaning step, is the same as the previous embodiment, and the step of depositing the adhesive layer is not performed.
In the step of depositing the N-lean silicon nitride and the N-rich silicon nitride alternating multilayer structure,
applying a bias voltage of-50V to the substrate, and depositing a silicon nitride coating on the surface of the thermocouple wire for 100min. The N2 flow rate is periodically changed in the silicon nitride deposition process, and is kept for 5min at 25min for 1 period, wherein the N2 flow rate is kept for 0sccm for 5min, then the N2 flow rate is kept for 20min at 20sccm, and 4 periods are repeated, so that the nitrogen-lean/nitrogen-rich multilayer silicon nitride coating with the nitrogen element content being alternately changed can be obtained. And after the coating is deposited, cooling to below 50 ℃ in a vacuum environment, deflating to atmospheric pressure, and obtaining the metal Ti bonding layer and the multilayer silicon nitride coating on the surface of the substrate.
A step of preparing an alumina coating layer,
preparing aluminum sol with the mass fractions of 40wt% and 30wt% of aluminum nitrate and sodium carbonate respectively, pulling the aluminum sol on the surface of a thermocouple wire deposited with silicon nitride by adopting a pulling method, drying the thermocouple wire by using an oven after each pulling, repeatedly pulling for 50 times, and finally preserving the temperature in a high-temperature furnace at 800 ℃ for 4 hours to obtain an aluminum oxide layer on the surface.
And finally, measuring the internal stress SiN layer internal stress of the SiN multilayer coating prepared on the silicon substrate by using a cantilever beam method to be 160MPa, wherein the internal stress is 800MPa when only the deposition layer is increased, and only the N-poor silicon nitride and N-rich silicon nitride alternating multilayer structure is increased, so that the internal stress is 160MPa, and the N-poor silicon nitride and N-rich silicon nitride alternating multilayer structure in the invention in the embodiment has the effect of obviously reducing the internal stress.
To further demonstrate that the multilayer structure of alternately N-lean and N-rich silicon nitride is effective in reducing internal stress in the coating, the applicant devised two further embodiments based on the foregoing examples.
In one embodiment, the preparation method is specifically as follows:
a pre-plating treatment step, an Ar ion sputter cleaning step is identical to that in the previous embodiment,
step of depositing an adhesive layer
Maintaining the Ar gas flow at 40sccm, applying 2A current on the Cr target, applying-50V bias voltage on the substrate, and depositing Cr bonding layer for 3min; the Ar gas flow is kept unchanged, and then N2 with the purity of 99.999% is introduced into the cavity as reaction gas.
A step of depositing an alternating multilayer structure of lean N silicon nitride and rich N silicon nitride,
the current of the Si target was set to 2A, a-50V bias was applied to the substrate, and a silicon nitride coating was deposited on the thermocouple wire surface for 100 minutes. The N2 flow rate is periodically changed in the silicon nitride deposition process, and the period is 1 in 25min, wherein the N2 flow rate is 0sccm and is kept for 5min, then the N2 flow rate is 10sccm and is kept for 20min, and 4 periods are repeated, so that the nitrogen-lean/rich multilayer silicon nitride coating with the nitrogen element content being alternately changed can be obtained. And after the coating is deposited, cooling to below 50 ℃ in a vacuum environment, deflating to atmospheric pressure, and obtaining the metal Cr bonding layer and the multilayer silicon nitride coating on the surface of the substrate.
A step of preparing an alumina coating layer,
preparing aluminum sol with the mass fractions of aluminum nitrate and sodium carbonate of 30wt% and 25wt%, pulling the surface of the thermocouple wire deposited with silicon nitride in the aluminum sol by adopting a pulling method, drying the thermocouple wire by using an oven after each pulling, repeatedly pulling for 40 times, and finally preserving the temperature in a high-temperature furnace for 4 hours at 900 ℃ to obtain an aluminum oxide layer on the surface.
In one embodiment, the preparation method is specifically as follows:
a pre-plating treatment step, an Ar ion sputter cleaning step is identical to that in the previous embodiment,
step of depositing an adhesive layer
Maintaining the Ar gas flow at 40sccm, applying 2A current on the Ti target, applying-50V bias voltage on the substrate, and depositing the Ti bonding layer for 5min; the Ar gas flow is kept unchanged, and then N2 with the purity of 99.999% is introduced into the cavity as reaction gas.
A step of depositing an alternating multilayer structure of lean N silicon nitride and rich N silicon nitride,
the current of the Si target was set to 2A, a-50V bias was applied to the substrate, and a silicon nitride coating was deposited on the thermocouple wire surface for 90 minutes. The N2 flow rate is periodically changed in the silicon nitride deposition process, and is kept for 5min at 25min for 1 period, wherein the N2 flow rate is kept for 0sccm for 20min, and then the N2 flow rate is kept for 15sccm for 4 periods, so that the nitrogen-lean/nitrogen-rich multilayer silicon nitride coating with the nitrogen element content being alternately changed can be obtained. And after the coating is deposited, cooling to below 50 ℃ in a vacuum environment, deflating to atmospheric pressure, and obtaining the metal Cr bonding layer and the multilayer silicon nitride coating on the surface of the substrate.
A step of preparing an alumina coating layer,
preparing aluminum sol with the mass fractions of aluminum nitrate and sodium carbonate of 30wt% and 25wt%, pulling the surface of the thermocouple wire deposited with silicon nitride in the aluminum sol by adopting a pulling method, drying the thermocouple wire by using an oven after each pulling, repeatedly pulling for 40 times, and finally preserving the temperature in a high-temperature furnace for 4 hours at 900 ℃ to obtain an aluminum oxide layer on the surface.
In the two embodiments, the internal stress SiN layer internal stress of the SiN multilayer coating prepared on the silicon substrate is 28MPa and 33MPa respectively by using a cantilever beam method. It can be seen that its internal stress is at a lower level. On the basis of the detection in the previous embodiment, the applicant further performs a bonding force (bending method) test, and the test result shows that when the coating structural material of the deposition layer-lean N-nitride and rich N-nitride alternating multilayer structure disclosed in the present embodiment is applied, the coating material is not peeled off, and the coating peeling occurs only in the structure of one of the deposition bonding layer or the lean N-nitride and rich N-nitride alternating multilayer structure. The foregoing experimental contents demonstrate that the inventive structure in this embodiment has a good bonding property.
After the previous experimental results, the applicant measured the resistance of the coating at high temperature using a keithley 6514 electrometer in the united states for all the materials obtained in the previous examples, with resistance values of 1.2mΩ,0.95mΩ,1.1mΩ,1.05mΩ,0.86mΩ in that order. It can be seen that the coating material prepared in the present invention can still maintain good dielectric properties at 1000 ℃ and there is no insulating coating material having the aforementioned good dielectric properties at a high temperature of 1000 ℃ in the prior art.
The applicant defined parameters of the coating based on experimental results, and examined the data obtained in the various examples.
Firstly, the coating material is Ti or Cr-deposited N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure-aluminum oxide structure, the thickness of the deposited bonding layer, namely Ti or Cr, is 0.2-0.3 mu m, the thickness of the deposited N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure is 5-20 mu m, and the thickness of the aluminum oxide layer is 0.6-1.0 mu m.
The above is only an example portion of the application and is not intended to limit the application in any way. Any simple modification, equivalent variation and modification of any of the simple modification embodiments described above still fall within the scope of the claims.
Claims (7)
1. The preparation method of the low-stress strong-bonding high-temperature insulating coating comprises the following steps of sequentially performing a pre-plating treatment step, an Ar ion sputtering cleaning step, a bonding layer depositing step, an N-poor silicon nitride and N-rich silicon nitride alternating multilayer structure depositing step, and is characterized in that: the step of depositing the lean N silicon nitride and rich N silicon nitride alternating multilayer structure is to deposit silicon nitride on the surface of a deposited bonding layer by a magnetron sputtering technology to obtain the lean N silicon nitride and rich N silicon nitride alternating multilayer structure, wherein the silicon nitride is obtained by reactive sputtering of a Si target and nitrogen by the magnetron sputtering technology;
in the magnetron sputtering process, the nitrogen content in two adjacent layers of silicon nitride is regulated and controlled by periodically changing the nitrogen flow, so that the N-lean silicon nitride and N-rich silicon nitride alternate multilayer structure is a multilayer structure formed by alternately lean N silicon nitride and rich N silicon nitride;
the step of depositing the bonding layer is to deposit bonding metal on the surface of the base metal through a magnetron sputtering technology to obtain the deposited bonding layer, wherein the thickness of the deposited bonding layer is controlled by controlling the deposition time, the bonding metal is Ti or Cr, and the deposition time of the bonding metal is 2-5min;
the nitrogen in the step of carrying out the alternating multilayer structure of lean N silicon nitride and rich N silicon nitride is 99.999 percent, the time for depositing the silicon nitride is 100 minutes, the periodic period is 20-30 minutes, and the total steps are carried out for 3-5 periods;
n in one period 2 The flow rate is 0-5sccm for 5min, followed by N 2 The flow rate is 10-20sccm and kept for 20min, N 2 The partial pressure is kept between 0 and 0.15Pa.
2. The method for preparing the low-stress strong-bonding high-temperature insulating coating according to claim 1, which is characterized by comprising the following steps: the parameters of the magnetron sputtering are that the cavity is vacuumized to 1 multiplied by 10 before the step of depositing the bonding layer -3 Pa～5×10 -3 Pa；
In the Ar ion sputtering cleaning step, the Ar gas flow is 20-80 sccm, the Ar purity is over 99.9 percent, and the air pressure is 0.2-2.0 Pa;
in the step of alternately forming the multilayer structure of the lean N silicon nitride and the rich N silicon nitride and the step of depositing the bonding layer, the current of the Si target, the Ti target or the Cr target is 1-5A, and the purity of the Ti target or the Cr target and the Si target is more than 99%;
the negative bias voltage of the substrate is-50 to-100V.
3. The method for preparing the low-stress strong-bonding high-temperature insulating coating according to claim 1, which is characterized by comprising the following steps: the method comprises the steps of depositing the N-lean silicon nitride, the N-rich silicon nitride and the metal bonding layer, and then preparing an alumina coating, wherein the alumina coating is prepared by coating a denser alumina layer on the N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure by a sol-gel method.
4. A method for preparing a low stress, strong bond, high temperature insulating coating according to claim 3, characterized by: the sol-gel method comprises the steps of preparing aluminum sol, wherein the aluminum sol is mixed liquid of aluminum nitrate and sodium carbonate;
the step of preparing the aluminum oxide coating comprises the steps of pulling the material deposited with the N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure in aluminum sol for 30-40 times by adopting a pulling method, and finally preserving heat in a high-temperature furnace;
the mass fraction of the aluminum nitrate is 30wt%, the mass fraction of the sodium carbonate mixed solution is 20-20wt%, and the heat preservation temperature is 900 ℃ and the duration time is 1-2 hours.
5. The method for preparing the low-stress strong-bonding high-temperature insulating coating according to claim 1, which is characterized by comprising the following steps: the thickness of the deposited adhesive layer is 0.2-0.3 mu m.
6. The method for preparing the low-stress strong-bonding high-temperature insulating coating according to claim 4, which is characterized in that: the thickness of the N-lean silicon nitride and N-rich silicon nitride alternating multilayer structure is 5-20 mu m.
7. The method for preparing the low-stress strong-bonding high-temperature insulating coating according to claim 4, which is characterized in that: the thickness of the alumina layer is 0.6-1.0 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310129637.XA CN116180075B (en) | 2023-02-17 | 2023-02-17 | Preparation method of low-stress strong-bonding high-temperature insulating coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310129637.XA CN116180075B (en) | 2023-02-17 | 2023-02-17 | Preparation method of low-stress strong-bonding high-temperature insulating coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116180075A CN116180075A (en) | 2023-05-30 |
| CN116180075B true CN116180075B (en) | 2024-02-23 |
Family
ID=86445813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310129637.XA Active CN116180075B (en) | 2023-02-17 | 2023-02-17 | Preparation method of low-stress strong-bonding high-temperature insulating coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116180075B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280412A (en) * | 2007-12-29 | 2008-10-08 | 电子科技大学 | Aluminum nitride piezoelectric film and preparation thereof |
| US7727882B1 (en) * | 2007-12-17 | 2010-06-01 | Novellus Systems, Inc. | Compositionally graded titanium nitride film for diffusion barrier applications |
| KR20120012891A (en) * | 2010-08-03 | 2012-02-13 | 삼성모바일디스플레이주식회사 | Substrate for flexible display and Method for manufacturing the same |
| CN102634753A (en) * | 2011-02-12 | 2012-08-15 | 深圳职业技术学院 | Hard coating and preparation method thereof |
| CN104513958A (en) * | 2013-09-29 | 2015-04-15 | 无锡慧明电子科技有限公司 | Method for preparing silicon nitride film through magnetron sputtering |
| CN106148904A (en) * | 2015-04-17 | 2016-11-23 | 中国科学院金属研究所 | A kind of nano-stack CrN plated film and its preparation method and application |
| CN106191770A (en) * | 2015-05-05 | 2016-12-07 | 中国科学院宁波材料技术与工程研究所 | Porous silicon nitride based sealing coating and preparation method and application |
| CN108265272A (en) * | 2016-12-30 | 2018-07-10 | 中国科学院宁波材料技术与工程研究所 | Nanometer multilayer silicon nitride ceramics coating, preparation method and application |
| CN114990481A (en) * | 2022-06-10 | 2022-09-02 | 吉林大学 | Self-adaptive nano multilayer film for intelligently assembling root-shaped capillary diffusion channel and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7550067B2 (en) * | 2004-06-25 | 2009-06-23 | Guardian Industries Corp. | Coated article with ion treated underlayer and corresponding method |
| DE102008054139B4 (en) * | 2008-10-31 | 2010-11-11 | Schott Ag | Glass or glass-ceramic substrate with scratch-resistant coating, its use and process for its preparation |
-
2023
- 2023-02-17 CN CN202310129637.XA patent/CN116180075B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7727882B1 (en) * | 2007-12-17 | 2010-06-01 | Novellus Systems, Inc. | Compositionally graded titanium nitride film for diffusion barrier applications |
| CN101280412A (en) * | 2007-12-29 | 2008-10-08 | 电子科技大学 | Aluminum nitride piezoelectric film and preparation thereof |
| KR20120012891A (en) * | 2010-08-03 | 2012-02-13 | 삼성모바일디스플레이주식회사 | Substrate for flexible display and Method for manufacturing the same |
| CN102634753A (en) * | 2011-02-12 | 2012-08-15 | 深圳职业技术学院 | Hard coating and preparation method thereof |
| CN104513958A (en) * | 2013-09-29 | 2015-04-15 | 无锡慧明电子科技有限公司 | Method for preparing silicon nitride film through magnetron sputtering |
| CN106148904A (en) * | 2015-04-17 | 2016-11-23 | 中国科学院金属研究所 | A kind of nano-stack CrN plated film and its preparation method and application |
| CN106191770A (en) * | 2015-05-05 | 2016-12-07 | 中国科学院宁波材料技术与工程研究所 | Porous silicon nitride based sealing coating and preparation method and application |
| CN108265272A (en) * | 2016-12-30 | 2018-07-10 | 中国科学院宁波材料技术与工程研究所 | Nanometer multilayer silicon nitride ceramics coating, preparation method and application |
| CN114990481A (en) * | 2022-06-10 | 2022-09-02 | 吉林大学 | Self-adaptive nano multilayer film for intelligently assembling root-shaped capillary diffusion channel and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116180075A (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Structure and properties of Cr2O3 coatings deposited using DCMS, PDCMS, and DOMS | |
| Kester et al. | Deposition and characterization of boron nitride thin films | |
| CN105908126B (en) | The AlTiN composite coatings and preparation method of a kind of high Al content | |
| JPH01281A (en) | overlay coating | |
| TW200427870A (en) | Fluoride-containing coating and coated member | |
| RU2553803C2 (en) | Tribology combined with corrosion resistance: new family of pvd- and pacvd coatings | |
| CN107313013A (en) | Compound gold coated films and preparation method thereof | |
| Wolf et al. | Ion bombardment during thin film deposition and its influence on mechanical and chemical surface properties | |
| CN108611613B (en) | Preparation method of nano multilayer structure carbon-based film | |
| CN105525273B (en) | A kind of stainless steel carborundum hydrogen permeation preventing coating and preparation method thereof | |
| Monteiro et al. | Deposition of mullite and mullite-like coatings on silicon carbide by dual-source metal plasma immersion | |
| CN114196914B (en) | Carbide high-entropy ceramic material, carbide ceramic layer and preparation method and application thereof | |
| CN108330455B (en) | Cr (chromium)2Preparation method of coating with adjustable AlC phase purity | |
| CN116180075B (en) | Preparation method of low-stress strong-bonding high-temperature insulating coating | |
| WO2014109425A1 (en) | Method for producing thin film on nanocrystalline max | |
| Sippola et al. | Comparison of mechanical properties and composition of magnetron sputter and plasma enhanced atomic layer deposition aluminum nitride films | |
| CN101586227A (en) | Adopt ion plating on growth substrates, to prepare the method for aluminium nitride material | |
| KR101695590B1 (en) | ELECTRODE FOR WATER TREATMENT WITH DIAMOND COATING LAYER ON Ti SUBSTRATE AND MANUFACTURING METHOD THREREOF | |
| JP2022507087A (en) | Al-rich cubic AlTiN coating deposited from a ceramic target | |
| TW201945566A (en) | Coating comprising MCrAl-X coating layer | |
| Järvinen et al. | Improved adhesion between a sputtered alumina coating and a copper substrate | |
| Monteiro et al. | Synthesis of multi-element thin-films using mixed metal plasma streams | |
| JP2013221215A (en) | Surface coated member and method for manufacturing the same, and method for coating the surface coated member | |
| Rao et al. | Electron cyclotron resonance plasma assisted sputter deposition of boron nitride films | |
| CN113874540B (en) | Cubic aluminum-rich AlTiN coatings deposited from ceramic targets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231205 Address after: 610031 No. two, section 111, ring road, Chengdu, Sichuan, China Applicant after: SOUTHWEST JIAOTONG University Applicant after: ULTRA-HIGH-SPEED AERODYNAMICS INSTITUTE, CHINA AERODYNAMICS RESEARCH AND DEVELOPMENT CENTER Address before: 610031 No. two, section 111, ring road, Chengdu, Sichuan, China Applicant before: SOUTHWEST JIAOTONG University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |