CN116332630A - Preparation method of alumina ceramic for semiconductor equipment - Google Patents
Preparation method of alumina ceramic for semiconductor equipment Download PDFInfo
- Publication number
- CN116332630A CN116332630A CN202310589432.XA CN202310589432A CN116332630A CN 116332630 A CN116332630 A CN 116332630A CN 202310589432 A CN202310589432 A CN 202310589432A CN 116332630 A CN116332630 A CN 116332630A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- alumina ceramic
- powder
- alumina
- sintering
- 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.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000004065 semiconductor Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000000919 ceramic Substances 0.000 claims abstract description 75
- 238000005245 sintering Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052574 oxide ceramic Inorganic materials 0.000 claims abstract description 4
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 31
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000748 compression moulding Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 238000005452 bending Methods 0.000 claims description 9
- 238000001020 plasma etching Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000009694 cold isostatic pressing Methods 0.000 claims description 4
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 32
- 238000005260 corrosion Methods 0.000 abstract description 32
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 16
- 239000012752 auxiliary agent Substances 0.000 abstract description 11
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 abstract description 10
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract description 10
- 239000003292 glue Substances 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 56
- 230000000052 comparative effect Effects 0.000 description 26
- 210000002381 plasma Anatomy 0.000 description 22
- 238000005530 etching Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- -1 rare earth compound Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67069—Apparatus for fluid treatment for etching for drying etching
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
- C04B2235/445—Fluoride containing anions, e.g. fluosilicate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to the field of semiconductor ceramic materials, in particular to a preparation method of alumina ceramic for semiconductor equipment, which takes alumina and magnesium fluoride as raw materials and is prepared through simple mixing, ball milling, glue injection, granulation, molding and sintering procedures. According to the invention, the sintering auxiliary agents of the upper layer and the lower layer of the aluminum oxide ceramic can completely escape by adjusting the content of magnesium fluoride among the layers of the ceramic and the thickness of each layer and combining with the optimization of technological parameters, so that the corrosion resistance of the ceramic is improved. The ceramic has the advantages of higher density, good compactness, low grain size, stronger connectivity among layers inside and excellent mechanical strength. Meanwhile, the material thickness is controllable and adjustable, and the preparation and acquisition of large-size ceramic materials can be realized, so that the ceramic sintered material can be used for manufacturing various key components of semiconductor vacuum manufacturing equipment.
Description
Technical Field
The invention relates to the field of semiconductor ceramic materials, in particular to a preparation method of alumina ceramic for semiconductor equipment, and an alumina ceramic structural member obtained by the method has higher corrosion resistance and can be widely applied to semiconductor etching equipment.
Background
Plasma processing apparatus are widely used in semiconductor manufacturing, and are mainly used for etching, surface cleaning, and other processes. The working principle is that halogen-containing compound gas in a reaction chamber is ionized into plasma, and free radicals in the plasma are used for bombarding or sputtering surface molecules of etched materials to form volatile substances, so that the purpose of etching is realized. In addition to reducing the service life of the components, the components in the reaction chamber are exposed to plasma and are subjected to plasma corrosion to different degrees, so that the use cost of the plasma processing device is increased, and metal/ceramic particles generated by plasma corrosion pollute the reaction chamber and the surface of a workpiece to be processed and affect the quality of the workpiece to be processed, so that the necessity of corrosion resistance of a chamber used in a semiconductor manufacturing process using a deposition device such as Chemical Vapor Deposition (CVD) or an etching device such as plasma etching or the like to highly corrosive gases or plasmas is higher and higher. In order to improve the plasma corrosion resistance of the component, various technical measures are adopted, such as spraying inorganic coating of yttrium oxide, aluminum oxide and the like on the metal component, but the sprayed coating has weak binding force with the metal component, and the expansion coefficients of the inorganic coating and the metal component are not matched, so that the risk of falling off exists in the use process. As CN1288108C, a plasma resistant member method is disclosed, Y being carried out thermally on an alumina substrate 2 O 3 Or a YAG thermal spray coating improves the plasma etch resistance of the material. In order to improve the adhesion of the component, the surface roughness of the alumina substrate is adjusted by chemical etching on the surface of the alumina substrate. The method is complex to prepare, a composite component with a thicker corrosion-resistant layer cannot be obtained, meanwhile, the adhesion between the film and the substrate obtained by the method is poor, the volume porosity is high, particles fall into a process chamber, the mechanical property of yttrium oxide is poor, and the peeling and damage phenomena of the chamber component of the etching machine are easier to generate in the manufacturing, transportation and service processes due to the lower mechanical property of the yttrium oxide. For the preparation of dense ceramics, the melting point of yttria up to 2430 ℃ makes densification thereof generally require higher temperatures, which is common in the preparation of yttria ceramicsThe addition of additives promotes densification of the yttria ceramic, which will also result in the creation of corrosion resistant weak areas. In addition, the ceramic material such as alumina, yttria and the like is sintered and densified to manufacture a component, so that the plasma corrosion resistance is improved to a certain extent, but some sintering aids added in the preparation process of the ceramic material such as alumina, yttria and the like are easy to be corroded by plasma, abnormal growth of crystal grains of the ceramic material in the sintering process can cause poor ceramic microstructure so as to degrade the ceramic performance, the service life of the ceramic component is greatly shortened, and in addition, the rare earth compound is expensive and has poor mechanical property.
Alumina ceramic is a ceramic material with low price, excellent comprehensive performance and the most widely applied, has the characteristics of heat resistance, corrosion resistance, high strength, small dielectric loss and the like, is widely applied to the parts of high-frequency plasma etching devices for semiconductors and liquid crystals, but the currently used high-purity alumina ceramic also contains high-content SiO (silicon oxide) 2 Impurity phases such as MgO, caO, etc., for example, CN1288872A discloses a translucent alumina sintered body and a method for producing the same, which selects an alpha-alumina powder having substantially no polyhedral primary particles of broken surfaces, and obtains a high-purity alumina ceramic having a good corrosion resistance by strictly controlling the total content of alkali metal elements and alkaline earth metal elements in a sintered ceramic material, which is considered to be doped with metal ions in a sintering agent such as a sintering agent containing alkali metal or alkaline earth metal ions during the sintering of the alumina ceramic, and which is chemically reacted with plasma and halogen gas and an acid solution or alkali solution, etc. when used. However, the ceramic material has higher purity of the required raw materials, has strict requirements on production conditions, and is difficult to realize in actual production. On the other hand, the density of the alumina ceramic still needs to be improved, and a certain number of pores and the like still exist. Under the combined action of the plasma and the reaction gas, the problem of defects, particles, metal impurities and the like can be generated in an undensified area with pores inside the alumina ceramic. In addition, the existing preparation method of the large-size and ultra-high-purity alumina ceramic also has the problems of easy deformation, cracking, difficult sintering, compactness and the like. If it isThe corrosion-resistant alumina ceramic film is directly deposited on the sintering substrate, and the film thickness cannot meet the requirement, so that even if the thin film is artificially thickened, the thick film coating mostly has inherent cracks and holes, and the corrosion resistance of the ceramic structural member is poor.
In addition, the industry of high performance alumina ceramics for high-end semiconductor process etching equipment is currently mainly focused on developed countries such as the united states and japan, and mainly includes international first-class ceramic manufacturers such as Kyocera and CoorsTEK in japan. Research in this regard is less common in China due to the particularities of industry and application.
In view of this, there is a need to develop a thick film alumina ceramic material and device with high corrosion resistance that is convenient for industrial use.
Disclosure of Invention
Accordingly, there is a need for a method of preparing alumina ceramics for semiconductor devices that can produce a semiconductor device having good resistance to plasma etching.
The invention aims to overcome the defects in the prior art and provide an alumina ceramic body with excellent plasma etching resistance and a manufacturing method thereof, wherein the alumina ceramic body can simultaneously realize the effects of thick film, good mechanical property, strong corrosion resistance and the like.
The invention provides a preparation method of alumina ceramic for semiconductor equipment, which comprises the following steps:
(1) Weighing alumina ceramic raw material and MgF 2 An additive; according to MgF 2 The weight of the additive is C of the weight of the alumina ceramic 1 Mixing to obtain material a, and mixing according to MgF 2 The weight of the additive is C of the weight of the alumina ceramic 2 Mixing to obtain a material b; the alumina ceramic raw material is alpha-Al 2 O 3 The purity is more than 99.5 percent, and the average grain diameter is 1-10 mu m. The alumina in the proposal can be purchased directly, the price is cheaper than that of high-purity nano alumina, the particle size of the alumina is not particularly limited, preferably 1-5 μm, more preferably 1-3 μm. The alumina ceramic raw material with smaller grain diameter can be sinteredA denser alumina ceramic body is obtained that has fewer internal voids and better plasma etch resistance for use in semiconductor devices. The magnesium fluoride plays a role of a sintering aid, and the existence of a small amount of magnesium fluoride can firstly obviously reduce the sintering temperature of the alumina during sintering, and can also inhibit the growth of alumina grains, promote the ceramic of the product to be more densified and improve the corrosion resistance of the product. In step 1, C is 0.1% to C 1 ≤0.5％，0.5%≤C 2 Less than or equal to 3 percent, and C 2 ≤10C 1 . The applicant found that alpha-Al containing magnesium fluoride 2 O 3 When the sintering temperature exceeds 1300 ℃, magnesium fluoride can slowly escape from an alumina ceramic phase, so that when the amount of sintering auxiliary agents in an upper layer alumina green body and a lower layer alumina green body is reduced to 0.1% -0.5% of the weight of the alumina ceramic body in the production of a multi-layer alumina ceramic body with upper and lower protective layers, the magnesium fluoride in the surface layer alumina can escape by nearly 100% after the sintering at the temperature above 1300 ℃ for 4 hours, the purity of the upper and lower layers of the alumina ceramic body is further improved, and corrosion sites possibly generated by residual auxiliary agents are greatly reduced. When C 1 When the temperature is less than 0.1%, the sintering temperature of the ceramic exceeds 2000 ℃, the energy consumption is high, and the size of the sintered ceramic grains is increased; when C 1 When more than 0.5%, mgF appears on both the upper and lower layers of the sintered alumina 2 Residual, residual auxiliary agents tend to form plasma etching sites and dielectric loss of ceramic products increases. When C 2 When the dielectric loss is less than 0.5%, the sintering temperature of the ceramic is also increased, the compact alumina can be obtained after long-time sintering, the dielectric loss is increased, and the grain size of the ceramic after sintering is also increased; when C 2 When the content of the additive is more than 3%, the additive in the middle layer can diffuse into the upper layer and the lower layer, so that the upper layer and the lower layer have certain MgF 2 Residual auxiliary agents can influence the compactness of the ceramic material, plasma corrosion sites are easy to form, and dielectric loss of the ceramic product is increased. In the application, the high-concentration magnesium fluoride in the aluminum oxide intermediate layer can effectively realize the complete sintering of aluminum oxide, and in addition, a solid solution phase can be formed at the joint of the intermediate layer and the upper layer and the lower layer, so that the three-layer connecting force is stronger, and the aluminum oxide ceramic material is improvedOverall strength.
(2) Respectively putting the materials a and b into a ball mill for ball milling for 8-12 hours, wherein the ball milling medium is zirconium balls, the ball milling solvent is ethanol, and drying treatment is carried out after ball milling is finished to obtain powder; the ball milling adopts a conventional ball milling device, and the ball milling solvent can also be water, glycerol and other common ball milling solvents. The proportion of the materials, the ball milling solvent and the ball milling medium in the ball milling is not particularly limited, so that the complete dispersion is suitable.
(3) Respectively putting the powder obtained in the step (2) into a low-speed stirring tank, and adding a binder into the low-speed stirring tank to stir for 6-8 hours; the binder is one or more of polyvinyl alcohol Ding Quanzhi (PVB), ethylene-methacrylic acid polymer and polyvinyl alcohol, preferably the binder is polyvinyl alcohol. The addition amount of the binder is 5% -20% of the mass of the powder, preferably 5% -10% of the mass of the powder, and more preferably 6% -8% of the mass of the powder. The rotating speed of the low-speed stirring tank is 50-200 r/min, the stirring time is 5-20 h, the rotating speed of the optimized stirring tank is 100r/min, and the stirring time is 10h.
(4) Feeding the materials obtained in the step (3) into centrifugal granulators for granulation respectively to obtain powder A, B respectively; the centrifugal granulation principle is that when slurry is sent to a high-speed rotating disc, the slurry stretches into a film on the surface of the rotating disc under the action of the centrifugal force of the rotating disc and moves towards the edge of the disc at a continuously increasing speed, liquid is atomized when the slurry leaves the edge of the disc, the atomized liquid is contacted with hot air, and the hot air evaporates water, so that dry powder is finally obtained. The centrifugal granulation process parameters in the step are as follows: temperature of hot air: 100-300 ℃; preferably 120-200 ℃, the rotating speed of the atomizing disk is as follows: 8000-12000 rpm; the water content of the granulated powder is 1-5%, and the particle size of the granulated powder is 20-100 mu m.
(5) Sequentially combining mass M 1 Powder A, mass M 2 Powder B and mass M of (2) 1 Filling the powder A into a mould, and sending the powder A into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 100-200 MPa, the 0.1M 2 ≤M 1 ≤5M 2 The method comprises the steps of carrying out a first treatment on the surface of the The raw materials after granulation are respectively added into a mould to obtain the ceramic green body, and the ceramic green body is prepared by controlling the used ceramicsThe quality of the granulated material adjusts the thickness of each layer in the product ceramic. In the specific step (5), the mass M 1 After the powder A is added into a mould, jolt and stricken, and then a layer of mass M is paved on the upper surface of the powder A 2 After jolt ramming and stricken, a layer of mass M is spread on the upper surface of the powder B 1 In order to improve the stability of each layer, the powder A can be pre-compacted under low pressure after each powder tiling and jolt-ramming treatment, and the pressure used for pre-compaction is 1-5 MPa, so that the powder is convenient for preliminary solidification and forming. For M 1 、M 2 The numerical value of (2) is not particularly limited, and it is preferable that the ceramic layer is obtainable by pressing.
The cold isostatic pressing process can further improve the density of the blank body and the uniformity of the ceramic microstructure, and can also improve the density of ceramic products, thereby improving the plasma corrosion resistance of the products. In the present invention, the pressure of the cold isostatic pressing is preferably 150MPa.
The applicant finds that the three-layer ceramic has better corrosion resistance not in any thickness, and the quality M of the upper and lower layers of ceramic 1 Mass M with intermediate ceramic layer 2 Satisfy 0.1M 2 ≤M 1 ≤5M 2 The alumina ceramic has better corrosion resistance. In addition, the thickness relation of the upper layer and the lower layer can be the same or different, for example, the quality of the upper layer and the lower layer and the quality of the middle layer only need to meet the relation independently at different times.
(6) And (3) sending the ceramic green body subjected to cold isostatic pressing treatment into an electric furnace or a gas furnace for sintering, wherein the sintering adopts two sections, the first section is sintered for 2-3 hours at 500-700 ℃, the second section is sintered for 4-10 hours at 1300-1500 ℃, and the aluminum oxide ceramic is obtained after cooling to room temperature. The sintering atmosphere is not particularly limited, and air or oxygen atmosphere can be used, or inert atmosphere can be selected, and air or oxygen atmosphere is preferable. The first stage sintering is mainly used for discharging glue, and can basically realize the discharge of more than 90% of binder of the ceramic body at 500 ℃ for 2 hours, and due to certain organic matters in the green body, the organic matters can be decomposed and volatilized during sintering, so that the green body deforms, cracks or air holes are formed, and meanwhile, the organic matters contain more carbon, so that the sintering quality can be influenced when the oxygen is insufficient to form a reducing atmosphere. Therefore, organic matters in the green body are required to be removed before the green body is sintered, so that the requirements of the shape, the size and the quality of the product are ensured. The firing temperature in the second stage is related to the sintering aid in the system, and the applicant has found that when the sintering aid and the layer thickness settings in the present invention are used, the firing at 1300-1500 ℃ for 4-10 hours can achieve complete firing of the alumina ceramic.
As a preferable mode of the invention, in the step (6), the two-stage sintering is performed at 600 ℃ for 3 hours, and then the temperature is raised to 1400 ℃ for 8 hours. And naturally cooling the ceramic at room temperature after sintering to obtain the alumina ceramic with higher corrosion resistance and meeting the thickness requirement.
The invention also aims to provide the alumina ceramic with good mechanical and corrosion resistance, and the density of the alumina ceramic is more than or equal to 3.95g/cm 3 The bending strength is more than or equal to 450MPa, the grain size is less than or equal to 5 mu m, and the dielectric loss is less than or equal to 2 multiplied by 10 -4 . Kong Zhanbi in the ceramic is few, the grain size is small, the ceramic density is high, and the ceramic density in the alumina ceramic can be high. It can also be seen from the lower value of dielectric loss that the alumina ceramic prepared does not absorb part of radio waves or microwaves, resulting in a decrease in plasma generation efficiency. At the same time, the temperature rise caused by the heat generated by absorbing radio waves or microwaves can not be caused, and the thermal expansion is initiated, so that the ceramic component is cracked. Meanwhile, the three layers of the alumina ceramic material have the same main components, and the thermal expansion coefficients of the layers are basically consistent, so that the whole ceramic system has higher thermal stability, and the phenomena of layering, curling and the like can not occur.
It is also an object of the present invention to provide a plasma etching apparatus in which the alumina ceramic of the invention of the present application is applied.
Compared with the prior art, the beneficial effects of the technical scheme are as follows:
firstly, adopting low-valence alumina and combining magnesium fluoride as sintering auxiliary agents, and synergistically obtaining the alumina ceramic with high plasma corrosion resistance new performance by means of adjusting the content of the magnesium fluoride among layers and the thickness of each layer, optimizing preparation parameters and the like. The ceramic has higher density and lower grain size; the upper layer and the lower layer of sintering aid in the alumina ceramic can be effectively completely escaped through the cooperative control of the preparation process, and meanwhile, the connecting interface between the upper layer and the lower layer and the middle layer is effectively formed through the control of the content of the auxiliary agents in each layer, so that the mechanical strength of the alumina ceramic is enhanced, and the alumina ceramic has higher bending strength.
Secondly, the method has simple process and higher universality compared with the existing ceramic preparation equipment; the thickness of the ceramic material is controllable, and the large-size ceramic material with higher corrosion resistance can be conveniently obtained, so that the localization development level of semiconductor equipment is improved, and the technical advantages of the semiconductor industry in China are further improved.
Drawings
FIG. 1 is a schematic illustration of an alumina ceramic with good mechanical and corrosion resistance properties according to an embodiment of the present invention. Wherein, 1, upper layer; 2. an intermediate layer; 3. and a lower layer.
FIG. 2 is an SEM photograph of the upper layer of alumina ceramic in example 1 of the present invention.
Detailed Description
In order to make the technical problems solved, the technical solutions adopted and the technical effects achieved by the present invention more clear, the technical solutions in the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the terms "upper," "lower," "inner," "outer," "front," "rear," "both ends," "one end," "the other end," and the like indicate orientations or positional relationships based on the orientations or positional relationships shown herein, merely to facilitate description of the present invention and simplify the description, and do not indicate or imply that the devices or elements being referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. The terms "comprising" and "having" and any variations thereof, in embodiments of the present application, are intended to cover non-exclusive inclusions.
In the examples, the alumina ceramic material is alpha-Al 2 O 3 The purity is more than 99.5 percent, and the average grain diameter is 1-10 mu m. The centrifugal granulation process parameters are as follows: temperature of hot air: 100-300 ℃; preferably 120-200 ℃, the rotating speed of the atomizing disk is as follows: 8000-12000 rpm; the water content of the granulated powder is 1-5%.
Example 1: this example discloses a method for preparing alumina ceramic for semiconductor device, which is shown in FIG. 1, wherein MgF is contained in the raw materials of upper layer 1 and lower layer 3 2 C, the weight of which is the weight of the alumina ceramic 1 MgF in intermediate layer 2 2 C, the weight of which is the weight of the alumina ceramic 2 The thickness of the upper layer 1 and the lower layer 3 are the same. Thickness d of the intermediate layer 2 With an upper or lower layer thickness d 1 Is 0.1d 2 ≤d 1 ≤5d 2 。
The preparation method of the alumina ceramic in the embodiment comprises the following steps:
(1) Weighing alumina ceramic raw material and MgF 2 An additive; according to MgF 2 The weight of the additive is 0.1 percent of the weight of the alumina ceramic, and the mixture is mixed to obtain a material a according to MgF 2 Mixing the weight of the additive accounting for 0.5 percent of the weight of the alumina ceramic to obtain a material b;
(2) Respectively putting the materials a and b into a ball mill for ball milling for 10 hours, wherein the ball milling medium is zirconium balls, the ball milling solvent is ethanol, and drying treatment is carried out after ball milling is finished to obtain powder;
(3) Respectively putting the powder obtained in the step (2) into a low-speed stirring tank, and adding a binder polyvinyl alcohol with the mass accounting for 5% of the mass of the powder into the low-speed stirring tank for stirring; the rotating speed of the stirring tank is 100r/min, and the stirring time is 5h;
(4) Feeding the materials obtained in the step (3) into centrifugal granulators for granulation respectively to obtain powder A, B respectively; the particle size of the granulated powder in the step (4) is 50 mu m;
(5) Sequentially filling 5g of powder A, 10g of powder B and 5g of powder A into a die, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 100MPa;
(6) And (3) sending the ceramic green body subjected to cold static pressure treatment into an electric furnace or a gas furnace for sintering, wherein the sintering adopts two sections, the first section is sintered for 2 hours at 500 ℃, the second section is sintered for 4 hours at 1300 ℃, and the alumina ceramic is obtained after cooling to room temperature.
FIG. 2 is an SEM image of the upper layer of alumina ceramic obtained in this example, and it can be seen from the image that the upper layer of the ceramic is relatively dense and uniform, the average particle size of the particles is about 4.76 μm, and the particle size distribution is uniform.
Example 2 the alumina ceramic preparation method in this example is different from example 1 in that: c in the step (1) 1 、C 2 Is adjusted to C 1 0.5% C 2 3%; the amount of the polyvinyl alcohol binder in the step (3) is adjusted to 8% of the mass of the powder, the rotating speed of the stirring tank is 200r/min, and the stirring time is 15h; the pressing pressure in step (5) was set to 150MPa.
Example 3: the preparation method of the alumina ceramic in the embodiment comprises the following steps:
(1) Weighing alumina ceramic raw material and MgF 2 An additive; according to MgF 2 The weight of the additive is 0.2 percent of the weight of the alumina ceramic, and the mixture is mixed to obtain a material a according to MgF 2 Mixing the weight of the additive accounting for 2 percent of the weight of the alumina ceramic to obtain a material b;
(2) Respectively putting the materials a and b into a ball mill for ball milling for 12 hours, wherein the ball milling medium is zirconium balls, the ball milling solvent is ethanol, and drying treatment is carried out after ball milling is finished to obtain powder;
(3) Respectively putting the powder obtained in the step (2) into a low-speed stirring tank, and adding a binder ethylene-methacrylic acid polymer with the mass of 10% of the mass of the powder into the low-speed stirring tank to stir; the rotating speed of the stirring tank is 150r/min, and the stirring time is 20h;
(4) Feeding the materials obtained in the step (3) into centrifugal granulators for granulation respectively to obtain powder A, B respectively; the particle size of the granulated powder in the step (4) is 80 mu m;
(5) Sequentially filling 1g of powder A, 10g of powder B and 1g of powder A into a die, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 200MPa;
(6) And (3) sending the ceramic green body subjected to cold static pressure treatment into an electric furnace or a gas furnace for sintering, wherein the sintering adopts two sections, the first section is sintered for 2 hours at 700 ℃, the second section is sintered for 6 hours at 1500 ℃, and the alumina ceramic is obtained after cooling to room temperature.
Example 4: the preparation method of the alumina ceramic in the embodiment comprises the following steps:
(1) Weighing alumina ceramic raw material and MgF 2 An additive; according to MgF 2 The weight of the additive is 0.2 percent of the weight of the alumina ceramic, and the mixture is mixed to obtain a material a according to MgF 2 Mixing the weight of the additive accounting for 1 percent of the weight of the alumina ceramic to obtain a material b;
(2) Respectively putting the materials a and b into a ball mill for ball milling for 8 hours, wherein the ball milling medium is zirconium balls, the ball milling solvent is ethanol, and drying treatment is carried out after ball milling is finished to obtain powder;
(3) Respectively putting the powder obtained in the step (2) into a low-speed stirring tank, and adding a binder polyvinyl butyral (PVB) with the mass of 6% of the powder into the low-speed stirring tank to stir; the rotation speed of the stirring tank is 50r/min, and the stirring time is 10h;
(4) Feeding the materials obtained in the step (3) into centrifugal granulators for granulation respectively to obtain powder A, B respectively; the particle size of the granulated powder in the step (4) is 100 mu m;
(5) Sequentially filling 10g of powder A, 10g of powder B and 10g of powder A into a die, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 150MPa;
(6) And (3) sending the ceramic green body subjected to cold static pressure treatment into an electric furnace or a gas furnace for sintering, wherein the sintering adopts two sections, the first section is sintered for 3 hours at 600 ℃, the second section is sintered for 8 hours at 1400 ℃, and the alumina ceramic is obtained after cooling to room temperature.
Example 5: the alumina ceramic preparation method in this example is different from that in example 3 in that step (5) is set as follows: sequentially filling 20g of powder A, 10g of powder B and 20g of powder A into a die, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 180MPa; the first stage sintering in step (6) is set to fire at 700 ℃ for 3 hours.
Example 6: the alumina ceramic preparation method in this example is different from that in example 4 in that: adjusting the binder amount in the step (3) to 20% of the powder mass, wherein the rotating speed of a stirring tank is 200r/min, and the stirring time is 20h; setting the step (5) as follows: sequentially filling 50g of powder A, 10g of powder B and 50g of powder A into a die, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 200MPa; firing the first stage of sintering in step (6) at 550 ℃ for 2.5 hours, and setting the second stage of sintering at 1300 ℃ for 10 hours.
Comparative example 1: comparative example 1 differs from example 1 in that C was adjusted 2 Wherein C in comparative example 1 1 2%. Other parameter settings were the same as in example 1.
Comparative examples 2 to 5: comparative examples 2 to 5 differ from example 1 in that C was adjusted 1 、C 2 Wherein C in comparative example 2 1 0.06%, C 2 0.5%; comparative example 3C 1 0.07%, C 2 1%; comparative example 4C 1 0.6% C 2 3%; comparative example 5C 1 0.6% C 2 4%.
Comparative example 6: comparative example 6 differs from example 4 in that step (5) was modified as follows: filling 0.5g of powder A, 10g of powder B and 0.5g of powder A into a die in sequence, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 150MPa.
Comparative example 7: comparative example 7 differs from example 3 in that step (5) was modified as follows: filling 0.5g of powder A, 10g of powder B and 0.5g of powder A into a die in sequence, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure was 200MPa.
Comparative example 8: comparative example 8 differs from example 6 in that step (5) was modified as: filling 53g of powder A, 10g of powder B and 53g of powder A into a die in sequence, and sending into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure was 200MPa.
The alumina ceramic products obtained in the above examples and comparative examples were tested to obtain corresponding values. The ceramic material density is obtained through a density balance test, and the bending strength is obtained through a test by adopting an electronic universal tester; the grain size is obtained by adopting a scanning electron microscope test; the dielectric loss is obtained through testing of a vector network analyzer and a dielectric property testing operation platform. The applicant finds that when the density of the alumina ceramic is more than or equal to 3.95g/cm through practical use experience and related standard and other documents 3 The bending strength is more than or equal to 450MPa, the grain size is less than or equal to 5 mu m, and the dielectric loss is less than or equal to 2 multiplied by 10 -4 When the ceramic is used, the ceramic has less inner holes and high material density, and has less overall defects or impurities, and the product has good corrosion resistance, and can be stably applied to semiconductor high-end equipment such as Chemical Vapor Deposition (CVD) deposition equipment or etching equipment using plasma etching and the like for a long time.
Test example: table 1: results of product Performance test in examples, comparative examples
| Density g/cm 3 | Flexural Strength MPa | Grain size μm | Dielectric loss | |
| Example 1 | 3.95 | 450 | 4.76 | 1.85×10 -4 |
| Example 2 | 3.96 | 470 | 4.67 | 1.93×10 -4 |
| Example 3 | 3.95 | 462 | 4.85 | 1.92×10 -4 |
| Example 4 | 3.95 | 455 | 4.76 | 1.85×10 -4 |
| Example 5 | 3.95 | 453 | 4.85 | 1.92×10 -4 |
| Example 6 | 3.96 | 467 | 4.83 | 1.9×10 -4 |
| Comparative example 1 | 3.87 | 460 | 4.75 | 2.13×10 -4 |
| Comparative example 2 | 3.83 | 440 | 5.3 | 3.47×10 -4 |
| Comparative example 3 | 3.84 | 451 | 5.7 | 2.15×10 -4 |
| Comparative example 4 | 3.95 | 465 | 5.1 | 2.87×10 -4 |
| Comparative example 5 | 3.95 | 470 | 5.5 | 3.05×10 -4 |
| Comparative example 6 | 3.94 | 450 | 4.78 | 2.32×10 -4 |
| Comparative example 7 | 3.94 | 452 | 4.94 | 2.13×10 -4 |
| Comparative example 8 | 3.95 | 463 | 4.73 | 2.52×10 -4 |
As can be seen from the above table, when the relation C is satisfied in the raw materials of the alumina ceramic prepared 2 ≤10C 1 When the alumina ceramic is used, the obtained alumina ceramic has higher density, which is shown by higher density of the product, which is basically more than 3.95. Meanwhile, the ceramic preparation process such as sintering process, thickness of each layer film and the like also have influence on the ceramic preparation process, and the ceramic density is reduced by firing at a lower temperature for a short time. As can be seen from the comparison between example 1 and comparative examples 1 and 2, when C is not satisfied 2 ≤10C 1 When the content of the sintering aid is lower than 0.1%, on the one hand, the sintering of the ceramic needs a higher temperature, and the complete firing of the ceramic cannot be realized at the temperature of 1300-1500 ℃ at this time, so that the internal crystal grain size is larger, the pores are more, and the ceramic density is lower. And when C 1 At more than 0.5%, the ceramic can be completely sintered in the temperature range, and the density of the product meets the requirement. But at the same time have high MgF 2 The presence of (2) may lead to residues within the ceramic, the residual auxiliary agents tend to form plasma corrosion sites during use of the ceramic, and internal impurities may also lead to increased dielectric losses in the ceramic product. On the other hand, the quality of sintering aid and alumina in the raw material of the ceramic interlayer is relatedThe mechanical properties such as bending strength of the ceramic product are affected, and the content ratio of the auxiliary agent in the intermediate layer needs to be increased to maintain the good bending strength of the ceramic product, but at the same time, when the content exceeds a certain value, excessive sintering auxiliary agent residues adversely affect the performance of the ceramic product, such as increasing internal impurities and increasing dielectric loss of the product.
The plasma corrosion resistance of the alumina ceramic is related to the properties of material density, pore distribution, impurity content, dielectric loss and the like, and the grain size and mechanical properties of the alumina ceramic such as bending strength can influence the actual use characteristics of the material. From the point of view of the density of the products obtained in the examples, the alumina ceramic obtained by the method has higher density, which can also laterally indicate that the distribution of pores in the ceramic body is small and the whole ceramic system is compact. The alumina obtained in the embodiment has better bending strength and can meet the practical application. The comparison of the examples shows that the method can obtain the alumina ceramic with good mechanical and corrosion resistance, the process is simpler, the conventional ceramic production line equipment can be adopted to realize the simple method to obtain the high-quality corrosion-resistant alumina ceramic by adjusting the content of the auxiliary agent and the thickness of each layer and combining the heat treatment process, and in addition, the method can also realize the preparation of the large-size ceramic.
The above detailed description of a method for preparing alumina ceramic with good mechanical and corrosion resistance properties disclosed in the examples of the present application is provided in connection with the detailed description of the present invention, and it should not be construed as limiting the practice of the present invention to these descriptions. For those skilled in the art, the architecture of the invention can be flexible and changeable without departing from the concept of the invention, and serial products can be derived. But a few simple derivatives or substitutions should be construed as falling within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing alumina ceramic for semiconductor equipment, comprising the steps of:
(1) Weighing alumina ceramic raw material and MgF 2 An additive; according to MgF 2 The weight of the additive is C of the weight of the alumina ceramic 1 Mixing to obtain material a, and mixing according to MgF 2 The weight of the additive is C of the weight of the alumina ceramic 2 Mixing to obtain a material b;
(2) Respectively putting the materials a and b into a ball mill for ball milling for 8-12 hours, wherein the ball milling medium is zirconium balls, the ball milling solvent is ethanol, and drying treatment is carried out after ball milling is finished to obtain powder;
(3) Respectively putting the powder obtained in the step (2) into a low-speed stirring tank, and adding a binder into the low-speed stirring tank to stir for 6-8 hours;
(4) Feeding the materials obtained in the step (3) into centrifugal granulators for granulation respectively to obtain powder A, B respectively;
(5) Sequentially combining mass M 1 Powder A, mass M 2 Powder B and mass M of (2) 1 Filling the powder A into a mould, and sending the powder A into a cold isostatic press for compression molding to obtain a ceramic green body; the pressure is 100-200 MPa, the 0.1M 2 ≤M 1 ≤5M 2 ；
(6) And (3) sending the ceramic green body subjected to cold isostatic pressing treatment into an electric furnace or a gas furnace for sintering, wherein the sintering adopts two sections, the first section is sintered for 2-3 hours at 500-700 ℃, the second section is sintered for 4-10 hours at 1300-1500 ℃, and the aluminum oxide ceramic is obtained after cooling to room temperature.
2. The method for producing an alumina ceramic for semiconductor equipment according to claim 1, wherein C is 0.1% or less 1 ≤0.5％，0.5%≤C 2 Less than or equal to 3 percent, and C 2 ≤10C 1 。
3. The method of claim 1, wherein the binder in the step (3) is one of polyvinyl butyral Ding Quanzhi (PVB), ethylene-methacrylic acid polymer, and polyvinyl alcohol.
4. The method for preparing alumina ceramic for semiconductor equipment according to claim 1, wherein the rotation speed of the stirring tank in the step (3) is 50-200 r/min, and the stirring time is 5-20 h.
5. The method for producing alumina ceramic for semiconductor equipment according to claim 1, wherein the centrifugal granulation process parameters in the step (4) are as follows: temperature of hot air: 100-300 ℃; the rotating speed of the atomizing disk is as follows: 8000-12000 rpm; the water content of the granulated powder is 1-5%.
6. The method for producing an alumina ceramic for a semiconductor device according to claim 1, wherein the alumina ceramic raw material is α -Al 2 O 3 The purity is more than 99.5 percent, and the average grain diameter is 1-10 mu m.
7. The method according to claim 1, wherein the two-stage sintering in the step (6) is performed at 600 ℃ for 3 hours, and then the temperature is raised to 1400 ℃ for 8 hours.
8. The method for producing alumina ceramic for semiconductor device according to claim 1, wherein the particle size of the granulated powder obtained in the step (4) is 20 to 100. Mu.m.
9. The alumina ceramic obtained by the method for producing alumina ceramic for semiconductor device according to claim 1, wherein the alumina ceramic has a density of 3.95g/cm or more 3 The bending strength is more than or equal to 450MPa, the grain size is less than or equal to 5 mu m, and the dielectric loss is less than or equal to 2 multiplied by 10 -4 。
10. A plasma etching apparatus comprising the alumina ceramic of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310589432.XA CN116332630B (en) | 2023-05-24 | 2023-05-24 | Preparation method of alumina ceramic for semiconductor equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310589432.XA CN116332630B (en) | 2023-05-24 | 2023-05-24 | Preparation method of alumina ceramic for semiconductor equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116332630A true CN116332630A (en) | 2023-06-27 |
| CN116332630B CN116332630B (en) | 2023-08-11 |
Family
ID=86891520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310589432.XA Active CN116332630B (en) | 2023-05-24 | 2023-05-24 | Preparation method of alumina ceramic for semiconductor equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116332630B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844916A (en) * | 2009-03-26 | 2010-09-29 | 日本碍子株式会社 | Alumina sintered body, its method for making and semiconductor manufacturing apparatus member |
| WO2011012125A1 (en) * | 2009-07-30 | 2011-02-03 | Fraunhofer Gesellschaft Zur Förderung Der Angewandten Forschung E. V. | α-AL2O3- SINTERING MATERIAL, METHOD FOR PRODUCING A HIGH-DENSITY AND VERY FINELY CRYSTALLINE MOLDED BODY MADE OF SAID MATERIAL, AND USE THEREOF |
| JP2011168472A (en) * | 2009-03-26 | 2011-09-01 | Ngk Insulators Ltd | Alumina sintered body, method for producing the same and semiconductor manufacturing apparatus member |
| CN115321960A (en) * | 2022-08-22 | 2022-11-11 | 南充三环电子有限公司 | Alumina ceramic and preparation method and application thereof |
| CN116023123A (en) * | 2023-01-13 | 2023-04-28 | 广东风华高新科技股份有限公司 | Low-temperature co-fired ceramic material and preparation method and application thereof |
-
2023
- 2023-05-24 CN CN202310589432.XA patent/CN116332630B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844916A (en) * | 2009-03-26 | 2010-09-29 | 日本碍子株式会社 | Alumina sintered body, its method for making and semiconductor manufacturing apparatus member |
| JP2011168472A (en) * | 2009-03-26 | 2011-09-01 | Ngk Insulators Ltd | Alumina sintered body, method for producing the same and semiconductor manufacturing apparatus member |
| WO2011012125A1 (en) * | 2009-07-30 | 2011-02-03 | Fraunhofer Gesellschaft Zur Förderung Der Angewandten Forschung E. V. | α-AL2O3- SINTERING MATERIAL, METHOD FOR PRODUCING A HIGH-DENSITY AND VERY FINELY CRYSTALLINE MOLDED BODY MADE OF SAID MATERIAL, AND USE THEREOF |
| CN115321960A (en) * | 2022-08-22 | 2022-11-11 | 南充三环电子有限公司 | Alumina ceramic and preparation method and application thereof |
| CN116023123A (en) * | 2023-01-13 | 2023-04-28 | 广东风华高新科技股份有限公司 | Low-temperature co-fired ceramic material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 董伟霞;包启富;顾幸勇;: "MgF_2对低温烧结75氧化铝陶瓷性能的影响", 中国陶瓷, no. 10 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116332630B (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113200747B (en) | Low-temperature sintered aluminum nitride ceramic material, aluminum nitride casting slurry and application | |
| CN114149260B (en) | Low-thermal-conductivity high-entropy ceramic thermal barrier coating material | |
| CN110128117B (en) | High-purity alumina ceramic material and preparation method thereof | |
| WO2022156635A1 (en) | Batch sintering method for high-performance silicon nitride ceramic substrate | |
| JP5339214B2 (en) | Method for manufacturing silicon nitride substrate and silicon nitride substrate | |
| WO2020052453A1 (en) | Silicon nitride ceramic material for mobile phone back plate and preparation method therefor | |
| CN112028637A (en) | Preparation method of high-reliability long-life silicon nitride ceramic ball for aviation bearing | |
| CN106048596A (en) | Method for preparing Ti2AlC phase ceramic coating through cold spraying in-situ formation | |
| CN101475393B (en) | Composition and method for connecting silicon nitride ceramics | |
| CN114890797A (en) | Preparation method of silicon nitride ceramic substrate | |
| CN114988895A (en) | Impact-resistant thermal cycle and CMAS corrosion resistant complex phase eutectoid environmental barrier coating and preparation method thereof | |
| CN115724663A (en) | full-3D printing silicon carbide ceramic optical component and preparation method thereof | |
| CN114988896A (en) | High-emissivity coating and application thereof | |
| CN116332630B (en) | Preparation method of alumina ceramic for semiconductor equipment | |
| CN114340896B (en) | Multi-zone silicon nitride wafer heater assembly with corrosion protection layer, and method of making and using the same | |
| CN117051279A (en) | Nickel-platinum-cerium alloy target and preparation method thereof | |
| CN111201208B (en) | Alumina sintered body and method for producing same | |
| CN114751754B (en) | Preparation method of silicon nitride ceramic substrate biscuit | |
| JP3904874B2 (en) | Components for semiconductor manufacturing equipment | |
| JP7231367B2 (en) | Alumina sintered body | |
| CN114853479B (en) | Method for preparing silicon carbide or boron carbide ceramic plate based on reaction sintering | |
| CN116253560B (en) | Alumina target and preparation method thereof | |
| CN118324496A (en) | Composite insulator substrate, preparation method thereof and electrostatic chuck device | |
| CN110218090B (en) | Preparation method of niobium oxide rotary target material | |
| CN116396081A (en) | Method for preparing high-strength aluminum nitride ceramic by low-temperature sintering |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |