CN101665352A - Aluminum oxide sintered product and method for producing the same - Google Patents
Aluminum oxide sintered product and method for producing the same Download PDFInfo
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- CN101665352A CN101665352A CN200910168386A CN200910168386A CN101665352A CN 101665352 A CN101665352 A CN 101665352A CN 200910168386 A CN200910168386 A CN 200910168386A CN 200910168386 A CN200910168386 A CN 200910168386A CN 101665352 A CN101665352 A CN 101665352A
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Abstract
The invention provides an aluminum oxide sintered product which can be provided with volume resistivity adjusted between the coulombian and Johnson type and excellent corrosion resistance. The aluminum oxide sintered product of the invention is the sintered product with layer phase containing a rare-earth element and fluorine among grains of aluminum oxide serving as a main component, or a phase containing a rare-earth element and fluorine along edges of grains of aluminum oxide serving as a main component. Such an aluminum oxide sintered product includes a phase containing a rare-earth element and a fluorine element among grains of aluminum oxide, the phase not being in the form of localized dots but in the form of line segments, when viewed in an SEM image. An aluminum oxide sintered product according to the present invention can be readily adjusted to have a volume resistivity in the range of 1*10 <13> to 1*10<16> omega.cm, wherein the volume resistivity is calculated from a currentvalue after the lapse of 1 minute from the application of a voltage of 2 kV/mm to the aluminum oxide sintered product at room temperature.
Description
Technical field
The present invention relates to alumina sintered body and manufacture method thereof.
Background technology
In the past, in semiconductor-fabricating device, used electrostatic chuck to fix wafer.Electrostatic chuck possesses the internal electrode that applies voltage and the dielectric layer that is laminated in this internal electrode, and it is to constitute in the mode that produces electrostatic adhesion power under being placed with the state of wafer during to inner electrode application voltage between dielectric layer and the wafer.Electrostatic chuck has one pole mode with an internal electrode and separates the bipolar fashion that is provided with a pair of (promptly two) internal electrode.In the electrostatic chuck of one pole mode, electrostatic adhesion power is by portion's electrode within it and is arranged at and applies voltage between the outer electrode of outside of electrostatic chuck and produce, in the electrostatic chuck of bipolar fashion, electrostatic adhesion power produces by pair of internal electrodes is applied voltage.Such electrostatic chuck as shown in Figure 6, roughly is divided into following two types: utilizing volume specific resistance is 10
8～10
12Material about Ω cm produces Johnson as dielectric medium and draws Buick power, thus Johnson La Bieke type of absorption wafer; (volume specific resistance surpasses 10 to utilize isolator
16The material of Ω cm) produce the Coulomb's force as dielectric medium, thus the coulomb type of absorption wafer.Johnson La Bieke type, although can obtain high adsorptive power, the power supply of the costliness of not only essential high current capacity, and, therefore, might cause electric injury to the unicircuit that forms on the wafer because its leakage current thereby pettiness electric current flow to wafer.Because above-mentioned situation, it is more and more that the coulomb type that leakage current is few adopts, but there is the little problem of electrostatic adhesion force rate Johnson La Bieke type in a coulomb type.In order to address this problem, to study dielectric volume specific resistance is being controlled at 1 * 10
14About Ω cm, take into account the raising of adsorptive power and the minimizing of leakage current.For example, disclose in the patent documentation 1 and burnt till, thereby adjusted volume specific resistance in aluminum oxide, adding the material that has the silicon carbide of electroconductibility and obtain.In addition, disclose the material that obtains in aluminum oxide, adding magnesium oxide with electroconductibility and titanium oxide in the patent documentation 2 and burnt till, thereby adjusted volume specific resistance.
Patent documentation 1: TOHKEMY 2003-152065 communique
Patent documentation 2: TOHKEMY 2004-22585 communique
Summary of the invention
But the silicon compound, the titanium compound that use in the patent documentation 1,2 be that etchant gas or their plasma body do not have sufficient erosion resistance for fluorine particularly, so wafer may be contaminated owing to these electroconductive particle.
The present invention obtains in view of such problem just, and main purpose provides the volume specific resistance between coulomb type of can adjusting and Johnson La Bieke type and the alumina sintered body of excellent corrosion resistance.
To achieve these goals, discoveries such as the inventor, in as the aluminum oxide of principal constituent, add various metal oxides, nitride, carbide, fluorochemical etc., when burning till by hot pressing, added under the situation of rare earth fluorine, can access alumina sintered body, thereby finish the present invention with the volume specific resistance between coulomb type and Johnson La Bieke type.
That is, alumina sintered body of the present invention is layeredly to have the sintered compact mutually that contains rare earth element and fluorine element each other at the aluminium oxide particles as principal constituent.Here, so-called stratiform except comprising continuous cambial situation, also comprises cambial by spells situation.In addition, form other states, alumina sintered body of the present invention is layeredly to have the sintered compact mutually that contains rare earth element and fluorine element along the aluminium oxide particles rib each other as principal constituent.Here, so-called " existing ",, also comprise existing by spells along rib except along the situation of rib continued presence along rib.
With regard to alumina sintered body of the present invention, can easily will adjust between coulomb type and Johnson La Bieke type through the volume specific resistance that the current value after 1 minute is calculated by apply 2kV/mm voltage in room temperature, therefore not only can obtain the adsorptive power stronger than coulomb type, and compare with Johnson La Bieke type, leakage current reduces.In addition, aluminum oxide has sufficient erosion resistance, the erosion resistance mutually that contains rare earth element and fluorine element is also than silicon element compound, titanium compound height, has equal above erosion resistance with respect to aluminum oxide, therefore, erosion resistance as a whole, particularly increase for the corrosive gases of fluorine element system or the erosion resistance of its plasma body.Here, volume specific resistance adjusts to coulomb type easily and Johnson La Bieke type intermediary reason is also uncertain, but think that a reason is, the resistance mutually that contains rare earth element and fluorine element that layeredly exists each other or exist along aluminium oxide particles rib each other at aluminium oxide particles is lower than aluminum oxide.
Description of drawings
Fig. 1 is the SEM image of the rupture cross-section of alumina sintered body, (a) expression embodiment 2 (additive YbF
3, 1600 ℃ of firing temperatures), (b) expression comparative example 5 (additive Yb
2O
3, 1600 ℃ of firing temperatures).
Fig. 2 is the SEM image of the rupture cross-section of alumina sintered body, (a) expression embodiment 3 (additive YbF
3, 1700 ℃ of firing temperatures), (b) expression comparative example 6 (additive Yb
2O
3, 1700 ℃ of firing temperatures).
Fig. 3 is the SEM image of the mirror ultrafinish face of embodiment 7.
Fig. 4 is the map that the EPMA of the mirror ultrafinish face of embodiment 7 obtains, and is each element of F, Al, Yb to the same visual field image when carrying out face scanning.
Fig. 5 is the figure of expression with respect to the relation of the addition of fluoridizing ytterbium of aluminum oxide 100 weight parts and room temperature volume specific resistance.
Fig. 6 is with YbF
3Weight part be transverse axis, added the chart of intensity near the each point when being the longitudinal axis with the weight part of MgO.
Fig. 7 is that the weight part with MgO is a transverse axis, the chart when being the longitudinal axis with intensity.
Fig. 8 is that the weight ratio with Mg/Yb is a transverse axis, the chart when being the longitudinal axis with intensity.
Fig. 9 is that the aluminum oxide particle diameter with sintered compact is a transverse axis, the chart when being the longitudinal axis with intensity.
Figure 10 is the SEM photo of the rupture cross section of alumina sintered body, and (a) expression embodiment 4, (b) expression embodiment 16, (c) represent embodiment 17.
Figure 11 is the chart of the relation of expression volume specific resistance and adsorptive power.
Embodiment
Alumina sintered body of the present invention, be layeredly to have the sintered compact mutually that contains rare earth element and fluorine element each other, or have the sintered compact mutually that contains rare earth element and fluorine element along aluminium oxide particles rib each other as principal constituent at aluminium oxide particles as principal constituent.
Alumina sintered body of the present invention, when observing the SEM image, what contain rare earth element and fluorine element is not to form an existence partly at aluminium oxide particles each other, but exists in the mode that forms line segment.Such SEM image has confirmed when observing alumina sintered body of the present invention three-dimensionally, what contain rare earth element and fluorine element layeredly is present in aluminium oxide particles each other mutually, perhaps contains existing along aluminium oxide particles rib each other of rare earth element and fluorine element.
With regard to alumina sintered body of the present invention, be preferably 1 * 10 by apply the volume specific resistance that the current value of 2kV/mm voltage after 1 minute calculate in room temperature
13～1 * 10
16Ω cm.Like this, volume specific resistance can reach between coulomb type and Johnson La Bieke type, therefore, when alumina sintered body of the present invention is used as the dielectric medium of electrostatic chuck, not only can obtain the adsorptive power stronger than coulomb type, and compare with Johnson La Bieke type, leakage current reduces.
In the alumina sintered body of the present invention, aluminium oxide particles can be that spheroid (spherical or ellipsoid shape etc.) also can be a polyhedron, preferably polyhedron.In addition, median size is not particularly limited, if but the excessive intensity that may cause reduce, therefore be preferably below the 40 μ m.The not special infringement of too small situation, but in fact usually more than 0.3 μ m.The mensuration of median size of this moment is, the fracture surface of sample of carrying out after the pliability test is carried out electron microscope observation, and the median size calculated by method of bisector multiply by 1.5 again and draws.
In the alumina sintered body of the present invention, rare earth element is not particularly limited, but for example preferred yttrium, lanthanum, ytterbium.Here, as well-known, so-called rare earth element is meant that lanthanon adds that scandium, yttrium amount to 17 kinds of elements, and so-called lanthanon is meant that lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium amount to 15 kinds of elements.The content of such rare earth element is not particularly limited, if too much, then at aspects such as thermal conductivity, coefficient of thermal expansions, have the tendency that increases with the deviation of aluminum oxide, consider that from this viewpoint the content of rare earth element is preferably below the 20 weight %, more preferably below the 5 weight %.If very few, the amount that then is considered to the crystal boundary phase that helps conducting electricity reduces, the resistance characteristic that might can not obtain to expect, and from this viewpoint consideration, the content of rare earth element is preferably more than the 0.1 weight %, more preferably more than the 0.3 weight %.In addition, the content of fluorine element also is not particularly limited, if but too much, then have the tendency that is difficult to densification, if very few, then have and be difficult to the microstructure that obtains to expect and the tendency of resistance characteristic.Consider that from this viewpoint the content of fluorine element is preferably in the scope of 0.05～5 weight %, more preferably in the scope of 0.1～2 weight %.
In the alumina sintered body of the present invention, described contain rare earth element and fluorine element mutually in contain magnesium, all with respect to sintered compact, the content of this magnesium is preferably with respect to more than all 0.1 weight % of sintered compact.All with respect to sintered compact, the content of this magnesium is compared with not magniferous situation during less than 0.1 weight %, and the intensity of sintered compact reduces, and when surpassing 0.1 weight %, the intensity of sintered compact improves on the contrary.In addition, the content of magnesium is not particularly limited, if but too much, then volume specific resistance can surpass 1 * 10
16Therefore Ω cm is preferably below the 5 weight %.
In the alumina sintered body of the present invention, described contain rare earth element and fluorine element mutually in contain magnesium, this magnesium is preferably 0.1～0.33 with respect to the weight ratio of described rare earth element.If in this numerical range, compare with not magniferous situation, can access the higher sintered compact of intensity.
In the alumina sintered body of the present invention, the particle diameter of described aluminum oxide is preferably below the 7 μ m.If the particle diameter of aluminum oxide is below the 7 μ m, then can obtain high-intensity sintered compact.Particularly, if below 6 μ m, then can obtain more high-intensity sintered compact.
Alumina sintered body of the present invention can use as the dielectric medium of electrostatic chuck.Specifically, can make electrostatic chuck by in alumina sintered body of the present invention, imbedding internal electrode, also can by the alumina sintered body of the present invention of covering on internal electrode and below internal electrode and the side cover other sintered compacies and make electrostatic chuck, also can on internal electrode and the side covers alumina sintered body of the present invention and below internal electrode other sintered compacies of covering make electrostatic chuck.Here electrostatic chuck can be that the one pole mode also can be a bipolar fashion.
With regard to alumina sintered body of the present invention,, also can contain other additive, for example metal oxide, metal nitride etc. so long as do not become element or the amount that semi-conductor pollutes.As metal oxide, can enumerate magnesium oxide etc., as metal nitride, can enumerate aluminium nitride etc.These additives play the particle shape of the aluminum oxide in the control sintered compact, the effect of particle diameter.But, consider from the viewpoint of erosion resistance, wish that the content of these compositions is few.
The manufacture method of alumina sintered body of the present invention is that under vacuum or inert atmosphere, the mixture that will be added with the fluorochemical of rare earth element in the aluminum oxide of main raw material carries out hot pressing and burns till, thereby obtains alumina sintered body.By this manufacture method, make easily by applying 2kV/mm voltage in room temperature through the alumina sintered body of volume specific resistance between coulomb type and Johnson La Bieke type that the current value after 1 minute is calculated.
In the manufacture method of alumina sintered body of the present invention, the preferably highly purified aluminum oxide of the aluminum oxide of use, for example aluminum oxide of purity more than 99%, the especially preferably aluminum oxide of purity more than 99.5%.In addition, the particle shape of aluminum oxide can be that spheroid (spherical or ellipsoid shape etc.) also can be a polyhedron, preferably polyhedron.
In the manufacture method of alumina sintered body of the present invention, the fluorochemical of rare earth element preferably from by scandium fluoride, yttrium fluoride, lanthanum fluoride, cerium fluoride, praseodymium fluoride, neodymium fluoride, samaric fluoride, europium, gadolinium fluoride, fluoridize terbium, dysprosium fluoride, holmium fluoride, fluoridize erbium, fluoridize thulium, fluoridize ytterbium, fluoridize more than one that select the group that lutetium forms, be more preferably yttrium fluoride, lanthanum fluoride or fluoridize ytterbium.
In the manufacture method of alumina sintered body of the present invention, too small then volume specific resistance is high and might can not obtain sufficient adsorptive power if the fluorochemical of rare earth element is with respect to the weight ratio of aluminum oxide, if this weight ratio greatly, volume specific resistance is reduced to 10
13Ω cm has just stopped, but may detrimentally affect be arranged to other materials characteristics such as intensity.Consider from this viewpoint,, preferably, more preferably add with 1～5 scope to add the fluorochemical of rare earth element in the scope of 0.5～10 weight part with respect to aluminum oxide 100 weight parts.In addition, use contains magnesian material when pressing the mixture burn till as heat supply, preferably adding magnesium oxide more than 0.3 weight part with respect to aluminum oxide 100 weight parts, is that 0.1～0.4 mode is added magnesium oxide with magnesium oxide with respect to the weight ratio of the fluorine element compound of rare earth element perhaps.Do like this and can obtain when not adding magnesium oxide the higher sintered compact of specific tenacity mutually.
In the manufacture method of alumina sintered body of the present invention, the mixture of the fluorochemical by will being added with rare earth element in the aluminum oxide of main raw material carries out wet mixing in organic solvent, thereby makes slurries, and this slurry dried is obtained concocting powder.Here, when carrying out wet mixing, also can use a jar shape material grinder, trommel screen, buhrstone mill etc. to mix pulverizer.In addition, also can carry out dry type mixes and replaces wet mixing.In the operation that the blending powder that obtains is formed, when making tabular molding, can use the metal die pressing.Compacting pressure is preferably 100kgf/cm
2More than, as long as but can keep shaping then to be not particularly limited.Also can be filled in the hot-die with the state of powder.Usually, fluorochemical hinders the sintering of aluminum oxide, in normal pressure burns till, is difficult to obtain fine and close sintered compact.Therefore, being suitable for hot pressing as material of the present invention burns till.If moulding pressure when hot pressing is burnt till low excessively, then has the tendency that is difficult to densification, if too high, then when having the crystal boundary phase composition of liquid phaseization, this crystal boundary may run off or easy residual airtight air vent and hinder densification from sintered compact mutually.Consider that from this viewpoint under the top temperature when burning till, moulding pressure is preferably 30～300kgf/cm at least
2, 50～200kgf/cm more preferably
2In addition, if firing temperature is low excessively, then possibly can't carry out densification, if too high, then might aluminium oxide particles become excessive or fluorochemical evaporates.Consider from this viewpoint, preferably firing temperature is set in 1400～1850 ℃ scope, more preferably be set in 1500～1750 ℃ scope.And then, it can be to carry out under vacuum or inert atmosphere that hot pressing is burnt till, but also can be from normal temperature to the specified temperature, to be vacuum atmosphere till (for example 1500 ℃ or 1550 ℃ or 1600 ℃), till from the specified temperature to the firing temperature during and keep this firing temperature during be inert atmosphere.Specified temperature also can be identical temperature with firing temperature.Here, so-called inert atmosphere so long as do not have the atmosphere of influence to get final product to burning till, for example can be enumerated nitrogen atmosphere, helium atmosphere, argon gas atmosphere etc.
According to the manufacture method of alumina sintered body of the present invention, obtain percentage of open area easily and be 0～0.50%, volume density is 3.90～4.10g/cm
3Alumina sintered body.In addition, to obtain content by the rare earth element of inducing the coupled plasma emission spectroanalysis to measure easily be 0.5～2.5 weight %, be the alumina sintered body of 0.1～0.6 weight % by the content of the fluorine element of thermal hydrolysis separation-particle chromatography determination.
Embodiment
As raw material powder, with the ratio of 100 weight parts, 1.25 weight parts weighing purity more than 99.99% and the commercially available aluminum oxide (Al of median size 0.6 μ m respectively
2O
3) powder, purity be more than 99.9% and the following commercially available ytterbium (YbF that fluoridizes of median size 10 μ m
3) powder, as solvent, use the alumina balls wet mixing 4 hours of jar, the diameter 5mm of nylon system with Virahol.The particle diameter of raw material powder records by laser diffractometry.After the mixing, slurries are fetched in the big basin, in nitrogen gas stream in 110 ℃ of dryings 16 hours.Cross 30 purpose sieves then, make the blending powder.With the blending powder that obtains with 200kgf/cm
2Pressure carry out the single shaft press molding, make the discoid molding about diameter 50mm, thick 20mm, be accommodated in and burn till with in the graphite casting mould.What burn till use is pressure sintering.Moulding pressure when burning till is 100kgf/cm
2, atmosphere is, is vacuum till room temperature to 1600 ℃, imported 1.5kgf/cm afterwards till 1600 ℃ of end are burnt till
2Nitrogen.Here, burn till at firing temperature and kept 2 hours and finish.So, obtain the alumina sintered body of embodiment 1.
Process the sintered compact that obtains, carry out the mensuration of following (1)～(8) project.Measurement result is shown in table 1.In the table 1, the power of " E " expression 10.For example, " 1E+14 " expression " 1 * 10
14".Here,, used the multiple high-purity mangesium oxide aluminium powder form of other commercially available purity 99.0～99.995%, but obtained the result identical with embodiment 1 as aluminum oxide.
(1) percentage of open area, volume density
By measuring with the vehicular Archimedes's method of pure water.
(2) volume specific resistance
According to the method for JIS C2141, in atmosphere, measure in room temperature.Make test film be shaped as diameter 50mm * thickness 0.5～1mm, form each electrode with silver, make that the diameter of main electrode is 20mm, the internal diameter of grid is 30mm, and the external diameter of grid is 40mm, and the diameter of additional electrodes is 40mm.Making impressed voltage is 2kV/mm, reads the current value of impressed voltage after 1 minute, calculates the room temperature volume specific resistance by this current value.
(3) crystallization phases
Be to identify by rotation anticathode X-ray diffraction device (RINT that motor of science is made).Condition determination is, CuK α, 50kV, 300mA, 2 θ=10-70 °.
(4) content of rare earth
Try to achieve by inducing coupled plasma (ICP) emission spectroanalysis.
(5) fluorine element content
Try to achieve by thermal hydrolysis separation-particle chromatography.
(6) Mg content
Try to achieve by inducing coupled plasma (ICP) emission spectroanalysis.
(7) intensity
Be based on that JIS R1601 measures according to the four-point bending test method.
(8) aluminum oxide particle diameter
The mensuration of aluminum oxide particle diameter is by electron microscope the fracture surface of sample of pliability test to be observed, and multiply by 1.5 and obtain on the median size of calculating through method of bisector.
According to embodiment 1, by the composition and the firing condition of table 1 and table 2, make the alumina sintered body of embodiment 2～13, comparative example 1～9, according to operation similarly to Example 1, carry out (1)～mensuration of (8) project.The results are shown in table 1 and table 2.Atmosphere when firing temperature is 1700 ℃ the burning till of situation is vacuum till room temperature to 1600 ℃, afterwards from 1600 ℃ be warmed up to during 1700 ℃ and to 1700 ℃ burn till till the end during imported 1.5kgf/cm
2Nitrogen.In addition, in the comparative example 9,, therefore do not carry out atmosphere control especially owing to be burning till of in atmosphere, carrying out.
As known from Table 1, embodiment 1～13, that is, and and for the fluorochemical (YbF that in the aluminum oxide of main raw material, is added with rare earth element
3, YF
3, LaF
3) mixture carry out that hot pressing is burnt till and the alumina sintered body that obtains, its room temperature volume specific resistance is 1 * 10
13～1 * 10
16Ω cm.Therefore, when these alumina sintered bodies are used for the dielectric layer of electrostatic chuck, not only can obtain the adsorptive power stronger than coulomb type, and compare with Johnson La Bieke type, leakage current reduces.In addition, aluminum oxide has sufficient erosion resistance, the erosion resistance mutually that contains rare earth element and fluorine element is also than silicon element compound, titanium compound height, therefore, erosion resistance as a whole, particularly increases for the corrosive gases of fluorine element system or the erosion resistance of its plasma body.In addition as can be known, the kind of the fluorochemical by changing rare earth element or addition, firing temperature perhaps add oxide compound or nitride in addition, thereby can adjust the room temperature volume specific resistance.On the other hand, comparative example 1～9, promptly, carry out that hot pressing is burnt till and the alumina sintered body that obtains for the mixture of the compound beyond the fluorochemical that in the aluminum oxide of main raw material, is added with rare earth element, the alumina sintered body that is fired into even perhaps add the fluorochemical of rare earth element also not pressurize, its room temperature volume specific resistance surpasses 1 * 10
16Ω cm perhaps can not get fine and close sintered compact and can not measure resistance value.In addition, add the oxide compound of rare earth element and the sintered compact that obtains, though be fine and close, the volume specific resistance of room temperature has surpassed 1 * 10
16Ω cm.
Fig. 1 is the SEM image of the fracture that breaks of alumina sintered body, (a) expression embodiment 2 (additive YbF
3, 1600 ℃ of firing temperatures), (b) expression comparative example 5 (additive Yb
2O
3, 1600 ℃ of firing temperatures).Fig. 2 also is the SEM image of the fracture that breaks of alumina sintered body, (a) expression embodiment 3 (additive YbF
3, 1700 ℃ of firing temperatures), (b) expression comparative example 6 (additive Yb
2O
3, 1700 ℃ of firing temperatures).In addition, Fig. 3 is the SEM image of the mirror ultrafinish face of embodiment 7, and Fig. 4 carries out the image that the face distributional analysis obtains for each element that the mirror ultrafinish face of embodiment 7 uses EPMA to carry out F, AL, Yb.By Fig. 1 and Fig. 2 as can be known, among the embodiment 2,3, layeredly there is the phase of white each other in the polyhedron particle of gray aluminum oxide.Change a saying, also we can say the phase that has white along the polyhedron particle rib each other of aluminum oxide.In addition, among the embodiment 7 of Fig. 3, there is the phase of same white.For the phase of such white, be to comprise rare earth element and fluorine element at least mutually as can be known by X-ray diffraction or EPMA, be the material that mainly constitutes by the crystallization phases of table 1 record.About the record of the crystallization phases among each embodiment of table 1, YbF
3-xExpression is with YbF
2.35, YbF
2.41Position etc. definite peak.In addition, Yb
3Al
5O
12Expression is with Yb
3Al
5O
12Determine the position at peak, exist part to contain the possibility of fluorine.In addition, there is the possibility that contains fluorine element in other rare earth-aluminum oxide oxide compound too.On the other hand, in the comparative example 5,6, the polyhedron particle of aluminum oxide is scattered with the phase of white each other.For this white phase, known by X-ray diffraction and chemical analysis is not contain fluorine element mutually in fact.So as can be known, the alumina sintered body of embodiment is compared with the alumina sintered body of comparative example, and microstructure is obviously different.
YbF
3Addition and the relation of room temperature volume specific resistance
Among the figure of Fig. 5, transverse axis is the addition of fluoridizing ytterbium (weight part) with respect to aluminum oxide 100 weight parts, and the longitudinal axis is room temperature volume specific resistance (with reference to above-mentioned (2)).The addition of fluoridizing ytterbium is that 0 point (two) is a comparative example, and point in addition is embodiment,, has omitted the numbering of comparative example and embodiment here.Each alumina sintered body is made according to embodiment 1.As shown in Figure 5, be added with the mixture of fluoridizing ytterbium in will the aluminum oxide at main raw material under vacuum or the inert atmosphere and carry out hot pressing and burn till and obtain alumina sintered body, its room temperature volume specific resistance is 1 * 10
14～1 * 10
16The scope of Ω cm.
In addition, as shown in Table 1, embodiment 8 and embodiment 14～21, that is, and in the aluminum oxide of main raw material, being added with the fluorine element compound (YbF of rare earth element
3) and magnesium oxide and the mixture that forms carry out that hot pressing is burnt till and the alumina sintered body that obtains, with other embodiment similarly, the room temperature volume specific resistance is 1 * 10
13～1 * 10
16Ω cm when therefore these alumina sintered bodies being used for the dielectric layer of electrostatic chuck, can obtain the adsorptive power stronger than coulomb type, compares with Johnson La Bieke type, can obtain the effect that leakage current reduces.In addition, can also obtain erosion resistance as a whole, the effect that particularly erosion resistance of fluorine prime system etchant gas or its plasma body is improved, perhaps obtain by changing YbF
3Thereby addition, MgO addition or change the effect that firing temperature can be adjusted the room temperature volume specific resistance.Particularly, only be YbF at additive as embodiment 1～7
3The time, the room temperature volume specific resistance is reduced to 3 * 10
14(embodiment 6,7) when adding MgO altogether, are reduced to 2.2 * 10 about Ω cm
14Ω cm (embodiment 8) or 4.3 * 10
13Ω cm (embodiment 17).
The data of embodiment 1,2,4,6～8,14～21 have been summed up in the chart of Fig. 6～Fig. 9.Fig. 6 is with YbF
3Weight part be transverse axis, added the chart of intensity near the each point when being the longitudinal axis with the weight part of MgO; Fig. 7 is that the weight part with MgO is a transverse axis, the chart when being the longitudinal axis with intensity.The weight part of each is that each composition is with respect to Al
2O
3The addition of 100 weight parts.By these charts as can be known, with respect to Al
2O
3100 weight parts, when adding the MgO more than 0.3 weight part, intensity reaches more than the 250MPa, compares with the situation of not adding MgO, forms high strength.
Fig. 8 is that the weight ratio with Mg/Yb is a transverse axis, the chart when being the longitudinal axis with intensity.By this chart as can be known, Mg/Yb is 0.10～0.33 o'clock, and intensity reaches more than the 250MPa, compares with the situation of not adding MgO, forms high strength.
Fig. 9 is that the aluminum oxide particle diameter with sintered compact is a transverse axis, the chart when being the longitudinal axis with intensity.By this chart as can be known, the aluminum oxide particle diameter is below the 7 μ m, when particularly 6 μ m are following, can accesses high-intensity sintered compact.
Figure 10 is the SEM photo of the fracture fracture of alumina sintered body, and (a) expression embodiment 4, (b) expression embodiment 16, (c) represent embodiment 17.As can be known clear and definite by this SEM photo, be at embodiment 4,16,17 arbitrary SEM photos, have the part that links to each other of white each other at the polyhedron particle of gray aluminum oxide.Specifically, the phase of white forms stratiform partly and exists, and perhaps exists (in the SEM photo of the embodiment 17 of Figure 10 (c) along the polyhedron particle rib each other of aluminum oxide partly, the white that exists along the rib of polyhedron particle be difficult to identification mutually, therefore marked arrow).This white mainly be that crystallization phases by table 1 record forms mutually, among the embodiment 17, owing to added MgO altogether, so contain MgF
2This MgF
2Be considered to MgO and YbF
3Reaction generates.In addition, among the embodiment 16,, therefore can't confirm MgF because MgO is a trace
2The peak, but think and in fact have MgF
2As can be known clear and definite by Figure 10, with the addition of MgO is that 0 embodiment 4 compares, in the embodiment 16 that has added 0.2 weight part MgO, the aluminum oxide particle diameter increases, cause intensity to reduce, but in the embodiment 17 that has added 0.4 weight part MgO, the aluminum oxide particle diameter reduce, compare with not adding MgO, intensity improves.That is, can learn, add the MgO of specified amount altogether, have thickization of inhibited oxidation aluminum sinter grain, improve the effect of intensity, but the addition of MgO after a little while, promote grain to grow up.Its reason is also uncertain, but thinks following reason.That is, learn,, generate MgF by adding MgO by the crystallization phases parsing of sintered compact
2Known this MgF
2With YbF
3Phasor (MgF
2-YbF
3) in, generate liquid phase at 967 ℃, in the embodiment 16 that has added 0.2 weight part MgO, be equivalent to the composition level of forming near this eutectic temperature (967 ℃) just.Therefore, among the embodiment 16, reduce along with liquid phase generates temperature, the liquid phase growing amount in the intensification way when burning till increases, and has promoted grain to grow up.On the other hand, think in the embodiment 17 that has added 0.4 weight part MgO, with MgF
2The temperature that intersects of the composition level and liquidus line phasor may surpass YbF
3Fusing point, thereby compare with embodiment 4, the amount of liquid phase in burning till tails off, and grain is grown up and may be suppressed.In addition, added the embodiment 18 of 0.6 weight part MgO and added among the embodiment 19 of 1.0 weight part MgO, though compare with embodiment 17, the room temperature volume specific resistance has increased, infer be since with the YbF of MgO reaction
3Amount increase, therefore,, white mutually in corresponding to the contained YbF of this part
3Amount reduce, resistance is difficult to reduce.
Claims (13)
1. an alumina sintered body is characterized in that, layeredly exists each other at the particle as the aluminum oxide of principal constituent and contains rare earth element and fluorine element mutually.
2. an alumina sintered body is characterized in that, layeredly exists along the particle rib each other as the aluminum oxide of principal constituent and contains rare earth element and fluorine element mutually.
3. according to the alumina sintered bodies of claim 1 or 2 records, wherein, be 1 * 10 by apply the volume specific resistance that the current value of 2kV/mm voltage after 1 minute calculate in room temperature
13～1 * 10
16Ω cm.
4. according to the alumina sintered body of each record in the claim 1～3, wherein, described rare earth element is select from yttrium, lanthanum and ytterbium at least a.
5. according to the alumina sintered body of each record in the claim 1～4, wherein all with respect to sintered compact, the content of described rare earth element is 0.1～20 weight %, and the content of described fluorine element is 0.05～5 weight %.
6. according to the alumina sintered body of each record in the claim 1～5, wherein, described contain rare earth element and fluorine element mutually in contain magnesium, all with respect to sintered compact, the content of this magnesium is 0.1 weight %～5 weight %.
7. according to the alumina sintered body of each record in the claim 1～6, wherein, described contain rare earth element and fluorine element mutually in contain magnesium, the sintered compact content of this magnesium is 0.1～0.33 with respect to the weight ratio of the sintered compact content of described rare earth element.
8. according to the alumina sintered body of each record in the claim 1～7, wherein, the particle diameter of described aluminum oxide is 5 μ m～7 μ m.
9. according to the alumina sintered body of each record in the claim 1～8, it is used for electrostatic chuck.
10. the manufacture method of alumina sintered body is characterized in that, under vacuum or inert atmosphere, will be added with the fluorine cpd of rare earth element in the aluminum oxide of main raw material and the mixture that obtains carries out hot pressing burns till, thereby obtain alumina sintered body.
11., wherein,, add the fluorochemical of described rare earth element with the scope of 0.5～10 weight part with respect to described aluminum oxide 100 weight parts according to the manufacture method of the alumina sintered body of claim 10 record.
12. according to the manufacture method of alumina sintered bodies of claim 10 or 11 records, wherein, as described mixture, use be to add the magnesium oxide more than 0.3 weight part and the mixture that obtains with respect to described aluminum oxide 100 weight parts.
13. according to the manufacture method of the alumina sintered body of claim 12 record, wherein, as described mixture, use be to be that 0.1～0.4 mode is added the mixture that magnesium oxide obtains with respect to the weight ratio of the fluorochemical of described rare earth element with magnesium oxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098686A (en) * | 2010-03-30 | 2017-08-29 | 日本碍子株式会社 | Use in semiconductor manufacturing apparatus corrosion-resistant member and its preparation method |
| CN110248910A (en) * | 2017-02-23 | 2019-09-17 | 住友大阪水泥股份有限公司 | Composite sinter, electrostatic chuck component and electrostatic chuck apparatus |
| CN112759373A (en) * | 2015-03-26 | 2021-05-07 | 日本碍子株式会社 | Method for producing alumina sintered body and alumina sintered body |
-
2009
- 2009-08-31 CN CN200910168386A patent/CN101665352A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098686A (en) * | 2010-03-30 | 2017-08-29 | 日本碍子株式会社 | Use in semiconductor manufacturing apparatus corrosion-resistant member and its preparation method |
| CN112759373A (en) * | 2015-03-26 | 2021-05-07 | 日本碍子株式会社 | Method for producing alumina sintered body and alumina sintered body |
| CN110248910A (en) * | 2017-02-23 | 2019-09-17 | 住友大阪水泥股份有限公司 | Composite sinter, electrostatic chuck component and electrostatic chuck apparatus |
| CN110248910B (en) * | 2017-02-23 | 2022-09-09 | 住友大阪水泥股份有限公司 | Composite sintered body, electrostatic chuck member, and electrostatic chuck device |
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Application publication date: 20100310 |