CN106164325A - The film deposition apparatus used in the manufacture of resistant to plasma body component, the manufacture method of resistant to plasma body component and resistant to plasma body component - Google Patents
The film deposition apparatus used in the manufacture of resistant to plasma body component, the manufacture method of resistant to plasma body component and resistant to plasma body component Download PDFInfo
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- CN106164325A CN106164325A CN201580017990.2A CN201580017990A CN106164325A CN 106164325 A CN106164325 A CN 106164325A CN 201580017990 A CN201580017990 A CN 201580017990A CN 106164325 A CN106164325 A CN 106164325A
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- Prior art keywords
- oxide
- coverlay
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- plasma
- body component
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- 230000008021 deposition Effects 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 111
- 238000000151 deposition Methods 0.000 claims abstract description 98
- 239000010419 fine particle Substances 0.000 claims abstract description 19
- 230000002776 aggregation Effects 0.000 claims abstract description 10
- 238000004220 aggregation Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 50
- 238000002347 injection Methods 0.000 claims description 46
- 239000007924 injection Substances 0.000 claims description 46
- 238000007747 plating Methods 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 45
- 239000002994 raw material Substances 0.000 claims description 45
- 238000005507 spraying Methods 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000000859 sublimation Methods 0.000 claims description 7
- 230000008022 sublimation Effects 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000008187 granular material Substances 0.000 abstract description 17
- 230000008929 regeneration Effects 0.000 abstract description 6
- 238000011069 regeneration method Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 210000002381 plasma Anatomy 0.000 description 125
- 239000010408 film Substances 0.000 description 82
- 238000001020 plasma etching Methods 0.000 description 19
- 239000011148 porous material Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000004531 microgranule Substances 0.000 description 10
- 210000002469 basement membrane Anatomy 0.000 description 9
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- 230000008859 change Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 241001232787 Epiphragma Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
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- 238000001312 dry etching Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
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- 230000008646 thermal stress Effects 0.000 description 1
- 210000001215 vagina Anatomy 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
Abstract
An embodiment of the invention relates to resistant to plasma body component and the manufacture method of resistant to plasma body component, wherein, the oxide coverlay of described plasma source components is that the fine particle of 0.05～3 μm becomes multiple grain and then the oxide deposition coverlay formed with the form of the aggregation of this polycrystalline particle each other in component base surface sinter bonded, thickness is 10 μm～200 μm, and film density is more than 90%.According to above-mentioned composition, can obtain stably and effectively suppressing to come from the generation of the granule of coverlay and then be difficult in Regeneration Treatment and be corroded or the resistant to plasma body component of the infringement such as deformation and the manufacture method of resistant to plasma body component.
Description
Technical field
Embodiments of the present invention relate to resistant to plasma body component, the manufacture method of resistant to plasma body component and resistance to etc. from
The film deposition apparatus used in the manufacture of daughter parts.
Background technology
In the past, in the fine process of the manufacturing process of semiconductor device and liquid crystal indicator etc., generally utilized
The SiO carried out by sputter equipment or CVD device2Deng the film forming of dielectric film and Si and SiO that carried out by Etaching device2Each to
Property etching and anisotropic etching and form fine wiring and electrode etc..
In general, these devices, in order to improve film forming speed and etching, typically utilize plasma discharge.
Such as, as above-mentioned Etaching device, generally use RIE (etching of Reactive Ion Etching: reactive ion)
The plasma-etching apparatus of device etc.
RIE device is in low-pressure state in making chamber, import in chamber fluorine-based gas or chlorine system gas and make its etc. from
Daughter, thus implement etching.
In the past, in plasma-etching apparatus, the parts managing to make the irradiation plasmas such as chamber will not reaction of formation
Product, and parts easily corrode because being exposed in plasma, thus substrate surface formed plasma-resistance and
The coverlay that corrosion resistance is higher is carried out the most widely.
As this coverlay, known has by yittrium oxide (Y2O3) or aluminium oxide (Al2O3) oxide that constitutes covers
Film.These oxide coverlays are in the suppression generation of product and the damage that prevents the parts produced because of plasma etch
Aspect plays effect.
Such as, in No. 4084689 description of Japanese Patent No. (patent documentation 1), recite by coating base material
On Y (OH)3The Y that sol solutions carries out heat treatment and formed2O3Film, at Japanese Unexamined Patent Publication 2006-108178 publication (patent documentation
2), in, recite Al2O3Spraying plating coverlay.
Prior art literature
Patent documentation
Patent documentation 1: No. 4084689 description of Japanese Patent No.
Patent documentation 2: Japanese Unexamined Patent Publication 2006-108178 publication
Summary of the invention
Invent problem to be solved
But, metallikon before using and the spraying plating oxide coverlay such as the yittrium oxide that formed or aluminium oxide is yittrium oxide
Or the coverlay of the oxide particle such as aluminium oxide deposition, this particle is the oxide particle of melted yittrium oxide or aluminium oxide
Collide and be quenched solidification with substrate surface and formed.Furthermore, the particle diameter of the oxide powder used in former metallikon is relatively
Greatly, it is about 5～45 μm.Therefore, the spraying plating oxide of metallikon before using and the yittrium oxide that formed or aluminium oxide etc. covers
What epiphragma existed technical problem is that: easily produce many micro-cracks because of the internal and thermal expansion difference on surface, strain easily residual,
Thus durability insufficient.
It is to say, the oxide particle of the yittrium oxide melted by spraying plating thermal source or aluminium oxide etc. touches with substrate surface
Hit, thus be easily deformed and reduce for thickness on the direction be perpendicular to substrate surface and particle elongation on parallel direction
So-called flat pattern, then quenching solidifies and becomes the particle (hereinafter referred to as " melted flaky particles ") of flat shape.Now,
In the case of the mean diameter of oxide powder particle is more than 5 μm relatively greatly, produce main in the surface of melted flaky particles
Will on the thickness direction be perpendicular to substrate surface it can be seen that crackle (hereinafter referred to as " micro-crack "), thus strain is molten
The internal residual melting flaky particles gets off.Above-mentioned so-called flat pattern, refers to by the grain on the direction being perpendicular to substrate surface
When the length (L) of the thickness (t) of son and the particle on the direction being parallel to substrate surface calculates asperratio (L/t), should
Asperratio is the shape of more than 1.5.
If in the state in which under yittrium oxide coverlay or aluminium oxide coverlay irradiate because of plasma
Electric discharge and the living radical that produces, then micro-crack described in living radical etch and make micro-crack expand, internal strain simultaneously
Being released, now micro-crack spreads.As a result of which it is, spraying plating coverlay defect and make to derive from the granule of spraying plating coverlay
Become easily to produce, be attached to the stripping of the product above spraying plating coverlay simultaneously and make to derive from the granule change of product
Obtain and easily produce.And producing of granule will cause the short circuit of fine wiring etc. or broken string to make the product of semiconductor device etc. become
Product rate reduces, and makes the cleaning of plasma device parts and the replacing of parts become frequent simultaneously, thus causes productivity ratio
Reduce and the rising of film forming cost.
The particle diameter of the oxide powder used in the metallikon before it addition, is relatively big, is about 5～45 μm, thus in shape
In the spraying plating coverlay become, pore (hole) rate is higher, is about 15%, and pore produces in a large number, and spraying plating coverlay surface
Roughness in terms of average roughness Ra, slightly reach about 6～10 μm.Described pore (hole) is suitable with interparticle gap, institute
State micro-crack and represent that melted flaky particles there occurs the surface configuration of cracking.
If using the plasma defining the thicker spraying plating coverlay of more and surface the roughness of such pore
Device feature, then generate the problem that: carried out the plasma etching of base material by pore, so that plasma device portion
The lost of life of part, and plasma discharge concentrates on the protuberance of spraying plating coverlay and makes spraying plating coverlay become fragile, thus
The generating capacity of grain increases.
Furthermore, such as, in nearest semiconductor element, in order to realize high integration, carrying out the narrow and small of wiring width
Change.Narrowing such as even up to 32nm, 19nm of wiring width, and then even up to below 15nm.The most narrowing
Wiring or there is the element of this wiring, even if in the case of being mixed into the atomic little granule about the most a diameter of 0.2 μm,
Also the bad or element of wiring can be produced bad etc..Therefore, in recent years, even if atomic little granule, it is strongly required to the greatest extent the most always
Its generation of amount suppression.
It addition, formed before spraying plating coverlay in the case of, as coverlay formed pre-treatment, generally at high pressure
Under carry out processing abrasive particle etc. together with grain to the injection of substrate surface winding-up.But, if carried out in this wise at injection
, then there is the residual sheet of the i.e. abrasive particle of blasting materials at substrate surface, or form crushable layer because of injection at substrate surface in reason.
If having such blasting materials in remaining or being formed with the spray before the substrate surface of crushable layer is formed
Plating epiphragma, then, under the effect of the thermal stress of film produced by the variations in temperature of plasma discharge, stress acts on base
Material and the interface of spraying plating coverlay, thus whole spraying plating coverlay easily produces film and peels off.Especially, increasing what injection processed
In the case of pressure or grit size, film is peeled off and is become notable.Therefore, the life-span of former spraying plating coverlay is because of injection
The difference for the treatment of conditions also varies widely.
So, the method for the spraying plating coverlay before the substrate surface at plasma device parts is formed exists
Following problem: spraying plating coverlay easily becomes the occurring source of granule, easily makes finished product rate reduce, and spraying plating coverlay
The change of situation that processes along with injection of life-span and change, thus the deviation of the quality of each parts increases.
Furthermore, in the coverlays such as yittrium oxide are formed at again plasma device parts inwall or Inner Constitution portion
In Regeneration Treatment on part, the medicinal liquid that stripping uses when using the coverlays such as the yittrium oxide of spraying plating formation processes or injection process is deposited
Problem be: parts are produced corrosion or the infringement such as deformation.
As the improvement measure for this problem, such a is had to impact sintering process: for former spraying plating, to use and adjust
Whole for less than the high-temperature gas of the combustion flame of temperature etc of fusing point make particle to be carried out at high speed injection so that particle is almost
Will not melt and form epithelium, by means of the method for this formation epithelium, be formed and make the corrosion resistance ratio for plasma former
The coverlay that the coverlay that metallikon is formed more improves.
But, melted and in the particle shape portion that deposits, exist unobservable in described melted flaky particles, do not melt
Melt and be deposited as the i.e. pore in granular particle gap each other (hole).Accordingly, it is difficult to more densification, and then corrosion resistance
More improve be difficult.Furthermore, at the inwall that the coverlays such as yittrium oxide are formed at again plasma device parts
Or in the Regeneration Treatment on Inner Constitution parts, stripping uses the oxide coverlays such as the yittrium oxide of described impact sintering process formation
Time the medicinal liquid that uses process or injection processes in described particle gap i.e. pore (hole) each other, although damage ratio with
Front metallikon is few, but there is the problem producing the infringements such as corrosion or deformation.
An embodiment of the invention completes in view of the foregoing, its object is to provide resistant to plasma body
The film deposition apparatus used in the manufacture of part, the manufacture method of resistant to plasma body component and resistant to plasma body component, this is resistance to
Gas ions parts can reduce the porosity of coverlay, thus improves corrosion resistance and intensity, and stably and effectively suppresses source
In the generation of granule and the stripping of coverlay of coverlay, and then in Regeneration Treatment, at the medicinal liquid used when peeling off coverlay
Reason, injection process etc. are difficult to produce component the infringements such as corrosion or deformation.
For solving the means of problem
The present invention for the surface at base material, cover with by powder sintered and as the sintered body that formed, make particle each other
Between the coverlay of aggregation of sinter bonded fine and close polycrystalline particle together to replace with former metallikon formation
Spraying plating coverlay, has carried out research with great concentration and investigation to its forming method, condition, and result is found that as technology opinion finally
The method, and complete the present invention based on this opinion.
Specifically, if the oxidation of yittrium oxide etc. that formed of fine particle that formation mean diameter is 0.05～3 μm
Thing coverlay, then in the oxide such as yittrium oxide constitute this coverlay substantially without produce internal flaw, internal strain and
Micro-crack, fine particle becomes multiple grain in the surface sinter bonded of component base each other together, forms pore
Low and the fine and close coverlay of rate is as its aggregation, thus the corrosion resistance of coverlay and intensity are improved.
As a result, it is possible to given play to following effect: can be stable and effectively suppression come from the granule of coverlay
Generation and the stripping of coverlay, and the generation of the product on coverlay surface can be suppressed and come from this product
In the generation of granule, and then the Regeneration Treatment after parts use, the medicinal liquid process of use, injection process etc. when peeling off coverlay
It is difficult to component is produced the infringements such as corrosion or deformation.
The present invention is the membrane structure in order to realize described coverlay, it was found that its forming method, condition and complete.With by
Sintered body that is powder sintered and that formed similarly makes fine particle sinter bonded each other fine and close polycrystalline particle together
Including: sinter bonded that the solid-phase sintering mechanism that do not melted by particle produces and melted by occurring between particle surface or particle
And both sinter bonded of the liquid phase sintering mechanism sintered.The polycrystalline particle of described sinter bonded is not single crystal
Particle, but the particle that can see crystal boundary in particle is observed by microscope, the coverlay of the present invention is seen by microscope
Examine, observe similarly as the coverlay deposited by these polycrystalline particles.
In fine and close polycrystalline particle that obtained by the present invention, sinter bonded, it is barely perceivable and not can confirm that
With outer portion every the non-particle shape portion of crystal boundary, and use microscope to observe in the covering for example with formation such as impact sintering process
Film is it is observed that.When the section vertical with substrate surface to coverlay carries out microscope observation, coverlay is not
Can confirm that described with outer portion every the area occupation ratio in non-particle shape portion of crystal boundary be less than 10%.
Present in the described oxide deposition coverlay of the present invention, particle diameter is that the fine particle of below 3 μm is to coverlay
The section vertical with substrate surface carry out microscope when observing, be calculated as less than 10% with area occupation ratio, described oxide deposition covers
Present in film, melted flaky particles is when the section vertical with substrate surface to film carries out microscope observation, is calculated as with area occupation ratio
Less than 10%, in any case, it is barely perceivable.
An embodiment of the invention provides a kind of plasma device, and it has holding in chamber and processes object
Process object maintaining body and make the plasma generating mechanism of the gaseous plasma being directed in described chamber, and making
With the plasma generated, described process object is processed.Composition in the inwall and described chamber of described chamber
The surface of the side, formation zone of the plasma using the generation of described plasma generating mechanism of parts, is formed with oxide and covers
Epiphragma.This oxide coverlay is the deposition coverlay being made up of oxide particles such as yittrium oxide.
Above-mentioned deposition coverlay is characterised by: its be particle diameter be that the fine particle of 0.05～3 μm is each other at parts
Substrate surface sinter bonded and become multiple grain and then the deposition that formed with the form of the aggregation of this polycrystalline particle covers
Film, its thickness is 10 μm～200 μm, and film density is more than 90%.In described deposition coverlay, particle diameter is the micro-of below 3 μm
Small particles (raw particles) is existed in the ratio being calculated as less than 10% with area occupation ratio, but owing to being formed as the polycrystalline particle of densification
Aggregation, thus can fully keep plasma-resistance.
Furthermore, oxide coverlay can also attach basement membrane and constitute.That is, it is also possible to be configured to as base
Have by the oxide of oxide particle deposition on the former oxide spraying plating coverlay of the yittrium oxide etc. that counterdie is formed
Deposition coverlay, and the total film of the stacked film that coverlay is constituted is deposited by basement membrane (spraying plating coverlay) and described oxide
Thickness is 20 μm～300 μm, and the film density of described oxide deposition coverlay is more than 90%.
Furthermore, described oxide coverlay can also be made up of three-decker, and this three-decker is by by substrate surface
The oxide-film that such as carries out pellumina process and formed, the basement membrane formed on this oxide-film surface and at this basement membrane
Surface formed oxide deposition coverlay constitute.That is, it is characterised in that: it is being formed at the shape carrying out peroxide film
As on the former oxide spraying plating coverlay of the yittrium oxide etc. of basement membrane, there is described oxidation on the substrate surface that one-tenth processes
Thing deposition coverlay, and the total thickness being deposited the stacked film that coverlay is constituted by basement membrane and described oxide be 20 μm～
200 μm, the film density of described oxide deposition coverlay is more than 90%.
Moreover, it relates to a kind of film stacked laminator, it has base material and the oxygen of this substrate surface coating for manufacturing
The described resistant to plasma body component of compound deposition coverlay, it is characterised in that described film stacked laminator has: generation chamber, and it leads to
Cross plasma arc, produce high-temperature plasma injection stream or high-temperature gas；Raw material slip supply mouth, it will be containing oxide raw material
The raw material slip of powder is to above-mentioned high-temperature plasma injection stream or the central part supply of high-temperature gas；Fuel supply mouth, it will
Fuel or oxygen supply to above-mentioned generation chamber；Gas supply port, working gas is supplied by it to above-mentioned generation chamber；And nozzle
(spray nozzle), it makes raw material slip aerify, by the oxygen in gas by above-mentioned working gas with fuel or oxygen
Compound raw material is heated to below the boiling point of oxide and the temperature less than sublimation point, and controls starting oxides for base material
The state of surface injection so that it is jet velocity reached for 400～1000m/ seconds.
Furthermore, in above-mentioned film stacked laminator, the top ends of the nozzle that oxide raw material is sprayed to substrate surface and institute
State the jet length between substrate surface and be preferably 100～400mm.It addition, the oxide raw material powder in described raw material slip
Content be preferably 30～80 volume %.
The effect of invention
Resistant to plasma body component, the manufacture method of resistant to plasma body component and resistant to plasma body component according to the present invention
Manufacture in use film deposition apparatus, it is provided that plasma-resistance is improved and can stably and effectively suppress
Granule occur parts and manufacture method and its manufacture in use film deposition apparatus.
Accompanying drawing explanation
Fig. 1 is the sectional view of the example representing the parts carried in the plasma device of embodiment.
Fig. 2 is taken as an example of the oxide coverlay that former metallikon is formed, and is to represent to be perpendicular to base material
The microphotograph (enlarged photograph) of the tissue of the aluminium oxide coverlay of the section on the direction on surface.
Fig. 3 shows the one of the aggregation of the melted flaky particles of the oxide coverlay of the metallikon formation before using
The schematic diagram of individual example.On base material 4, deposition has melted flaky particles 5, and the surface observation at melted flaky particles 5 exists to main
It is perpendicular on the thickness direction of substrate surface produce the micro-crack 6 of cracking.Further, it was observed that the i.e. pore in many interparticle gaps
(hole) 7.
Fig. 4, as an example of the oxide coverlay of embodiment, is to represent on the direction being perpendicular to substrate surface
The microphotograph (enlarged photograph) of tissue of aluminium oxide coverlay of section.
Fig. 5 is the sectional view of an example of the aggregation of the polycrystalline particle of the oxide coverlay representing embodiment.
Polycrystalline particle 8 is not single fine particle 10, but it can be seen that the particle of crystal boundary 9, the coverlay of the present invention in particle
The coverlay deposited on base material 4 for these polycrystalline particles 8.
Fig. 6 is the spray of the film stacked laminator used in the manufacture of the plasma device parts schematically illustrating embodiment
The sectional view of loophole, it is shown that raw material slip supply mouth 15 and plasma arc generation chamber or the work of high-temperature gas generation chamber 11
The configuration example that gas supply port 13 and fuel or oxygen supply mouth 14 are set up in parallel.
Fig. 7 is the spray of the film stacked laminator used in the manufacture of the plasma device parts schematically illustrating embodiment
The sectional view of loophole, it is shown that raw material slip supply mouth 15 is disposed in proximity to plasma arc generation chamber or high-temperature gas generation chamber
The configuration example in the place of the working gas supply mouth 13 of 11 and fuel or oxygen supply mouth 14.
Detailed description of the invention
Below with regard to resistant to plasma body component, the manufacture method of resistant to plasma body component and the resistant to plasma body of the present invention
The film deposition apparatus used in the manufacture of part illustrates.Additionally, the present invention is not exposed to the restriction of these embodiments.
[resistant to plasma body component]
The resistant to plasma body component of the present invention is to have base material and at least one of yittrium oxide etc. of coating substrate surface
The parts of oxide coverlay.
(base material)
The base material that uses in resistant to plasma body component, in parts, is intended to the oxide coverlay of yittrium oxide etc. coating
Component.
As base material, in the component of resistant to plasma body component, can list and be exposed to the life when Cement Composite Treated by Plasma
Component in the plasma become or free radical.As such component, such as, can list semiconductor-fabricating device and liquid
Component i.e. wafer configuration component, inner wall part, deposition shield, dead ring, upper electrode, baffle plate, the focusing of brilliant device manufacture apparatus
Ring, shading ring, bellows cover etc..As the material of base material, such as, can list the metals such as pottery and aluminum such as quartz.
(embodiment)
The oxide coverlay of the yittrium oxide etc. used in the resistant to plasma body component of embodiment is to use mean diameter
It is fine particle formation and the oxide deposition coverlay of coating substrate surface of 0.05～3 μm, with monolayer, two-layer or three
The form of layer is formed, and wherein, described monolayer is that above-mentioned oxide deposits coverlay, and described two-layer is to be coated to former sputtered films of bismuth
The oxide spraying plating coverlay of basement membrane and above-mentioned oxide deposition coverlay it is formed as after on base material, described three
The oxide-film that layer is formed for substrate surface is carried out oxidation processes, the spraying plating before the formation of this oxide-film surface cover
The oxide deposition coverlay on film and this spraying plating coverlay surface coating.
As one of embodiment, for being equipped with the plasma device of resistant to plasma body component, this resistant to plasma body
Part has the oxide coverlay formed by the fine particle that mean diameter is 0.05～3 μm, and this oxide coverlay is by oxygen
The deposition coverlay that compound particle is constituted.
Described deposition coverlay be mean diameter be that the fine particle of 0.05～3 μm is each other at the substrate surface of parts
Sinter bonded and become multiple grain and then the oxide deposition coverlay formed with the form of the aggregation of this polycrystalline particle,
The thickness of this oxide deposition coverlay is 10 μm～200 μm, and film density is more than 90%.
Or, it is, on the common oxide spraying plating coverlay of the yittrium oxide etc. formed as basement membrane, there is described oxygen
The double-layer structure of compound deposition coverlay, in the case of this double-layer structure, is deposited coverlay by above-mentioned basement membrane and oxide
The total thickness of the stacked film constituted is 30 μm～200 μm, and the film density of above-mentioned oxide deposition coverlay is more than 90%.
Fig. 1 is the sectional view of the example representing the parts carried in the plasma device of the 1st embodiment.?
In figure, 1 is plasma processing apparatus parts (resistant to plasma body components), and 2 deposit coverlay for oxide, and 3 is base material.As
Really oxide deposition coverlay 2 is such as formed with yittrium oxide, then for plasma etch, free radical etch (such as activity
F free radical) and fluorine system plasma there is stronger toleration.
It addition, the purity of the oxide raw material particle of yittrium oxide etc. is preferably more than 99.9%.If at oxide particle
Middle impurity is more, then become the reason that impurity is mixed in the manufacturing process of quasiconductor.It is therefore preferable that use purity more preferably
The oxide particle of more than 99.99%.
If the metallikon film forming before using, then the oxide such as yittrium oxide is the thick grain about 5～45 μm at particle diameter
Son occurs to penetrate under melted state and film forming is offset flat shape, easily produces at particle surface split thereby through quenching solidification
Stricture of vagina.In contrast, in embodiments of the present invention, due to be mean diameter be 0.05 μm～the fine particle of 3 μm, thus
Even if the conduction of heat on film forming on base material, inside particles and surface is also fast, because the heat of the inside under sedimentation state and surface is swollen
Swollen difference and the stress within film that causes produces hardly, the crackle etc. caused because of quenching solidification also will not produce.
Particle deposition coverlay is to heat fine particle, generation while ejection plasma spray jet or high-temperature gas
High velocity jet and deposit the coverlay of film forming, it uses following method to be formed: be heated to the temperature less than boiling point and sublimation point
The particle of degree collides with base material so that high speed more than the 400m/ second penetrates, and the particle of deposition combines in contact portion and formed
Coverlay.Due to combine be mean diameter be the fine particle of below 3 μm, thus the inside of particle and the heat on surface
Conduction is very fast, and the stress within film caused because of the inside under sedimentation state and the thermal expansion difference on surface produces hardly
Raw, become multiple grain in the substrate surface sinter bonded of parts, such that it is able to form the cause as polycrystalline particle agglomeration
The oxide deposition coverlay of the yittrium oxide etc. that close (film density is higher) and adhesion are stronger.
The thickness of the oxide deposition coverlay of yittrium oxide etc. needs more than 10 μm.If less than 10 μm, then can not fill
Get the effect of plasma-resistance, be likely to become the reason that film peels off on the contrary.The thickness of oxide deposition coverlay
The upper limit is not particularly limited, if but blocked up, then can not obtain the effect more than it, and easily because of internal stress
Gather and crack, also become the main cause of cost increase.Therefore, the thickness of oxide deposition coverlay is 10～200 μ
M, preferably 30～150 μm.
It addition, the film density (relative density) of oxide deposition coverlay needs more than 90%.So-called film density, be with
The term that the porosity is contrary, film density is more than 90% to be less than 10% same meaning with the porosity.Mensuration side at film density
In method, oxide is deposited coverlay and cuts off along film thickness direction, optically-based microscopical 500 times are shot with regard to its fractography
Enlarged photograph, and calculate the area occupation ratio of the pore that here it is shown that.Then by " area occupation ratio of film density (%)=100-pore "
Calculate film density.Calculating of film density is set to be analyzed the area of unit are 200 μ m 200 μm.Additionally, at film
When thickness is relatively thin, it is set as multiple positions are measured, until the unit are added up to is 200 μ m 200 μm.
The film density of oxide deposition coverlay needs to be set as more than 90%, more preferably more than 95%, and the most excellent
Elect 99%～100% as.If there is more pore (hole) in oxide deposition coverlay, then from this pore start into
Row plasma etches etc. are corroded, so that the service life reduction of oxide coverlay.It is therefore especially preferred that be oxide sink
The surface of long-pending coverlay has less pore.
The surface roughness Ra of oxide deposition coverlay is preferably below 3 μm.If the table of oxide deposition coverlay
Face is concavo-convex relatively big, then plasma etch etc. are easily concentrated, it is possible to make the service life reduction of deposition coverlay.Here, table
The mensuration of surface roughness Ra is carried out according to JIS-B-0601-1994.Surface roughness Ra is preferably below 2 μm.
As the material powder of use microgranule, the mean diameter of oxide powder is preferably in the scope of 0.05～3 μm.At it
In the deposition coverlay formed, interparticle adhesion is relatively big, the loss caused because of plasma etch and free radical etch
Reducing, thus granule generating capacity reduces, plasma-resistance is improved.If oxide particle flat as material powder
All particle diameters are more than 3 μm, then, when particle is deposited on base material, each particle easily produces the crackle caused because of quenching solidification, thus
Likely deposition coverlay is caused damage and crack.
The preferred value of mean diameter of particle is 0.05 μm～1 μm.If the mean diameter of particle is less than 0.05 μm, then
Particle can not obtain at high speed, even if deposition also becomes low-density coverlay, so that plasma-resistance and corrosion resistance fall
Low.But, as long as mean diameter is less than the 5% of whole oxide particle less than the particle of 0.05 μm, coverlay would not be made
Formed and deteriorate, even if thus using the powder containing the small particles less than 0.05 μm also to have no relations.
Then, just manufacture method as the device for dry etching parts (resistant to plasma body component) of one of embodiment is entered
Row explanation.Embodiment by microgranule formed the manufacture method of resistant to plasma body component of oxide deposition coverlay have with
Under operation: the supply slip containing the oxide particle such as yittrium oxide in high-temperature plasma injection stream or high-temperature gas, will
The oxide particles such as yittrium oxide are heated to the temperature less than boiling point and sublimation point, thus with the jet velocity of 400～1000m/ seconds
Spray on base material.Preferably the melting temperature of oxide is less than boiling point and the heating operation of sublimation point temperature, spray
Firing rate degree was 500～1000m/ seconds.The mean diameter of the oxide particles such as yittrium oxide is preferably 0.05～3 μm.More preferably
0.05～1 μm.Additionally, it is preferred that by the slip containing oxide particles such as yittrium oxide to producing high-temperature plasma injection stream or height
The central supply of the chamber of wet body.
The film deposition apparatus being carried out depositing by microgranule has high-temperature plasma injection stream or the supply of high-temperature gas
Mouthful and plasma torch associated therewith or high-temperature gas generation chamber.In high-temperature plasma injection stream or High Temperature Gas
The generation chamber of body has slip supply mouth, by oxide particle slips such as the yittrium oxide of slip supply mouth supply from high-temperature plasma
Injection stream or high-temperature gas generation chamber via nozzle to spraying method film forming.High-temperature gas can also use by oxygen, second
The combustion flame etc. that alkynes, ethanol, kerosene etc. produce.
The manufacture method of plasma etching device part has following operation: containing the raw material of oxide raw material powder
Slip is to high-temperature plasma injection stream or the operation (oxide raw material powder supply step) of the central part supply of high-temperature gas；
It is heated to less than boiling point and sublimation point temperature with the oxide raw material powder in high-temperature plasma injection stream or high-temperature gas,
And the operation (oxide raw material powderject operation) sprayed to substrate surface with the jet velocity of 400～1000m/ seconds.
If above-mentioned pulp density is in the range of 30～80 volume %, the most advantageously: raw material slip has
Suitable mobility and successfully supply to slip supply mouth, thus raw material slip quantity delivered in high-temperature gas is stable, because of
And the thickness of oxide deposition coverlay and composition become uniform.
＜ raw material slip supply ＞ in high-temperature plasma injection stream or high-temperature gas
As it has been described above, the slip supply mouth of film deposition apparatus is usually designed to: raw material slip is sprayed to high-temperature plasma
The central part supply of jet or high-temperature gas.It addition, the jet velocity of high-temperature plasma injection stream or high-temperature gas is higher.
In the present invention, when the oxide raw material powder in raw material slip is to high-temperature plasma injection stream or high-temperature gas
Central part supply time, the jet velocity of the oxide raw material powder in high-temperature plasma injection stream or high-temperature gas stable and
Being difficult in terms of jet velocity produce deviation, high-temperature plasma sprays stream or the temperature constant of high-temperature gas and easily enters simultaneously
The control of the tissue of row oxide deposition coverlay, thus be preferred.
Here, oxide raw material powder in so-called raw material slip is to high-temperature plasma injection stream or high temperature gas flow
Central part supplies, and refers to that the oxide raw material powder in raw material slip is from high-temperature plasma injection stream or the side of high temperature gas flow
Face is until central part supplies.It addition, so-called high-temperature plasma injection stream or the central part of high-temperature gas, refer to take vertical
The directly central part of this section when the section of high-temperature plasma injection stream or the injection direction of high-temperature gas.
On the other hand, if the oxide raw material powder in raw material slip is not to high-temperature plasma injection stream or High Temperature Gas
The central part of body stream supplies, only sprays stream or the side of high temperature gas flow or high-temperature plasma to high-temperature plasma
Injection stream or being externally supplied of high temperature gas flow, then the oxide raw material powder in high-temperature plasma injection stream or high-temperature gas
The jet velocity at end is unstable and easily produces deviation in terms of jet velocity, the stream of high-temperature plasma injection simultaneously or High Temperature Gas
The deviation of the temperature of body stream is relatively big, thus the control of the tissue of oxide deposition coverlay becomes difficulty.
As the method making the raw material slip central part to high-temperature plasma injection stream or high temperature gas flow supply, permissible
List the position adjustment of raw material slip supply mouth and adjust raw material slip to high-temperature plasma injection stream or high-temperature gas
In quantity delivered and the method etc. of feed speed.
The high-temperature plasma injection stream allocated in described operation or high-temperature gas and oxide raw material powder from
The nozzle of film deposition apparatus is to spraying method.High-temperature plasma sprays stream or high-temperature gas and the spray of oxide raw material powder
State of penetrating is controlled by by nozzle.As controlled spray regime, such as, can list the injection speed of oxide raw material powder
Degree etc..
The nozzle of film deposition apparatus is usually designed to: high-temperature plasma is sprayed stream or high-temperature gas and oxide is former
Material powder is to transverse injection.Base material is typically configured as: substrate surface is positioned at the extended line of the horizontal nozzle of film deposition apparatus
On.
In the case of formed oxide deposition coverlay by microgranule, the jet velocity of oxide particle is preferably at 400m/
Second～the scope of 1000m/ second.Jet velocity relatively slow and less than the 400m/ second in the case of, deposition when particle collides is also
It is insufficient, it is possible to the film that film density is higher will not be obtained.It addition, when jet velocity is more than the 1000m/ second, impact force
Too strong and produced jeting effect by oxide particle, thus it is difficult to obtain the oxide deposition coverlay of target.
It is that the oxide particle of 0.05～3 μm is as material powder that oxide particle slip is preferably containing mean diameter
Slip.The solvent of slip preferably methanol and ethanol etc. are easier the solvent of volatilization.Oxide particle is preferably at abundant powder
Broken and mix with solvent after being in oversize grain non-existent state.Such as, if there being thick more than 3 μm of mean diameter
Particle, then be difficult to be deposited film uniformly.It addition, the content of the oxide particle in slip is preferably 30～80 volume %'s
Scope.For having the slip of adequate liquidity, it becomes smooth to the supply of supply mouth, owing to quantity delivered is stable, thus can
To be deposited coverlay uniformly.Preferred content is 50～80 volume %.
Above plasma device parts can be applicable to various plasma device.Such as, film forming in
The microfabrication of the various thin film such as dielectric film, electrode film and wiring membrane on Si wafer and substrate can use RIE
(Reactive Ion Etching) device is carried out, described RIE be by between electrode apply high frequency voltage or
The interaction in microwave electric field and magnetic field makes halogen gas plasma, and utilizes the ion of generation and free radical to add
Work.
As long as the position that the plasma device parts of one of embodiment are exposed in plasma, anyplace
Can be suitable for.Therefore, it is not limited to the wafer configuration component of electrostatic chuck etc, as long as inner wall part etc. be exposed to etc. from
Parts in daughter, all can be suitable for.It addition, about the base material forming oxide deposition coverlay, it is not limited to quartz,
Can also be arranged on hardware and ceramic base material.Especially in the parts that plasma device is used, it is that one can
To be applicable to expose to the open air deposition shield in the plasma, dead ring, upper electrode, baffle plate, focusing ring, shading ring, corrugated tube
The technology of cover etc., but it is not limited to the field of semiconductor-fabricating device, even if the plasma device of liquid crystal device etc.
Parts can also be suitable for.
It addition, according to the present invention, the plasma-resistance of plasma device parts significantly improves such that it is able to realize
The long lifetime that the reduction of granule and parts use.Therefore, as long as use the plasma of such resistant to plasma body component
Body device, it is possible to realize reduction and the reduction of part replacement number of times of granule in Cement Composite Treated by Plasma.
It addition, in the RIE device utilizing high-density plasma, in order to keep applying with the generation because of plasma
The insulating properties of high frequency voltage, often use insulating component.
In the protecting film of the insulating component being exposed to as upper electrode in plasma, high forming insulating properties
Pellumina process after coverlay, form general oxide spraying plating coverlay, then use high speed particle deposition thereon
It is effective that method forms the three layer coating obtained by the deposition coverlay of oxide fine particle.
It addition, for insulating properties, in addition to pellumina processes coverlay, it would however also be possible to employ particle deposition forms oxygen
Change aluminum coverlay.In the case, for insulating properties, the adjustment of the thickness of aluminium oxide coverlay and the formation of high density coverlay
It is important, especially in the case of forming the fine and close aluminium oxide coverlay of α structure, in order to play further effect, excellent
Choosing is set as the condition equal with the formation of yittrium oxide coverlay.
In the protecting film of the insulating component being exposed to as dead ring in plasma, higher in deposition insulating properties
Aluminium oxide coverlay (pellumina process) after, then be formed on yittrium oxide deposition coverlay obtained by two layers of coatings
It is effective.
It is important for insulating properties, the adjustment of the thickness of aluminium oxide coverlay and the formation of high density coverlay, especially
In the case of forming the fine and close aluminium oxide coverlay of α structure, in order to play further effect, it is preferably set to and aoxidizes
Yttrium coverlay form equal condition.
Additionally, although basal layer is set as yittrium oxide coverlay but it also may be other oxide or their mixing
Thing, preferably carries out material according to necessary characteristic and selectes.
In the case of being set as more than 2 Rotating fields of yittrium oxide deposition coverlay and the basal layer with most surface, its
The upper limit of the thickness added up to is preferably below 500 μm.
Additionally, although basal layer is set as aluminium oxide coverlay but it also may be other oxide or their mixing
Thing, preferably carries out material according to necessary characteristic and selectes.Situation at 2 Rotating fields being set as aluminium oxide coverlay and basal layer
Under, the upper limit of its thickness is preferably below 500 μm.
According to the present invention it is possible to suppression because of be deposited on that the stripping of the attachment on plasma device parts causes
The generation of grain, can be greatly reduced device simultaneously and clean and the number of times of part replacement.The reduction of granule generating capacity helps significantly
Defect in film when defect during etching and processing in semiconductor manufacturing and various forming thin film, and then go far towards to make
With its element and the raising of the yield rate of parts.It addition, device cleans and the reduction of part replacement number of times, the use longevity of parts
The prolongation of life goes far towards the raising of productivity ratio and the reduction of operating cost.
Referring to following embodiment, one of embodiments of the present invention are described in detail.
Show that the oxide fine particle (embodiment 1～7) shown in employing table 1 and former metallikon (comparative example 1) become
The membrance casting condition of the yittrium oxide coverlay of film.When carrying out spraying plating, using plasma spraying plating process forms yittrium oxide coverlay,
Then utilize and use plasma-type film injection apparatus and the microgranule that penetrates, on the surface of aluminum base material (100mm × 200mm),
Yittrium oxide deposition coverlay is formed, as plasma device parts (resistant to plasma body under conditions of shown in table 1
Part).The solvent of yttrium oxide particle slip is all set as ethanol.It addition, the material powder used all uses purity to be 99.99%
Above high purity oxygen compound particle.Furthermore, as the yittrium oxide (Y of material powder2O3) particle is cubic crystal, use by filling
Point pulverizing and screening and be not above the powder of the oversize grain of 3 μm.It addition, comparative example 1 using plasma metallikon shape
Become yittrium oxide spraying plating coverlay.
Table 1
Table 1 shows that each embodiment of the yittrium oxide coverlay with film forming in each condition and the relevant film of comparative example are close
Degree.
In the way of the unit are of the total of film section is 200 μ m 200 μm, shoot enlarged photograph (500 times), by
The ratio of the pore of this display obtains film density.
Result as shown in Table 1 shows: in the yittrium oxide deposition coverlay of the resistant to plasma body component of the present embodiment, film
Density is the highest.
Although additionally, the most not shown, but the table of the deposition coverlay of each resistant to plasma body component of embodiment 1～7
Surface roughness Ra is below 3 μm.Furthermore, the surface roughness Ra of the yittrium oxide spraying plating coverlay of comparative example 1 is 6.3 μm.
Then, above-described embodiment 1～7 and the evaluation of plasma resistance of each resistant to plasma body component of comparative example
Result is as shown in table 2.It is to say, will be formed with the yittrium oxide deposition coverlay shown in each embodiment of table 1 and comparative example
Or the resistant to plasma body component of spraying plating coverlay is arranged in plasma etch process device (RIE) so that it is be exposed to
CF4(flow: 80sccm)+O2(20sccm) in the plasma generated in the mixed gas stream of+Ar (100sccm).It addition, will
Pressure in RIE chamber is set as 20mTorr, and RF output is set as 100W so that it is working 12 hours (" 20 points continuously
Clock discharges cooling in → 10 minutes " × 24 times), then use based on ス U ッ チ テ プ method that (ス U ッ チ テ プ is 3M company
Registered trade mark) peel off to evaluate the amount of coming off of the particle of yittrium oxide coverlay investigated.
Specifically, ス U ッ チ テ プ is attached to the deposition coverlay or spraying plating coverlay being made up of yittrium oxide
On, then stripping tape, adhesive tape is carried out SEM (Scanning Electron Microscope) and observes, to being attached with existence
The area of the particle of the threshing in the long wide 60 μm visual fields of 80 μ m is determined.It addition, it is above-mentioned to implementing with precision balance
The weight of the parts being formed with yittrium oxide coverlay before and after exposure test is determined, and determines parts before and after test
Weight decrement.Measurement result is as described in Table 2.
Table 2
Shown by the result shown in above-mentioned table 2: the oxide being made up of microgranule deposition coverlay is formed on base material
Compared with parts (embodiment 1～7) form the parts (comparative example 1) obtained by spraying plating coverlay with the metallikon before employing,
Weight decrement is greatly lowered, and the particle amount of coming off from yittrium oxide deposition coverlay also lacks more than an order of magnitude.By this
Result may validate that the RIE device parts plasma etch and the freedom that are formed protecting film by microgranule of the present embodiment
Base etch has stronger toleration.So-called anti-plasma etch and free radical etch are relatively strong, refer to for RIE device
Time, can effectively suppress the generation of granule.
Additionally, in the various embodiments described above, it is shown that yittrium oxide spraying plating coverlay before each substrate surface is formed, so
Rear employing microgranule forms the example of yittrium oxide deposition coverlay, or directly uses microgranule to form yittrium oxide deposition on base material
The example of coverlay, but by formed between the substrate surface of parts and yittrium oxide deposition coverlay at least 1 layer of aluminium oxide it
The dielectric film of class, and use microgranule to form yittrium oxide deposition coverlay in its most surface, can give play to and also be able to as parts
Improve the effect of insulating properties.
As indicated above, RIE (plasma etching) device portion according to the embodiment of the present invention
Part, can suppress to deposit the coverlay corrosion to the free radical of corrosive gas, can improve each parts and coverlay self
Stability, thus can suppress to come from the generation of the granule of parts and coverlay.Furthermore, owing to making parts use long lifetime,
And the product produced because of corrosion is also minimized, it is thus possible to cut down replacing number of times and the wash number of parts.
It addition, after parts use, plasma spraying method the yittrium oxide spraying plating coverlay formed is carried out injection
Reason, thus the attachment product of plating surface is removed, then use particle deposition yittrium oxide deposition coverlay thereon, thus can be suitable
Implement the Regeneration Treatment of parts sharply, alleviate the infringement to parts simultaneously, it is possible to carry out the recycling of parts, thus realize
The reduction of parts expense.
It addition, in the above-described embodiment, it is illustrated RIE (plasma etching) dress as plasma device
Put, but the invention is not limited in the parts used in them, in addition, for plasma CVD (Chemical
Vapor Deposition) device etc. produces plasma and carries out all devices processed, can be suitable for and have above-mentioned enforcement
The parts of the oxide deposition coverlay of mode.
As it has been described above, be illustrated with regard to several embodiments of the invention, but these embodiments are to add as an example
With prompting, it does not seek to limit the scope of invention.The embodiment of these novelties can be in addition real in other various modes
Execute, in the range of without departing from invention main idea, it is possible to carry out various omission, replace and change.These embodiments and change thereof
Shape is included in the scope or spirit of invention, and is included in the scope of the invention described in claims and substitute equivalents thereof
In.
Symbol description:
1 plasma device is with parts (resistant to plasma body component)
2 yittrium oxide deposition coverlays
3 base materials
4 base materials
5 melt flaky particles
6 micro-cracks
7 pores (hole)
8 polycrystalline particles
9 crystal boundaries
10 fine particles
11 plasma arc generation chamber or high-temperature gas generation chamber
12 nozzles
13 working gas supply mouths
14 fuel or oxygen supply mouth
15 raw material slip supply mouths
Claims (15)
1. a resistant to plasma body component, it is characterised in that: in the parts being used in plasma device, at the base material of parts
Surface at least some of on be formed with oxide coverlay, described oxide coverlay be mean diameter be 0.05～3 μm
Fine particle is become multiple grain each other and then is formed with the form of the aggregation of this polycrystalline particle by sinter bonded
Oxide deposition coverlay, its thickness is 10 μm～200 μm, and film density is more than 90%.
Resistant to plasma body component the most according to claim 1, it is characterised in that: form described oxide deposition coverlay
Polycrystalline particle is when the section vertical with substrate surface that oxide deposits coverlay carries out microscope observation, its mean diameter
It it is the polycrystalline particle of 0.5～10 μm.
Resistant to plasma body component the most according to claim 1 and 2, it is characterised in that: described oxide deposition coverlay exists
Micro-crack is there is not in polycrystalline particle.
4. according to the resistant to plasma body component according to any one of claims 1 to 3, it is characterised in that: it is present in described oxidation
The fine particle that particle diameter is below 3 μm in thing deposition coverlay is in break vertical with substrate surface to oxide deposition coverlay
When face carries out microscope observation, it is calculated as less than 10% with area occupation ratio.
5. according to the resistant to plasma body component according to any one of Claims 1 to 4, it is characterised in that: it is present in described oxidation
Melted flaky particles in thing deposition coverlay carries out micro-at the section vertical with substrate surface that oxide deposits coverlay
During sem observation, it is calculated as less than 10% with area occupation ratio.
6. according to the resistant to plasma body component according to any one of Claims 1 to 5, it is characterised in that: described oxide covers
The oxide spraying plating coverlay as basal layer that film is formed from base material and the oxide formed on the surface of this basal layer
The deposition such double-layer structure of coverlay is formed；Described oxide spraying plating coverlay and the total thickness of oxide deposition coverlay
Being 20 μm～300 μm, the thickness of described oxide deposition coverlay is 10 μm～200 μm.
7. according to the resistant to plasma body component according to any one of claim 1～6, it is characterised in that: described oxide covers
Oxide-film that film is formed by substrate surface is carried out oxidation processes, on the surface of this oxide-film, it is formed as basal layer
Oxide spraying plating coverlay and oxide such three layers of the coverlay of deposition formed on this oxide spraying plating coverlay
Structure is formed；Described oxide-film, as the oxide spraying plating coverlay of basal layer and the total thickness of oxide deposition coverlay
Being 20 μm～300 μm, the thickness of described oxide deposition coverlay is 10 μm～200 μm.
8. according to the resistant to plasma body component according to any one of claim 1～7, it is characterised in that: described oxide deposits
In the formation of coverlay use raw material fine particle be purity be the oxide particle of more than 99.9%.
9. according to the resistant to plasma body component according to any one of claim 1～8, it is characterised in that: described oxide deposits
The surface roughness Ra of coverlay is below 3 μm.
10. according to the resistant to plasma body component according to any one of claim 1～9, it is characterised in that: described oxide deposits
Coverlay is by Y2O3Constitute.
11. according to the resistant to plasma body component according to any one of claim 1～10, it is characterised in that: described oxide sinks
Long-pending coverlay is by Al2O3Constitute.
The manufacture method of 12. 1 kinds of resistant to plasma body components, it is characterised in that: it is any one of manufacturing claims 1～11
The manufacture method of described resistant to plasma body component, described manufacture method has following operation: to high-temperature plasma injection stream
Or the operation of the slip that the central part supply of high temperature gas flow is containing oxide particle；Oxide particle is heated to less than oxygen
The boiling point of compound and the temperature of sublimation point, thus the operation sprayed on base material with the jet velocity of 400～1000m/ seconds；And
Form the operation of oxide deposition coverlay on the substrate.
13. 1 kinds of film stacked laminators, it is characterised in that:
It is in the claim 1～11 manufacturing the oxide deposition coverlay with base material and coating described substrate surface
Resistant to plasma body component described in any one,
Described film stacked laminator has: generation chamber, and it passes through plasma arc, produces high-temperature plasma injection stream or High Temperature Gas
Body；Raw material slip supply mouth, its by the raw material slip containing oxide raw material powder to described high-temperature plasma injection stream or
The central part supply of high-temperature gas；Fuel supply mouth, fuel or oxygen are supplied by it to described generation chamber；Gas supply port,
Working gas is supplied by it to described generation chamber；And nozzle, it makes raw material by described working gas with fuel or oxygen
Slip aerifies, and the oxide raw material in gas is heated to the temperature of the boiling point less than oxide and sublimation point, and by former
Material oxide controls as the state to substrate surface injection so that it is jet velocity reached for 400～1000m/ seconds.
14. film stacked laminators according to claim 13, it is characterised in that: to the spray of substrate surface injection oxide raw material
Jet length between top ends and the described substrate surface of mouth is 100～400mm.
15. according to the film stacked laminator described in claim 13 or 14, it is characterised in that: the oxide in described raw material slip is former
The content of material powder is 30～80 volume %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014073959 | 2014-03-31 | ||
| JP2014-073959 | 2014-03-31 | ||
| PCT/JP2015/058458 WO2015151857A1 (en) | 2014-03-31 | 2015-03-20 | Plasma-resistant component, method for manufacturing plasma-resistant component, and film deposition device used to manufacture plasma-resistant component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106164325A true CN106164325A (en) | 2016-11-23 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580017990.2A Pending CN106164325A (en) | 2014-03-31 | 2015-03-20 | The film deposition apparatus used in the manufacture of resistant to plasma body component, the manufacture method of resistant to plasma body component and resistant to plasma body component |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20170022595A1 (en) |
| JP (1) | JPWO2015151857A1 (en) |
| KR (1) | KR20160119187A (en) |
| CN (1) | CN106164325A (en) |
| WO (1) | WO2015151857A1 (en) |
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| CN110465203A (en) * | 2018-05-09 | 2019-11-19 | 馗鼎奈米科技股份有限公司 | The method for improving the adhesive force of anti-pollution film |
| CN116096691A (en) * | 2020-09-09 | 2023-05-09 | 三菱综合材料株式会社 | Plasma-resistant coating film, sol-gel liquid for forming the film, method for forming plasma-resistant coating film, and substrate having plasma-resistant coating film |
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| JP2020084287A (en) * | 2018-11-29 | 2020-06-04 | 日本特殊陶業株式会社 | Filmed member and method of manufacturing the same, and method of evaluating the filmed member |
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| JP2020141123A (en) | 2019-02-27 | 2020-09-03 | Toto株式会社 | Member for semiconductor manufacturing device, semiconductor manufacturing device having the same, and display manufacturing device |
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Also Published As
| Publication number | Publication date |
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| WO2015151857A1 (en) | 2015-10-08 |
| JPWO2015151857A1 (en) | 2017-04-13 |
| US20170022595A1 (en) | 2017-01-26 |
| KR20160119187A (en) | 2016-10-12 |
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