WO2016080459A1 - 焼結体 - Google Patents
焼結体 Download PDFInfo
- Publication number
- WO2016080459A1 WO2016080459A1 PCT/JP2015/082452 JP2015082452W WO2016080459A1 WO 2016080459 A1 WO2016080459 A1 WO 2016080459A1 JP 2015082452 W JP2015082452 W JP 2015082452W WO 2016080459 A1 WO2016080459 A1 WO 2016080459A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sintered body
- mpa
- yttrium oxyfluoride
- yttrium
- sintering
- Prior art date
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- CHBIYWIUHAZZNR-UHFFFAOYSA-N [Y].FOF Chemical compound [Y].FOF CHBIYWIUHAZZNR-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000013001 point bending Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 43
- 238000005245 sintering Methods 0.000 claims description 41
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 29
- 229910052731 fluorine Inorganic materials 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 238000009826 distribution Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 125000001153 fluoro group Chemical group F* 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 10
- 229940105963 yttrium fluoride Drugs 0.000 description 10
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000001272 pressureless sintering Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000002706 hydrostatic effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- RFEISCHXNDRNLV-UHFFFAOYSA-N aluminum yttrium Chemical compound [Al].[Y] RFEISCHXNDRNLV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- C04B2235/668—Pressureless sintering
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
- C04B2235/81—Materials characterised by the absence of phases other than the main phase, i.e. single phase materials
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9692—Acid, alkali or halogen resistance
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/334—Etching
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- 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
Definitions
- the present invention relates to a sintered body containing an yttrium oxyfluoride.
- Fluorine-based corrosive gas, chlorine-based corrosive gas, and plasma using these are used in each process of semiconductor manufacturing, particularly dry etching, plasma etching, and cleaning. These corrosive gases and plasma corrode the constituent members of the semiconductor manufacturing apparatus, and fine particles separated from the surface of the constituent members tend to adhere to the semiconductor surface and cause product defects. Therefore, ceramics having high corrosion resistance against halogen-based plasma must be used as a bulk material for constituent members of a semiconductor manufacturing apparatus.
- aluminum oxide, yttrium oxide, aluminum yttrium composite oxide, and yttrium fluoride are used as such bulk materials (see Patent Documents 1 to 3).
- Patent Document 4 The applicant has previously proposed a thermal spray material containing yttrium oxyfluoride as a corrosion resistant material used to prevent corrosion of the etching apparatus.
- Aluminum-containing compounds such as aluminum oxide are concerned about aluminum contamination of semiconductor silicon. It has been pointed out that the plasma resistance of yttrium oxide is insufficient, and the surface is altered and yttrium fluoride (YF 3 ) is formed by fluorine plasma irradiation. Since yttrium fluoride is a fluoride, its chemical stability is questionable. In addition, when the inside of a semiconductor device is coated using yttrium oxyfluoride as a thermal spray material, there is a limit to the denseness of the resulting coating film, and it cannot be said that the performance of blocking halogen-based corrosive gas is sufficient. .
- an object of the present invention is to provide a sintered body that can eliminate various drawbacks of the above-described conventional technology.
- the present invention provides a sintered body containing yttrium oxyfluoride.
- the present invention is a method for producing the sintered body, Obtaining a raw material powder compact containing yttrium oxyfluoride; And obtaining the sintered body by sintering the molded body at a temperature of 800 ° C. or higher and 1800 ° C. or lower under a pressure of 5 MPa or higher and 100 MPa or lower. is there.
- the present invention is a method for producing the sintered body, Obtaining a raw material powder compact containing yttrium oxyfluoride; And a step of sintering the molded body at a temperature of 1000 ° C. or more and 2000 ° C. or less under no pressure.
- the sintered body of the present invention exhibits excellent resistance to halogen-based plasma, and is useful as a constituent material for semiconductor manufacturing apparatuses such as etching apparatuses. Moreover, the manufacturing method of the sintered compact of this invention can manufacture a dense sintered compact efficiently as a sintered compact of this invention.
- FIG. 2 is an X-ray chart by powder XRD diffraction measurement of the sintered body obtained in Example 1.
- FIG. 4 is an X-ray chart by powder XRD diffraction measurement of the sintered body obtained in Example 2.
- FIG. 6 is an X-ray chart by powder XRD diffraction measurement of the sintered body obtained in Example 3.
- FIG. 6 is an X-ray chart by powder XRD diffraction measurement of the sintered body obtained in Example 4.
- FIG. 3 is a SEM photograph of the sintered body obtained in Example 2 before and after plasma irradiation. It is a SEM photograph before and after plasma irradiation of the single crystal silicon which is the comparative example 1.
- FIG. 3 is a SEM photograph of the sintered body obtained in Example 2 before and after plasma irradiation. It is a SEM photograph before and after plasma irradiation of the single crystal silicon which is the comparative example 1.
- FIG. 3 is a SEM photograph of the sintered body
- FIG. It is a SEM photograph before and after plasma irradiation of the alumina which is the comparative example 2.
- FIG. It is a SEM photograph before and after plasma irradiation of the yttria which is the comparative example 3.
- FIG. It is a SEM photograph before and behind plasma irradiation of the yttrium fluoride which is the comparative example 4.
- FIG. It is a graph which shows the change of F / O ratio before and behind plasma irradiation in the sample surface of an Example and a comparative example.
- the sintered body of the present invention is characterized by containing yttrium oxyfluoride.
- the yttrium oxyfluoride in the present invention is a compound composed of yttrium (Y), oxygen (O), and fluorine (F).
- Examples of such compounds include Y 5 O 4 F 7 and Y 7 O 6 F 9 , and among these, one or more oxyfluorides are included. These can be used alone or in combination of two or more.
- YOF a sintered body excellent in mechanical strength can be obtained, a dense sintered body having no cracks can be obtained, and it has advantages such as excellent corrosion resistance compared to other compositions.
- Y 5 O 4 F 7 a dense sintered body without cracks can be obtained at a low temperature, and the formation of YOF after oxidation improves the corrosion resistance.
- the present invention by using yttrium oxyfluoride as a sintered body instead of a thermal spray material, it is possible to improve the barrier property of halogen-based corrosive gas.
- a thermal spray material When a thermal spray material is used, the particles formed from the thermal spray material are melted by thermal spraying to form a thermal spray film, and halogen-based corrosive gas flows into the minute gaps between the melted particles. There is.
- the sintered body has high density and excellent barrier properties against halogen-based corrosive gas. Therefore, when this is used as a component of a semiconductor device, for example, the flow of halogen-based corrosive gas into this member is prevented. Can be prevented.
- the sintered body of the present invention has a high performance of preventing corrosion caused by halogen-based corrosive gas.
- a member having a high barrier property against halogen-based corrosive gas is suitably used for, for example, a vacuum chamber constituent member of an etching apparatus, an etching gas supply port, a focus ring, a wafer holder and the like.
- the sintered body preferably has a relative density of 70% or more, more preferably 80% or more, and 90% or more. More preferred is 95% or more.
- the relative density (RD) is preferably as high as possible, and the upper limit is 100%.
- the porosity is preferably small.
- the open porosity is determined by the method described below, preferably 10% or less, more preferably 2% or less, and particularly preferably 0.5% or less.
- RD relative density
- OP open porosity
- the relative density (RD) and the open porosity can be measured by Archimedes method based on JIS R1634, and specifically by the following method.
- ⁇ 1 [g / cm 3 ] is the density of distilled water.
- the three-point bending strength ⁇ f of the sintered body of the present invention is a high value above a certain level.
- the three-point bending strength ⁇ f of the sintered body of the present invention is preferably 10 MPa or more, more preferably 20 MPa or more, still more preferably 50 MPa or more, and 100 MPa or more. It is particularly preferred.
- the higher the three-point bending strength ⁇ f the higher the strength as a constituent material of the semiconductor manufacturing apparatus, which is preferable.
- the upper limit is 300 MPa or less, such as the ease of manufacturing the sintered body. It is preferable from the viewpoint.
- the sintered body having the above strength can be obtained by producing the sintered body of the present invention by the production method (1) or (2) described later.
- the three-point bending strength ⁇ f is measured by the following method.
- ⁇ Method for measuring three-point bending strength ⁇ f > By cutting the sintered body and mirror polishing one side, a strip-shaped test piece having a thickness of 1.5 to 3.0 mm, a width of about 4 mm, and a length of about 35 mm is produced. This is placed on a SiC jig and a three-point bending test is performed with a universal material testing machine (1185 type, manufactured by INSTRON). The conditions are a distance between fulcrums of 30 mm, a crosshead speed of 0.5 mm / min, and the number of test pieces is 5. Based on JIS R1601, the bending strength ⁇ f [MPa] is calculated using the following equation.
- ⁇ f (3 ⁇ P f ⁇ L) / (2 ⁇ w ⁇ t 2 ) (MPa)
- P f is the load [N] when the test piece is broken
- L is the span distance [mm]
- w is the width [mm] of the test piece
- t is the thickness [mm] of the test piece.
- the sintered body of the present invention preferably has an elastic modulus of 25 GPa or more and 300 GPa or less, more preferably 50 GPa or more and 300 GPa or less, more preferably 100 GPa or more and 250 GPa or less, and most preferably 150 GPa or more and 200 GPa or less. is there.
- an elastic modulus of 25 GPa or more and 300 GPa or less, more preferably 50 GPa or more and 300 GPa or less, more preferably 100 GPa or more and 250 GPa or less, and most preferably 150 GPa or more and 200 GPa or less. is there.
- the elastic modulus By setting the elastic modulus in such a range, the material constituting the semiconductor manufacturing apparatus has high durability and exhibits excellent resistance to halogen-based plasma.
- One method for obtaining such an elastic modulus is a method of adjusting the average particle diameter of the raw material powder, the forming method, the pressing method, etc. in the method for producing a sintered body described
- the elastic modulus is obtained by the following method according to JIS R1602.
- the measurement uses an oscilloscope (WJ312A, manufactured by LECROY) and a pulsar receiver (5072PR, manufactured by Olympus NDT).
- Longitudinal wave vibrator (V110, 5 MHz) and transverse wave vibrator (V156, 5 MHz) are used for the test piece. ))
- the longitudinal wave velocity V l [m / s] and the transverse wave velocity V t [m / s] are measured from the propagation velocity of the pulse.
- the sintered body of the present invention preferably has a thermal conductivity of 5.0 W / (m ⁇ K) or more, more preferably 10.0 W / (m ⁇ K) or more.
- the sintered body having a high thermal conductivity can be suitably used for a component member that requires uniform temperature and a component member having a large temperature change.
- the thermal conductivity of the sintered body is 5.0 W / (m It is also preferable that the value is as low as K) or less, particularly about 3.0 W / (m ⁇ K) or less.
- the thermal conductivity can be measured as follows.
- ⁇ Measurement method of thermal conductivity> A square plate sample having a side of 10 mm and a thickness of 1 mm was used. Platinum coating was applied to both surfaces of the sample, and a spray containing carbon particles (FC-153, manufactured by Fine Chemical Japan) was thinly sprayed thereon. The blackened sample was placed in a jig, the surface was irradiated with a pulse (pulse width 0.33 ms) by a xenon flash lamp, and the temperature change on the back surface of the sample was measured to obtain the thermal diffusivity ⁇ . The temperature change was 10 times the half time as the calculation range. In addition, specific heat capacity C was determined using alumina as a standard sample.
- the sintered body of the present invention may be substantially composed only of yttrium oxyfluoride, but may contain components other than yttrium oxyfluoride. “Substantially” means that only unavoidable impurities are contained in addition to oxyfluoride, and specifically means that the content of oxyfluoride is 98% by mass or more. Examples of the inevitable impurities herein include by-products such as yttrium oxide produced by the following method (1) or (2).
- the content of the yttrium oxyfluoride in the sintered body of the present invention is 50% by mass or more from the viewpoint of further enhancing the plasma resistance effect of the present invention, and the mechanical strength. It is preferable from the viewpoint of improvement. From this viewpoint, the amount of yttrium oxyfluoride in the sintered body is more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 98% by mass or more. The higher the yttrium oxyfluoride content in the sintered body, the better.
- the content of yttrium oxyfluoride in the sintered body can be measured by the following method.
- the qualitative analysis in this case can be performed by, for example, X-ray diffraction measurement. X-ray diffraction measurement is performed on a powder sample in which yttrium oxide and yttrium oxyfluoride are mixed at a certain ratio. Of the obtained diffraction peaks, the ratio of the maximum peak intensity of yttrium oxide and the maximum peak intensity of yttrium oxyfluoride is taken and plotted against the mixing ratio to create a calibration curve.
- the mixing ratio of yttrium oxide and yttrium oxyfluoride is measured, and the ratio of yttrium oxyfluoride when the sum of the two is 100 is taken as the content of yttrium oxyfluoride.
- the X-ray diffraction measurement of the sintered body is a measurement of the sintered body as a powder, and can be performed by the method described in the examples described later.
- the substance and the oxyfluoride are analyzed in the same manner as described above. What is necessary is just to obtain
- the maximum peak height derived from yttrium oxyfluoride in the above scanning range is 1, the maximum peak height derived from components other than yttrium oxyfluoride is preferably 0.5 or less. , 0.05 or less is more preferable.
- the maximum peak height derived from YF 3 is 0. 1 or less is preferable, and 0.03 or less is more preferable.
- the maximum peak height derived from Y 2 O 3 is 0.2.
- X-ray diffraction measurement of the sintered powder can be performed by the method described in the examples described later.
- the peak ratio in the sintered body of the present invention can be set in the above range by adjusting the ratio of yttrium oxyfluoride in the raw material powder, the temperature of the sintering conditions, the sintering atmosphere, and the like.
- the sintered body of the present invention comprises a YOF, preferably contains rhombohedral as the YOF, if the sintered body of the present invention comprises a Y 5 O 4 F 7, oblique as the Y 5 O 4 F 7 It is preferable to include a tetragonal crystal. These crystal phases can be identified by performing X-ray diffraction measurement of the sintered body surface or powder.
- examples of components other than yttrium oxyfluoride include various sintering aids, binder resins, carbon, and the like.
- the sintered body of the present invention includes conventionally used aluminum oxide, yttrium oxide, aluminum yttrium composite oxide, yttrium fluoride, and other rare earth element-containing compounds other than yttrium.
- Various ceramic materials such as these may be contained.
- the sintered body of the present invention is a sintered body containing yttrium oxyfluoride, it has excellent resistance to halogen-based plasma as compared with sintered bodies of other ceramic materials. Compared with the thermal spray material containing yttrium oxyfluoride, it is excellent in denseness and barrier property against halogen-based corrosive gas.
- Examples of the method for producing a sintered body of the present invention include the following method (1). (1) a step of obtaining a molded body of raw material powder containing yttrium oxyfluoride; A step of obtaining the sintered body by sintering the molded body at a temperature of 800 ° C. to 1800 ° C. under a pressure of 5 MPa to 100 MPa.
- the step of obtaining a molded body and the step of sintering the molded body may be performed simultaneously.
- the method (1) includes putting a powder sample into a mold and pressure-sintering the powder sample as it is.
- Examples of the yttrium oxyfluoride in the raw material powder containing the yttrium oxyfluoride include those similar to the yttrium oxyfluoride contained in the sintered body.
- the yttrium oxyfluoride used as a raw material is usually in powder form.
- the average particle diameter of the yttrium oxyfluoride contained in the raw material powder is preferably 5 ⁇ m or less, more preferably 1.5 ⁇ m or less, still more preferably 1.1 ⁇ m or less, and particularly preferably 1 ⁇ m or less. preferable.
- the average particle diameter is a 50% diameter (hereinafter also simply referred to as “D50”) in the volume-based integrated fraction, and is measured by a laser diffraction / scattering particle size distribution measurement method.
- the specific measurement method is as follows.
- As a preferable particle diameter of the average particle diameter of the raw material powder the same particle diameter as the average particle diameter of the yttrium oxyfluoride contained in the raw material powder can be mentioned.
- Measurement method of average particle size Measure with Microtrack HRA manufactured by Nikkiso Co., Ltd. At the time of measurement, a 2 mass% sodium hexametaphosphate aqueous solution is used as a dispersion medium, and the sample (granule) is added to the sample circulator chamber of Microtrac HRA until the apparatus determines that the concentration is appropriate.
- the above-mentioned sintering aids and binders may be used as the other components in the raw material powder.
- the sintered body of the present invention includes sintering aids and binder resins.
- the amount of other components is preferably small.
- the sintering aid is preferably 5% by mass or less, and more preferably 2% by mass or less.
- the production method of the present invention is characterized in that a dense sintered body can be obtained even if a sintering aid is not used or the amount thereof is reduced as much as possible.
- the sintering aid here include SiO 2 , MgO, CaO, and various rare earth oxides.
- a die press method for molding the raw material powder, a die press method, a rubber press (hydrostatic pressure press) method, a sheet molding method, an extrusion molding method, a casting molding method, or the like can be used.
- the uniaxial pressure is preferably 20 MPa or more and 85 MPa or less, and more preferably 22 MPa or more and 75 MPa or less.
- the pressure in the hydrostatic press is preferably 85 MPa or more and 250 MPa or less, and more preferably 100 MPa or more and 220 MPa or less.
- the uniaxial pressure is preferably 10 MPa or more and 100 MPa or less, and more preferably 15 MPa or more and 80 MPa or less.
- the content of yttrium oxyfluoride is preferably 80% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
- the molded body obtained above is pressure-sintered.
- a specific pressure sintering method hot pressing, pulse current pressing (SPS), hot isostatic pressing (HIP) can be used.
- the pressure applied in the pressure sintering is preferably 5 MPa or more and 100 MPa or less. By setting the pressure to 5 MPa or more, a dense sintered body having high plasma resistance can be easily obtained, and by setting the pressure to 100 MPa or less, there are advantages such as suppressing damage to the press die. From these viewpoints, the pressure of pressure sintering is preferably 20 MPa or more, and more preferably 100 MPa or less.
- the sintering temperature is preferably 800 ° C. or higher and 1800 ° C. or lower.
- the temperature is 800 ° C. or higher, densification easily proceeds, decomposition and evaporation of the added binder proceeds, and unreacted components contained in the raw material react to form oxyfluoride.
- the sintering temperature is more preferably 1000 ° C. or higher and 1700 ° C. or lower.
- the time for pressure sintering at the pressure and temperature in the above range is preferably 0 hour or longer and 6 hours or shorter, and more preferably 20 minutes or longer and 2 hours or shorter.
- the pressure for pressure sintering is preferably from 30 MPa to 50 MPa, and the sintering temperature is preferably from 1300 ° C. to 1700 ° C.
- the pressure for pressure sintering is preferably 30 MPa or more and 100 MPa or less, and the sintering temperature is more preferably 1000 ° C. or more and 1500 ° C. or less.
- the sintered body of the present invention can be preferably produced by the following method (2) instead of the method (1).
- (2) a step of obtaining a molded body of raw material powder containing yttrium oxyfluoride; Sintering the molded body at a temperature of 1000 ° C. or more and 2000 ° C. or less under no pressure, and a method for producing a sintered body.
- the method (2) differs from the method (1) in that pressureless sintering is performed, but the step of obtaining a raw material powder compact is the same as the method (1).
- the sintering temperature is preferably 1000 ° C. or higher from the viewpoint of obtaining a dense sintered body and from the viewpoint of removing mixed organic substances, and the pressure of 2000 ° C. or lower is a pressure sintering apparatus that suppresses decomposition of oxyfluoride. It is preferable from the viewpoint of suppressing damage. From these viewpoints, the sintering temperature is more preferably 1200 ° C. or higher and 1800 ° C. or lower.
- the time for sintering at the above sintering temperature is preferably 0 hour or longer and 24 hours or shorter, more preferably 0 hour or longer and 6 hours or shorter.
- a sufficiently dense sintered body can be obtained by sintering the raw material powder at the above temperature even without pressureless sintering.
- Sintering in any of the methods (1) and (2) may be performed in an oxygen-containing atmosphere or in an inert atmosphere. However, it is preferably performed in an inert atmosphere from the viewpoint of preventing the formation of yttrium oxide.
- the oxygen-containing atmosphere includes air
- the inert atmosphere includes a rare gas such as argon, nitrogen, and vacuum.
- the sintering in any of the methods (1) and (2) is preferably performed at a temperature up to 1200 ° C. and at a temperature lowering of 0.5 ° C./min to 40 ° C./min. It is preferable to perform the temperature increase and decrease in the region at 1 ° C./min or more and 30 ° C./min or less.
- the sintered body obtained in this manner can be used for constituent members of a semiconductor manufacturing apparatus such as a vacuum chamber in an etching apparatus and a sample stage, chuck, focus ring, and etching gas supply port in the chamber.
- a semiconductor manufacturing apparatus such as a vacuum chamber in an etching apparatus and a sample stage, chuck, focus ring, and etching gas supply port in the chamber.
- the sintered compact of this invention can be used for the use of various plasma processing apparatuses and the structural member of a chemical plant besides the structural member of a semiconductor manufacturing apparatus.
- Example 1 (Production of sintered body containing YOF by pressureless sintering) About 1.4 g of YOF powder (average particle diameter 0.8 ⁇ m) was put in a circular mold having a diameter of 15 mm, and uniaxially pressed with a hydraulic press at a pressure of 25.5 MPa for 1 minute, followed by primary molding. The obtained primary molded article was further subjected to isostatic pressing at 200 MPa for 1 minute. This was put in an alumina crucible, spreaded with a powder, a compact was placed on it, covered, and the entire crucible was placed in a large carbon crucible. The temperature was raised to 1200 ° C.
- ⁇ XRD measurement of sintered powder Part of the sintered body was pulverized using a magnetic mortar and pestle to obtain a powder. This powder was set in a glass holder and subjected to XRD measurement.
- Example 2 (Production of sintered body containing YOF by pressure sintering) About 20 g of YOF powder (average particle diameter 0.8 ⁇ m) was placed in a rectangular mold having a length of 35 mm and a width of 35 mm, and primary molding was performed by a hydraulic press at a pressure of 18.4 MPa. This was put into a hot press die made of carbon having the same size as that of the square die and sintered by hot press. The temperature was raised to 1200 ° C. at 30 ° C./min in an Ar flow (flow rate 2 liters / minute), further raised to 1600 ° C. at 10 ° C./min, held at 1600 ° C. for 1 hour, and then 10 ° C./min.
- Ar flow flow rate 2 liters / minute
- the temperature was decreased to 1200 ° C., and then the temperature was decreased at 30 ° C./min. While being held at 1600 ° C. for 1 hour, uniaxial pressure was applied at a pressure of 36.7 MPa.
- the three-point bending strength measured by the above method was 120 MPa.
- the elastic modulus measured by the above method was 183 GPa, and the thermal conductivity measured by the above method was 17 W / (m ⁇ K).
- the XRD of the obtained sintered powder was measured.
- the obtained X-ray chart is shown in FIG. As shown in FIG.
- Example 3 (Production of sintered body containing Y 5 O 4 F 7 by pressureless sintering) About 1.4 g of Y 5 O 4 F 7 powder (average particle size 1.1 ⁇ m) is placed in a circular mold having a diameter of 15 mm, uniaxially pressed with a hydraulic press at a pressure of 25.5 MPa, and held for 1 minute. Temporarily molded. The obtained temporary molded article was further subjected to isostatic pressing at 200 MPa for 1 minute. This was put in an alumina crucible, spreaded with a powder, a compact was placed on it, covered, and the entire crucible was placed in a large carbon crucible.
- Example 4 (Production of sintered body containing Y 5 O 4 F 7 by pressure sintering). About 20 g of Y 5 O 4 F 7 powder (average particle diameter 1.1 ⁇ m) was placed in a rectangular mold having a length of 35 mm and a width of 35 mm, and was primary molded at a pressure of 18.4 MPa by a hydraulic press. This was put into a hot press die made of carbon having the same size as that of the square die and sintered by hot press. Under an Ar flow (flow rate 2 liters / minute), the temperature was raised to 1200 ° C. at 30 ° C./min, further raised to 1400 ° C. at 10 ° C./min, then lowered to 1200 ° C.
- Ar flow flow rate 2 liters / minute
- the XRD of the powder of the obtained sintered body was measured in the same manner as in Example 1.
- the obtained X-ray chart is shown in FIG.
- a peak considered to be derived from Y 5 O 4 F 7 is mainly observed, and very few peaks derived from components other than Y 5 O 4 F 7 are observed.
- this sintered body is considered to contain 95% by mass or more of Y 5 O 4 F 7 .
- Example 5 (Production of sintered body containing YOF by pressureless sintering)
- the relative density RD is 87% and the open porosity is the same as in Example 1 except that the sintering is performed from the Ar atmosphere to the air atmosphere and the holding time at 1600 ° C. is changed from 1 hour to 2 hours.
- a 0.2% sintered body was obtained.
- this sintered body contained a large amount of Y 2 O 3 in addition to YOF.
- CF 4 + O 2 plasma is irradiated to the surface of the sintered body obtained in Example 2, the single crystal of Comparative Example 1 and the sintered bodies of Comparative Examples 2 to 4 by a plasma processing apparatus (PT7160, Elminette). did. CF 4 was set to 0.8 scale, O 2 was set to 0.2 scale, and the output was 100 W and held for 30 minutes.
- the solid surfaces of Example 2 and Comparative Examples 1 to 4 before and after plasma irradiation were observed with a scanning electron microscope (SEM). SEM photographs of the respective solid surfaces are shown in FIGS. 5 to 9, the upper side is an SEM photograph before irradiation, and the lower side is an SEM photograph after irradiation.
- the yttrium oxyfluoride of Example 2 shows almost no change before and after irradiation.
- the silicon of Comparative Example 1 was flat before irradiation, but it was confirmed that the surface was rough after irradiation.
- the alumina which is Comparative Example 2 has a large number of white particles which were not seen before irradiation after irradiation.
- the yttria which is the comparative example 3 does not change so much before and after irradiation.
- the yttrium fluoride which is Comparative Example 4 has many cracks after irradiation.
- the sintered body of yttrium oxyfluoride of Example 2 and the sintered body of yttria of Comparative Example 3 are more halogen-based than other sintered bodies and single crystals. It was shown to be resistant to plasma.
- F / O atomic ratio before plasma irradiation F / O before irradiation
- F / O atomic ratio after plasma irradiation F / O after irradiation
- amount of change in F / O atomic ratio before and after plasma irradiation A graph showing (F / O after irradiation / F / O before irradiation) is shown in FIG.
- ⁇ density
- A is atomic weight
- E 0 acceleration voltage
- ⁇ 0 0.182
- Z is an average atomic number.
- the silicon (Si), alumina (Al 2 O 3 ), yttria (Y 2 O 3 ), and yttrium fluoride (YF 3 ) samples are irradiated with fluorine-based plasma.
- the F / O ratio was greatly increased. That is, penetration of F element into the surface of these samples was observed.
- the F / O ratio after irradiation is slightly less than twice before irradiation
- Yttrium fluoride (YF 3 ) of Comparative Example 4 the F / O ratio after irradiation is low.
- the upper left side is an SEM photograph
- the upper right side is a fluorine atom distribution map
- the lower right side is a platinum atom distribution map
- the lower left side is a platinum atom distribution map and a fluorine atom distribution map.
- the band-like one extending in the up-and-down direction is the platinum coat layer, and the left side is the sample.
- the right side of the platinum layer is a redeposition layer during ion milling, and is not an original sample.
- the left side of platinum is the surface of the sample.
- the sintered body of the present invention is made of YOF, it originally contains elemental fluorine.
- the gray portion other than the black portion corresponding to the platinum layer indicates the existence location of the fluorine atom, and this gray portion is from the black portion corresponding to platinum. Also spread across the left side.
- fluorine is uniformly distributed regardless of the depth from the surface.
- FIG. 12 in which a cross section of the sintered body after plasma irradiation is observed is gray in the fluorine atom distribution diagram on the upper right side. Since there is a part, fluorine exists in this part.
- the existence site of fluorine atoms in the sintered body of Comparative Example 3 is platinum. Concentrated just to the left of the layer, which is about 50 nm from the sample surface. That is, it can be seen that in the yttria sintered body in Comparative Example 3, fluorine atoms entered the surface by plasma irradiation.
- the sintered body of the present invention has higher corrosion resistance to the halogen-based plasma than any of the materials of Comparative Examples 1 to 4. Therefore, it is clear that the sintered body of the present invention is useful as a constituent member of a semiconductor manufacturing apparatus such as an etching apparatus.
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Abstract
Description
このようなバルク材料として、現在はアルミニウム酸化物、イットリウム酸化物、アルミニウムイットリウム複合酸化物や、イットリウムフッ化物が用いられている(特許文献1~3を参照)。
また、イットリウムのオキシフッ化物を溶射材料として用いて半導体装置の内部をコーティングした場合には、得られるコーティング膜の緻密性に限界があり、ハロゲン系腐食ガスを遮断する性能が十分なものと言えない。
イットリウムのオキシフッ化物を含む原料粉末の成形体を得る工程と、
前記成形体を、5MPa以上100MPa以下の圧力下、800℃以上1800℃以下の温度で焼結することにより前記焼結体を得る工程と、を有する、焼結体の製造方法を提供するものである。
イットリウムのオキシフッ化物を含む原料粉末の成形体を得る工程と、
前記成形体を、無加圧下、1000℃以上2000℃以下の温度で焼結する工程と、を有する、焼結体の製造方法を提供するものである。
YOFを用いることで、機械的強度に優れた焼結体が得られる、緻密で割れの無い焼結体が得られる、他の組成と比べて耐食性に優れる等の利点を有する。また、Y5O4F7を用いることで、緻密で割れの無い焼結体が低温で得られる、酸化後にYOFが生成することで耐食性が向上する等の利点を有する。
焼結体を蒸留水に入れ、ダイアフラム型真空ポンプによる減圧下で1時間保持した後、水中重量W2[g]を測定する。また、余分な水分を湿布で取り除き、飽水重量W3[g]を測定する。その後、乾燥器に入れて焼結体を十分に乾燥させた後、乾燥重量W1[g]を測定する。以下の式により、かさ密度ρb[g/cm3]と開気孔率OPを算出する。
ρb=W1/(W3-W2)×ρ1(g/cm3)
OP=(W3-W1)/(W3-W2)×100(%)
ここで、ρ1 [g/cm3]は蒸留水の密度である。得られたかさ密度ρbと、理論密度ρc[g/cm3]を用いて、相対密度(RD)[%]を以下の式により算出する。
RD=ρb/ρc×100(%)
3点曲げ強度σfは以下の方法で測定される。
焼結体を切断し、片面を鏡面研磨することにより、厚さ1.5~3.0mm, 幅約4mm、長さ約35mmの短冊形の試験片を作製する。これをSiC製治具に置き、万能材料試験機(1185型、INSTRON製)で3点曲げ試験を行う。条件は、支点間距離30mm、クロスヘッドスピード0.5mm/minとし、試験片本数は5本とする。JIS R1601に基づき、以下の式を用いて曲げ強度σf [MPa]を算出する。
σf =(3×Pf×L)/(2×w×t2) (MPa)
ここで、Pfは試験片が破断した時の荷重 [N]、Lはスパン距離 [mm]、wは試験片の幅[mm]、tは試験片の厚さ[mm]である。
弾性率はJIS R1602に従い、以下の方法で求められる。
測定はオシロスコープ(WJ312A、LECROY製)及びパルサーレシーバー(5072PR、Olympus NDT製)を用いる。試験片に縦波振動子(V110、5 MHz)、横波振動子(V156、5 MHz)を接着剤(縦波用:COUPLANT B GLYCERIN(オリンパス製)、横波用:ソニコートSHN-B25(ニチゴー日興製))を用いて固定し、パルスの伝搬速度から縦波速度Vl [m/s]と横波速度Vt [m/s]を測定する。得られたVl及びVt、試験片のかさ密度ρb [kg/mm3]から、以下の式を用いて弾性率E[GPa]を算出する。
E = ρb・(Vt 2・Vl 2- 4Vt 4)/(Vl 2 - Vt 2)×10-9 (GPa)
<熱伝導率の測定方法>
一辺10mm、厚さ1mmの正方形板状試料を用いた。試料の両面に白金コーティングをし、その上から炭素粒子入りスプレー(FC-153、ファインケミカルジャパン製)を薄く吹きつけた。黒化処理をした試料を治具に設置し、表面にキセノンフラッシュランプによるパルス(パルス幅0.33ms)を照射し、試料裏面の温度変化を測定することにより、熱拡散率αを求めた。温度変化はハーフタイムの10倍を計算範囲とした。また、標準試料としてアルミナを用い、比熱容量Cを求めた。温度25℃、湿度50%、空気中で測定を行い、測定は3回行った。測定には熱定数測定装置(LFA447、NETZSCH製)を用いた。
JIS R1611に基づき、以下の式を用いて熱伝導率λ [W/(m・K)]を求めた。
λ = α × C × ρ (W/(m・K))
ここでαは熱拡散率 [m2/s]、Cは比熱容量 [J/kg・K], ρは試料のかさ密度 [kg/m3]である。
酸化イットリウムとオキシフッ化イットリウムを一定割合で混合した粉末試料について、X線回折測定を行う。得られた回折ピークのうち、酸化イットリウムの最大ピーク強度とオキシフッ化イットリウムの最大ピーク強度の比をとり、混合比に対してプロットし、検量線を作成する。検量線に照らして酸化イットリウムとオキシフッ化イットリウムとの混合比を測定し、両者の合計を100とした場合のオキシフッ化イットリウムの比率を、オキシフッ化イットリウムの含有量とする。焼結体のX線回折測定は焼結体を粉末としたものの測定であり、後述した実施例に記載の方法により行うことができる。
また、上記の定性分析により、焼結体においてイットリウムのオキシフッ化物及びイットリウム酸化物以外の物質が含まれていることが判明した場合は、その物質について、上述した方法と同様にしてその物質とオキシフッ化イットリウムとの混合比を測定することで、オキシフッ化イットリウムの含有量を求めればよい。
(1)イットリウムのオキシフッ化物を含む原料粉末の成形体を得る工程と、
前記成形体を、5MPa以上100MPa以下の圧力下、800℃以上1800℃以下の温度で焼結することにより前記焼結体を得る工程と、を有する、焼結体の製造方法。
上記(1)の方法において、成形体を得る工程と成形体を焼結する工程は同時に行ってもよい。例えば、粉末試料を型に入れ、これをそのまま加圧焼結することも上記(1)の方法に含まれる。
日機装株式会社製マイクロトラックHRAにて測定する。測定の際には、分散媒として2質量%ヘキサメタリン酸ナトリウム水溶液を用い、マイクロトラックHRAの試料循環器のチャンバーに試料(顆粒)を適正濃度であると装置が判定するまで添加する。
(2)イットリウムのオキシフッ化物を含む原料粉末の成形体を得る工程と、
前記成形体を、無加圧下、1000℃以上2000℃以下の温度で焼結する工程と、を有する、焼結体の製造方法。
焼結温度は1000℃以上であることが緻密な焼結体を得る観点や、混入した有機物除去の観点から好ましく、2000℃以下であることがオキシフッ化物の分解を抑える、加圧焼結機器の損傷を抑える、等の観点から好ましい。これらの観点から、焼結温度は1200℃以上、1800℃以下がより好ましい。また、上記の焼結温度で焼結する時間(最高温度での保持時間)は、0時間以上24時間以下が好ましく、0時間以上6時間以下がより好ましい。本製造方法では無加圧焼結であっても上記の原料粉末を上記の温度で焼結することにより、十分に緻密な焼結体を得ることができる。
YOF粉末(平均粒子径0.8μm)を、直径15mmの円形の金型に、約1.4g入れ、油圧プレスで25.5MPaの圧力で一軸加圧して1分間保持し、一次成形した。得られた一次成形品についてさらに、200MPa、1分間保持で静水圧成形をした。これをアルミナ製るつぼに入れ、敷き粉を敷いて、その上に成形体を乗せ、ふたをして、さらにるつぼ全体をカーボン製の大きなるつぼに入れた。Ar流中(流速2リットル/分)下、30℃/minで1200℃まで昇温し、さらに10℃/minで1600℃まで昇温し、1600℃で1時間保持した後、10℃/minで1200℃まで降温し、その後30℃/minで降温した。これにより焼結体を得た。得られた焼結体について上記の方法で相対密度RDを測定したところ、96%であり、開気孔率は0.2%であった。下記の方法にて、得られた焼結体の粉末のXRDを測定した。得られたX線チャートを図1に示す。図1に示す通り、このX線チャートにおいては、YOFに由来するとみられるピークのみが観察され、YOF以外の成分に由来するピークは観察されなかったこと、原料粉末としてYOFのみを用いたことから、この焼結体はYOFをほぼ100質量%含むものとみられる。実際に得られた焼結体について、上記の方法でイットリウムのオキシフッ化物の量を測定したところ、100質量%であった。
焼結体の一部を、磁製乳鉢と乳棒を用いて粉砕して粉末を得、この粉末をガラス製ホルダーにセットし、XRD測定を行った。XRDの測定条件は、連続スキャンで、Cuターゲット、管球電圧40kV,管球電流30mA、走査範囲2θ=10°~80°、走査速度0.050°2θ/sとした。Kβ線はわん曲グラファイトフィルターにより除去した。
縦35mm、横35mmの四角形の金型に、YOF粉末(平均粒子径0.8μm)を約20g入れ、油圧プレスにより、18.4MPaの圧力で一次成形をした。これを前記の角型と同じサイズのカーボン製のホットプレス型に入れ、ホットプレスにより焼結した。Ar流中(流速2リットル/分)下、30℃/minで1200℃まで昇温し、さらに10℃/minで1600℃まで昇温し、1600℃で1時間保持した後、10 ℃/minで 1200℃まで降温し、その後 30℃/min で降温した。1600℃で1時間保持している間に36.7MPaの圧力で一軸加圧した。これにより焼結体を得た。実際に得られた焼結体について上記の方法で相対密度RDを測定したところ99.5%であり、開気孔率は0.1%であった。また上記の方法で3点曲げ強度を測定したところ120MPaであった。また上記の方法で弾性率を測定したところ183GPaであり、上記の方法で熱伝導率を測定したところ17W/(m・K)であった。実施例1と同様にして、得られた焼結体の粉末のXRDを測定した。得られたX線チャートを図2に示す。図2に示す通り、このX線チャートにおいては、YOFに由来するとみられるピークのみが観察され、YOF以外の成分に由来するピークは観察されなかったこと、原料粉末としてYOFのみを用いたことから、この焼結体はYOFを100質量%含むものとみられる。得られた焼結体について、上記の方法でイットリウムのオキシフッ化物の量を測定したところ、100質量%であった。
Y5O4F7粉末(平均粒子径1.1μm)を、直径15mmの円形の金型に、約1.4g入れ、油圧プレスで25.5MPaの圧力で一軸加圧して1分間保持し、一時成形した。得られた一時成形品についてさらに、200MPa、1分間保持で静水圧成形をした。これをアルミナ製るつぼに入れ、敷き粉を敷いて、その上に成形体を乗せ、ふたをして、さらにるつぼ全体をカーボン製の大きなるつぼに入れた。Ar流中(流速2リットル/分)下、30℃/minで1200℃まで昇温し、さらに10℃/minで1400℃まで昇温した後 10℃/minで1200℃まで降温し、その後30℃/minで降温した。これにより焼結体を得た。1400℃での保持時間は0時間であった。得られた焼結体について上記の方法で相対密度RDを測定したところ、99.6%であり、開気孔率は0.1%であった。また、得られた焼結体について、実施例1と同様にして、得られた焼結体の粉末のXRDを測定した。得られたX線チャートを図3に示す。図3に示す通り、このX線チャートにおいては、Y5O4F7に由来するとみられるピークが主として観察され、Y5O4F7以外の成分に由来するピークは極めてわずかしか観察されなかったこと、原料粉末としてY5O4F7のみを用いたことから、この焼結体はY5O4F7を95質量%以上含むものとみられる。
縦35mm、横35mmの四角形の金型に、Y5O4F7粉末(平均粒子径1.1μm)を約20g入れ、油圧プレスにより、18.4MPaの圧力で一次成形をした。これを前記の角型と同じサイズのカーボン製のホットプレス型に入れ、ホットプレスにより焼結した。Ar流中(流速2リットル/分)下、30℃/minで1200℃まで昇温し、さらに10℃/minで1400℃まで昇温した後 10℃/minで1200℃まで降温し、その後30℃/minで降温した。1400℃での保持時間は0時間であった。温度が1200℃以上である間に36.7MPaで一軸加圧した。これにより焼結体を得た。得られた焼結体について上記の方法で相対密度RDを測定したところ99.8%であり、開気孔率は0.1%であった。ままた得られた焼結体について上記の方法で3点曲げ強度を測定したところ26MPaであった。また上記の方法で弾性率を測定したところ157GPaであり、上記の方法で熱伝導率を測定したところ2.9W/(m・K)であった。また、得られた焼結体について、実施例1と同様にして、得られた焼結体の粉末のXRDを測定した。得られたX線チャートを図4に示す。図4に示す通り、このX線チャートにおいては、Y5O4F7に由来するとみられるピークが主として観察され、Y5O4F7以外の成分に由来するピークは極めてわずかしか観察されなかったこと、及び、原料粉末としてY5O4F7のみを用いたことから、この焼結体はY5O4F7を95質量%以上含むものとみられる。
焼結をAr雰囲気下から大気雰囲気下とし、1600℃での保持時間を1時間から2時間とした以外は、実施例1と同様にして、相対密度RDが87%であり、開気孔率が0.2%の焼結体を得た。XRD測定の結果、この焼結体にはYOFの他に多量のY2O3が含まれていた。
単結晶シリコン(Si)を用いた。
アルミナ(Al2O3)の焼結体を用いた。
イットリア(Y2O3)の焼結体を用いた。
フッ化イットリウム(YF3)の焼結体を用いた。
プラズマ処理装置(PT7160、エルミネット)により、実施例2で得られた焼結体、比較例1の単結晶及び比較例2~4の焼結体の表面に対し、CF4+O2プラズマを照射した。CF4を0.8目盛り、O2を0.2目盛りとし、出力を100Wとして30分保持した。
プラズマ照射前後における、実施例2及び比較例1~4の各固体表面を走査型電子顕微鏡(SEM)により観察した。それぞれ固体表面を撮影したSEM写真を図5~図9に示す。図5~図9においてそれぞれ上側が照射前のSEM写真であり、下側が照射後のSEM写真である。
以上より、焼結体表面のSEM観察によれば、実施例2のイットリウムのオキシフッ化物の焼結体及び比較例3のイットリアの焼結体が、他の焼結体や単結晶よりもハロゲン系プラズマに耐性があることが示された。
各試料表面について、走査型電子顕微鏡(S-4800、日立ハイテクノロジーズ)に附属の装置により、EDX分析を行った。倍率は5000倍とし、加速電圧を1kV, 3kV、10kVおよび30kVに変化させて測定を行い、ZAF法により下記式を用いて電子侵入深さRに対する原子の質量濃度Ciの変化を求めた。さらに求めた関係から各試料表面から電子侵入深さが0.1μm(100nm)までの部分におけるF原子及びO原子の質量濃度を求めた。得られた濃度により、この部分におけるF/Oの原子比を求めた。プラズマ照射前のF/Oの原子比(照射前F/O)、プラズマ照射後のF/Oの原子比(照射後F/O)及び、プラズマ照射前後におけるF/Oの原子比の変化量(照射後F/O/照射前F/O)の示すグラフを図10に示す。下記式においてρは密度、Aは原子量、E0は加速電圧、λ0は0.182である。Zは平均原子番号であり、それぞれの元素の原子番号をZi、質量濃度をCiとすると、Z=ΣCiZiで表される。
プラズマ照射後の試料の表面に目印として白金を蒸着したのち、日立イオンミリング装置IM4000により、表面に垂直にArイオンを照射して、断面観察用試料を作製した。この断面観察用試料を高感度のEDXを装備した走査型電子顕微鏡(SU-8200、日立ハイテクノロジーズ)により観察し、SEM写真を得るとともに、酸素、フッ素、白金、イットリウムの原子分布図を得た。実施例2の焼結体断面のSEM写真及び原子分布図を図11に示し、比較例3の焼結体断面のSEM写真及び原子分布図を図12に示す。図11及び図12のいずれにおいても上段左側がSEM写真であり、上段右側がフッ素原子分布図であり、下段右側が白金原子分布図であり、下段左側が白金原子分布図とフッ素原子分布図とを重ね合せた図である。
一方、比較例3であるイットリア焼結体はフッ素を元来含有していないにも関わらず、プラズマ照射後におけるこの焼結体断面を観察した図12では、上段右側のフッ素原子分布図において灰色部分が存在することからこの部分にフッ素が存在している。図12の下段左側の白金原子分布図とフッ素原子分布図とを重ね合せた図及び図12のSEM写真から明らかなように、比較例3の焼結体におけるフッ素原子の存在部位とは、白金層のすぐ左側に集中しており、これは試料表面から約50nmの範囲である。つまり比較例3におけるイットリアの焼結体ではプラズマ照射により表面にフッ素原子が侵入したことが判る。
Claims (10)
- イットリウムのオキシフッ化物を含む焼結体。
- イットリウムのオキシフッ化物がYOFである、請求項1に記載の焼結体。
- イットリウムのオキシフッ化物がY5O4F7である、請求項1に記載の焼結体。
- イットリウムのオキシフッ化物を、50質量%以上含む請求項1~3の何れか1項に記載の焼結体。
- 相対密度が70%以上である、請求項1~4の何れか1項に記載の焼結体。
- 開気孔率が10%以下である、請求項1~5の何れか1項に記載の焼結体。
- 弾性率が25GPa以上、300GPa以下である、請求項1~6の何れか1項に記載の焼結体。
- 3点曲げ強度が、10MPa以上、300MPa以下である、請求項1~7の何れか1項に記載の焼結体。
- 請求項1~8の何れか1項に記載の焼結体の製造方法であって、
イットリウムのオキシフッ化物を含む原料粉末の成形体を得る工程と、
前記成形体を、5MPa以上100MPa以下の圧力下、800℃以上1800℃以下の温度で焼結することにより前記焼結体を得る工程と、を有する、焼結体の製造方法。 - 請求項1~8の何れか1項に記載の焼結体の製造方法であって、
イットリウムのオキシフッ化物を含む原料粉末の成形体を得る工程と、
前記成形体を、無加圧下、1000℃以上2000℃以下の温度で焼結する工程と、を有する、焼結体の製造方法。
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