CN112534565A - 静电卡盘及静电卡盘的制造方法 - Google Patents
静电卡盘及静电卡盘的制造方法 Download PDFInfo
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- CN112534565A CN112534565A CN201980052004.5A CN201980052004A CN112534565A CN 112534565 A CN112534565 A CN 112534565A CN 201980052004 A CN201980052004 A CN 201980052004A CN 112534565 A CN112534565 A CN 112534565A
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- Prior art keywords
- alumina
- electrostatic chuck
- ceramic
- zirconium
- ceramic substrate
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 66
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 51
- 238000001179 sorption measurement Methods 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 37
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims description 34
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 30
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 11
- 238000003980 solgel method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 229910010293 ceramic material Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 150000004703 alkoxides Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- -1 aluminum alkoxide Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
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- 238000009616 inductively coupled plasma Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000011368 organic material Substances 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003826 uniaxial pressing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination 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
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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
- H01L21/683—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 for supporting or gripping
- H01L21/687—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 for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches
- H01L21/68714—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 for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support
- H01L21/6875—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 for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support characterised by a plurality of individual support members, e.g. support posts or protrusions
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- H01L21/687—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 for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches
- H01L21/68714—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 for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support
- H01L21/68757—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 for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support characterised by a coating or a hardness or a material
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Abstract
本公开的静电卡盘(1)具备板状的陶瓷基体(2)和静电吸附用电极(3)。上述陶瓷基体(2)包含主成分为氧化铝的多个粒子。该多个粒子包含具有镁原子和锆原子的粒子。
Description
技术领域
本公开涉及静电卡盘及静电卡盘的制造方法。
背景技术
作为静电卡盘,已知有例如PVD装置或CVD装置等成膜装置或曝光装置等所使用的静电卡盘。另外,例如已知有日本特开2008-251737号公报(以下,也称为专利文献1)中记载的静电卡盘。以往,在PVD装置、CVD装置或离子镀装置等成膜装置、曝光装置或蚀刻装置等中,为了高精度地固定硅晶片等被加工物,而使被加工物吸附于被精加工成平坦且平滑的板状体的表面。作为该吸附手段,使用利用静电吸附力的静电卡盘。
该静电卡盘在包含陶瓷的板状的基体的一个主面(一个最宽的面)具有试样保持面。静电卡盘在基体的内部或另一个主面(另一个最宽的面)具备静电吸附用电极。关于静电卡盘,对静电吸附用电极施加DC电压,从而在与被加工物之间显现由介电极化产生的库仑力、或者由微小的漏电流产生的约翰逊·拉别克力等静电吸附力。静电卡盘能够使被加工物吸附固定于试样保持面。
需要说明的是,在静电卡盘上,按照从与被加工物的周边部对应的试样保持面的周边部自如突出的方式,设置有用于使被加工物从试样保持面脱离的升降销。
发明内容
本公开的静电卡盘具备陶瓷基体和静电吸附用电极,上述陶瓷基体为板状,在一个主面具有试样保持面,上述静电吸附用电极设置于该陶瓷基体的内部或另一个主面,上述陶瓷基体包含主成分为氧化铝的多个粒子,该多个粒子包含具有镁原子和锆原子的粒子。
附图说明
图1是本公开的静电卡盘的俯视图。
图2是本公开的静电卡盘和被加工物的纵截面图。
图3是表示图1所示的陶瓷基体中的具有镁原子、锆原子的氧化铝粒子的存在形态以及该粒子内的上述原子的存在区域的图。
图4是表示本公开的静电卡盘的另一例的纵截面图。
具体实施方式
以下,使用附图对本公开的静电卡盘1的例子进行详细说明。
图1和图2所示的静电卡盘1具备陶瓷基体2和静电吸附用电极3。具体而言,陶瓷基体2也可以形成为具有与硅晶片等被加工物A相同程度的大小的圆板状,且在该陶瓷基体2的内部埋设有静电吸附用电极3。
并且,如图1所示,也可以在陶瓷基体2的一个主面设置多个凸部6,凸部6各自的突端具有平滑的面,构成试样保持面。需要说明的是,凸部6的数量不限于图中示出的图案的数量。
静电吸附用电极3与导线8连接,静电吸附用电极3可以介由导线8与直流电源9连接。另一方面,吸附于试样保持面的被加工物A也可以与接地(日文:アース)直接或利用等离子体进行电连接。由此,能够在静电吸附用电极3与被加工物A之间显现静电吸附力。其结果是,能够将被加工物A吸附固定。
在陶瓷基体2的中央部可以设置从另一个主面(图的下表面)贯通至一个主面(图的上表面)的气体导入孔7。另外,凸部6与凸部6之间成为气体流路5,该气体流路5与气体导入孔7可以连通。
在将加工物A吸附于试样保持面时,能够从气体导入孔7向由被加工物和气体流路5构成的空间供给氦气等冷却气体。由此,能够提高试样保持面与被加工物A之间的热传递性,均匀地控制被加工物的温度分布。
需要说明的是,如图1所示,静电卡盘1可以沿着陶瓷基体2的一个主面的外周形成有周壁4,而使凸部6、被加工物A和气体流路5所成的空间成为封闭的空间。由此,能够防止从气体导入孔7供给的冷却气体大量泄漏到外部。该周壁4可以根据目的设置,也可以不设置。另外,周壁4可以与陶瓷基体2一体地形成,也可以分体地形成。
陶瓷基体2包含主成分为氧化铝的多个粒子。这里所说的“粒子”是指构成多晶体的晶粒。在此,对于粒子而言,作为主成分的氧化铝的原子排列在一个方向上一致,但也可以包含原子排列与氧化铝不同的副成分。另外,这里所说的“主成分”是指构成粒子的成分中摩尔比率最高的成分。该摩尔比率如后所述,可以通过利用透射型电子显微镜(TEM)、能量色散型X射线分析法(EDS)、电子能量损失光谱法(EELS)测定元素比率而求出。另外,构成陶瓷基体2的全部粒子可以包含氧化铝作为主成分。另外,陶瓷基体2也可以具有主成分不是氧化铝的粒子。需要说明的是,以下将主成分为氧化铝的粒子简称为氧化铝粒子10。
静电吸附用电极3的材料可以设为铂或钨等金属。该静电吸附用电极3可以被设置为在陶瓷基体2的另一个主面(下表面)露出。另外,也可以如图4所示,位于陶瓷基体2的内部。
根据本公开的静电卡盘1,多个氧化铝粒子10包含具有镁原子和锆原子的粒子。由此,通过来自于锆原子向氧化铝粒子10固溶的自由电子,能够使存在于陶瓷基体2的空穴消失。并且,能够减少导致残留吸附的空穴。由此,能够降低残留吸附的发生。其结果是,能够提高试样保持面的试样的脱离性。
空穴可以是在氧化铝的烧结时在氧化铝粒子10内产生的空穴。空穴例如也可以是在1550℃附近烧结氧化铝时,在产生MgO·1.7Al2O3(不完全尖晶石)的情况下而产生的空穴。具体而言,空穴可以是MgO→MgAl’+Oo x+h·的式所示的、以的缺陷表示法所表示的h·。
自由电子例如可以通过使氧化锆固溶于氧化铝而产生。具体而言,可以通过ZrO2→ZrAl·+2Oo x+e’的式子产生。
氧化铝粉末例如可以是经由铝土矿精制的氧化铝粉末,也可以是由铵片钠铝石(NH4AlCO3(OH)2)等高纯度的前体合成的99.9质量%以上的高纯度氧化铝粉末。经由铝土矿精制的氧化铝粉末也可以使用灼烧损失后具有99.5质量%以上的纯度的氧化铝粉末。氧化铝可以通过将氧化铝粉末和氧化铝-氧化锆粉末混合·烧成而得到。氧化铝-氧化锆粉末可以使用通过后述的制造方法所示的溶胶-凝胶法制作的复合氧化物粉末。
镁原子可以是在氧化铝中作为烧结助剂而包含的氧化镁中所含的原子。镁原子在陶瓷基体2中可以含有300~4600ppm。
锆原子可以位于氧化铝的晶界附近,也可以位于氧化铝的晶粒内。锆原子在陶瓷基体2中可以含有1000~60000ppm。
需要说明的是,也可以并非在构成陶瓷基体2的全部氧化铝粒子10中存在镁原子和锆原子。仅通过部分地存在具有这些原子的氧化铝粒子10,就能够使空穴消失。
图3示意性地表示具有镁原子和锆原子的氧化铝粒子10在基体中的存在形态的例子。在图3中,将斜线所示的区域作为锆原子存在的区域(以下,称为锆原子存在区域11),将点图案所示的区域作为镁原子存在的区域(以下,镁原子存在区域12)。固溶于氧化铝粒子10的氧化镁能够通过Mg2+和Al3+的相互扩散而在氧化铝粒子10的内部形成尖晶石。锆原子可以在氧化铝粒子10的晶界附近以固溶体的形式存在。另外,也可以在氧化铝的晶界析出不含铝原子的氧化锆。
在氧化铝粒子10中,锆原子存在区域11与镁原子存在区域12可以彼此位于邻接的位置。由此,能够使空穴产生的原因即镁原子、与自由电子产生的原因即锆原子的距离接近。因此,能够有效地减少成为残留吸附的原因的空穴。由此,能够减少残留吸附。其结果是,能够提高试样保持面的试样的脱离性。
另外,锆原子存在区域11和镁原子存在区域12不需要明确地划分边界,可以彼此重叠。换言之,锆原子和镁原子可以存在于相同的区域。
另外,在氧化铝粒子10中,锆原子存在区域11可以包围镁原子存在区域12。由此,能够有效地减少成为残留吸附的原因的空穴。因此,能够减少残留吸附。其结果是,能够提高试样保持面的试样的脱离性。
需要说明的是,多个氧化铝粒子10包含具有镁原子和锆原子的粒子这一点可以通过利用以下方法进行结构解析来确认。首先,通过磨削、切断、研磨等公知的方法取出陶瓷基体2的规定的部分。接下来,将取出的部位利用氩离子铣削法等进行薄片化,作为试样。然后,通过透射型电子显微镜(TEM)、电子衍射、能量色散型X射线分析法(EDS)、电子能量损失光谱法(EELS)对该试样进行结构解析。另外,上述原子的定量可以通过公知的方法熔解(日文:溶解)陶瓷基体2,利用电感耦合等离子体发光分析法(ICP)、原子吸光法进行测定而求出。
如图4所示,在静电吸附用电极3埋设于陶瓷基体2的情况下,可以将基体2的上表面(在形成有凸部6的情况下为吸附面)与静电吸附用电极3之间的区域作为上表面侧区域21。此时,陶瓷基体2中,位于上表面侧区域21或位于上表面侧区域21及其附近的多个氧化铝粒子10也可以包含镁原子和锆原子。由此,在陶瓷基体2中的参与吸附的区域以外的部位即下表面侧区域22中产生的空穴以微弱的电流的形式作用于上表面侧区域21的情况下,能够通过存在于上表面侧区域21的自由电子使空穴消失。其结果是能够抑制残留吸附。
上表面侧区域21的厚度可以比下表面侧区域22大,也可以比下表面侧区域22小。例如,上表面侧区域21的厚度可以为0.2~0.4mm,上表面侧区域21的附近区域的厚度通常可以为0.1~0.5mm,上表面侧区域21和下表面侧区域22的合计的厚度可以为2~10mm。
另外,陶瓷基体2中,锆的含量C2(mol)相对于镁的含量C1(mol)之比,即原子数之比中,C2/C1可以为1以上。
作为现有的静电卡盘1,已知有通过在切断DC电压的状态下花费足够的时间进行等离子体照射(电子注入)来除去固定电荷的方法。另外,公开了在陶瓷基体2的试样保持面设置与吸附的硅晶片接触的带电控制用电极,在吸附解除时作为接地电极发挥功能的方法(参照专利文献1)。通过使用这样的固定电荷除去方法和静电卡盘2,能够抑制被加工物的变形或破损。然而,在以氧化铝为主成分的静电卡盘1中,在长期使用的过程中,即使出于除去上述固定电荷的目的而持续照射等离子体(具有高能量的被加速的电子),残留吸附的抑制力也有可能经时劣化。并且,随着时间经过,残留吸附有可能增大。其结果是,难以提高试样保持面的试样的脱离性。
通过使陶瓷基体2中所含的镁与锆的含量之比C2/C1为1以上,从而能够增加氧化锆的固溶量,因此能够产生更多的电子。因此,能够使氧化铝粒子10中产生的空穴更有效地迅速消失。因此,能够抑制反复施加电压时的残留吸附的经时增加。其结果是,能够使晶片更容易脱离。具体而言,可以将C1和C2设为1.2×10-5~1.9×10-4(mol)。
另外,陶瓷基体2中,上述C2(mol)相对于铝的含量C3(mol)之比C2/C3可以为0.01以下。由此,能够降低存在于晶界的氧化锆的量。因此,通过存在于晶界的氧化锆,能够降低介电损耗角正切(tanδ)增加的可能性。其结果是,能够提高静电卡盘1的耐久性。具体而言,可以将C2设为1.2×10-5~1.9×10-4(mol),将C3设为8.9×10-3~9.8×10-3(mol)。
以下,对本公开的静电卡盘1的制造方法进行说明。
陶瓷基体2可以包括:通过溶胶-凝胶法制作氧化铝-氧化锆粉末的工序;将上述氧化铝-氧化锆粉末与氧化铝粉末混合而制作陶瓷材料的工序;以及将上述陶瓷材料烧成的工序。
由此,能够由制成粉末的阶段使氧化锆固溶于氧化铝。因此,能够制作包含具有镁原子和锆原子的氧化铝粒子10的陶瓷基体2。由此,通过来自于锆原子向氧化铝粒子10的固溶的自由电子,能够使存在于陶瓷基体2的空穴消失。并且,能够减少成为残留吸附的原因的空穴。由此,能够减少残留吸附。其结果是,能够提高试样保持面的试样的脱离性。
首先,对通过溶胶-凝胶法制作氧化铝-氧化锆粉末的工序的一个例子进行说明。利用将作为氧化物前体的不同金属醇盐、络合物彼此以分子水平混合的溶胶-凝胶法,通过以下方法制作了氧化铝-氧化锆粉末。溶胶-凝胶法中使用的溶胶的制作可以是金属醇盐的水解,也可以是金属乙酸盐、络合物的水解,只要使用公知的方法即可。以金属醇盐的水解为例进行说明。
将作为起始原料的称量规定量的仲丁醇铝(Al(O(CH3)CHC2H5)3)和正丁醇锆(Zr(OC4H9)4)在2-丙醇中搅拌混合0.5~1小时。作为铝醇盐、锆醇盐,不限于上述物质,可以使用这些金属的包含烷氧基的化合物。如果具体地举出例子,则烷氧基为乙氧基、正丙氧基、仲丙氧基、正丁氧基、叔丁氧基等。
需要说明的是,这些溶液彼此的搅拌混合可以使用均质器、旋转型搅拌器、静态混合机等公知的方法。特别是,超声波均质器通过空化效应而进行破碎,因此在后述的溶胶-凝胶工艺中,能够用作得到微粒的方法。
在此,如果作为溶剂的2-丙醇量为金属醇盐的摩尔量的1倍以上或1.5倍以上的摩尔量,则醇盐溶液能够充分混合。溶剂根据与烷氧基的相容性适当选择即可,除了2-丙醇以外,还可以使用乙醇、正丙醇、正丁醇、2-丁醇、叔丁醇等醇。
接下来,一边将该溶液保持在25℃以上且所使用的金属醇盐、溶剂的沸点以下的温度(此时为40℃)一边进行搅拌,同时一边滴加蒸馏水与2-丙醇的混合溶液,一边在溶液中引起醇盐的水解反应、和缩聚反应,同时变为溶胶,进一步使其凝胶化。水(蒸馏水)与2-丙醇的混合溶液的各自的混合比率没有特别限制,例如相对于2-丙醇1摩尔可以混合4~10摩尔的水(蒸馏水)。由此,形成均质地分子混合而成的溶胶、凝胶。需要说明的是,为了促进·控制反应,也可以在水解用的水中添加盐酸、乙酸等酸、氨水等作为催化剂。
将该凝胶继续搅拌0.5~1小时后,在50℃~80℃下减压干燥,进一步在大气中,在100℃~120℃下干燥3~5小时,得到干燥凝胶。干燥凝胶是数nm~数10nm的微粒凝聚而成的多孔体,通过利用干式磨机、擂溃机等公知的方法将其粉碎,能够得到可通过规定的大小,例如330~500目的多孔凝胶粉末,所述干式磨机使用了包含用氨基甲酸酯、尼龙等树脂包覆的金属、陶瓷的球。更具体而言,能够得到可通过线径为0.025~0.035mm、筛孔为0.026~0.043mm、开孔率为25.8~30.5%的筛网的多孔凝胶粉末。
或者,如果在制作溶胶时用超声波均质器进行搅拌,则滴下的水破碎而产生微细的乳液,同时发生水解和缩聚,因此在干燥后得到多孔的微粉末(以平均粒径D50计为1~5μm)。
通过将这样制作的多孔粉末在大气中、500℃~1100℃下进行2~3小时用于结晶化·无孔化的预烧,能够得到氧化铝-氧化锆粉末。对该粉末进行基于X射线衍射的晶格常数的测定和TEM、EDS分析,结果确认了氧化铝和氧化锆的固溶。
以上所述的粉末制法具体地说明了本公开的一个例子,本公开并不限定于该方式。对于利用溶胶-凝胶法的粉末制法,例如,除此以外还可以使用pH控制法、喷雾法等。
接下来,对将氧化铝-氧化锆粉末和氧化铝粉末混合来制作陶瓷材料的工序的一个例子进行说明。首先,分别称量规定量的通过上述方法制作的氧化铝-氧化锆粉末和氧化铝粉末作为主成分的氧化铝,称量规定量的氧化镁作为烧结助剂成分,根据需要称量规定量的其他的烧结助剂(例如氧化硅),在用氨基甲酸酯、尼龙等树脂施加了内衬的球磨机中,与离子交换水、有机溶剂等溶剂、有机分散剂、以及包含用氨基甲酸酯、尼龙等树脂包覆的金属、99.5质量%以上的高纯度氧化铝等陶瓷的球一起,进行24~72小时湿式粉碎混合。对于该树脂内衬、树脂包覆球,所适用的树脂适当选择在使用的溶剂中不溶解、不溶胀的树脂即可。此时,从高体积电阻系数(日文:体積固有抵抗)的观点出发,烧成后陶瓷基体中的氧化铝含量可以至少为99.5质量%以上。
但是,在合成时需要聚合催化剂的情况下,关于适用于树脂内衬或树脂包覆球的树脂,只要满足可使用非金属系催化剂,此外,作为树脂的特性而不会在溶剂中溶解、溶胀的条件,则可以适当选择能够使用的树脂。
对于原料的粉碎而言,在中途和结束时适当选择原料浆料,用激光衍射散射法进行测定,控制浆料中的粉末粒度即可。即,将D10(10%粒径)设为0.1~0.5μm,或0.2~0.4μm,或0.3~0.4μm即可,可以将D50(50%粒径,中值粒径)设为0.4~0.9μm,或0.5~0.8μm,或0.5~0.6μm。
在这样粉碎混合后的原料浆料中,添加规定量的聚乙烯醇、聚乙烯醇缩丁醛、丙烯酸树脂等有机粘合剂、作为辅助性有机材料的增塑剂、消泡剂,进一步混合24~48小时。
在此,有机粘合剂、增塑剂、消泡剂等有机材料可以选择碱金属、碱土金属为100ppm以下,或50ppm以下,或10ppm以下的的材料。由此,能够有效降低烧结时残留于氧化铝陶瓷的晶界的量,在对陶瓷基板2施加直流高电压时,能够降低发生离子迁移的不良影响。
通过刮刀法、压延辊法、压制成形法、挤出成形法等将混合后的有机-无机混合浆料成形为厚度20μm~20mm,特别是100~300μm的陶瓷坯片。
然后,通过公知的丝网印刷法等在将会形成陶瓷基板2的陶瓷坯片上将用于形成静电吸附用电极3的铂、钨等糊状电极材料印刷成形。
在此,以在陶瓷基板2的规定的位置形成静电吸附用电极3的方式,将未印刷糊状电极材料的陶瓷坯片与印刷有糊状电极材料的电极形成坯片重叠并层叠。关于层叠,一边施加陶瓷坯片的屈服应力值以上的压力,一边以规定的温度进行层叠,作为压力施加方法,应用单轴压制法、等静压制法(干式、湿式法)等公知的技术即可。
最后,对将陶瓷材料烧成的工序的一个例子进行说明。将得到的层叠体在1530℃~1600℃的规定温度、大气中或非活性气体气氛中烧成2~6小时,使基于阿基米德法的堆积密度至少以相对于理论密度的相对密度计为98%以上或99.5%以上。
这样,能够制作埋设有静电吸附用电极3的陶瓷基板2。需要说明的是,在陶瓷基板2的试样保持面通常形成载置被保持物的凸部6、气体流路5,作为制法,可以使用利用掩模的喷砂法、机械加工法或超声波加工法等公知的方法,由此能够将例如高度为3~50μm的凸部6形成为规定的图案形状。
通过以上的制造方法,能够制作残留吸附不会随时间经过而增大、且长期间内被加工物的脱离容易的静电卡盘1。
实施例1
对于具有图1的结构的本公开的静电卡盘1,如下制作。具体而言,称量规定量的通过上述溶胶-凝胶法得到的氧化铝-氧化锆粉末(平均粒径D50为1.5μm)和纯度99.5质量%以上的氧化铝粉末(平均粒径D50为0.5μm)、作为烧结助剂的氧化镁粉末(平均粒径D50为1.5μm)、其它烧结助剂(氧化硅、碳酸钙)。
相对于上述原料粉末的总量100质量份,将甲苯80质量份、分散剂0.5质量份在施加了尼龙内衬的球磨机内与Φ20mm的树脂包覆球一起进行48小时湿式粉碎混合。
接下来,向该湿式粉碎混合浆料中添加增塑剂和粘合剂。对于增塑剂,相对于原料粉末100质量份添加DBP和DOP各2质量份,对于粘合剂,添加以固体成分换算为15质量份的聚乙烯醇缩丁醛,进一步进行30小时湿式混合。
接下来,通过刮刀法将混合后的有机-无机混合浆料成形为厚度100μm的陶瓷坯片。
接下来,通过丝网印刷法在成为陶瓷基板的陶瓷坯片上将成为静电吸附用电极3的钨糊印刷成形。
接下来,以在陶瓷基板中的规定位置形成静电吸附用电极3的方式,将未印刷钨糊的陶瓷坯片与印刷有钨糊的电极形成坯片重叠,一边通过单轴压制法施加坯片的屈服应力以上的压力、具体而言5MPa,一边在80℃以上的温度进行层叠。
接下来,将得到的层叠体在还原气氛中、1550℃下烧成3小时。
在得到的陶瓷基板上通过旋转磨削加工来实施厚度加工,通过机械加工形成气体导入孔7,试样保持面通过抛光加工(日文:ラシプ加工)而精加工成表面粗糙度Ra为0.1μm以下,进一步通过使用掩模的喷砂法,将高度为15μm的凸部6形成为规定的图案形状。另外,在吸附用电极上通过钎焊安装金属端子(未图示),制作静电卡盘1。
对于陶瓷基板,准备了包含对铝、镁、锆的摩尔比进行了各种改变的氧化铝质陶瓷的试样1~11。然后,对于各个试样测定了残留吸附力。具体而言,在减压至1×10-3Pa的真空室内,以静电卡盘1的试样保持面成为140℃的方式用卤素灯进行加热。
对于评价,首先通过以下方法测定静电卡盘1的初始残留吸附。对静电吸附用电极3施加规定的电压300秒,保持被加工物(硅晶片),然后,停止对静电吸附用电极3的电压施加,使用测力计对停止1秒后的残留吸附力进行测定。
接下来,使用相同的静电卡盘1,测定因长期使用而引起的残留吸附的变化。对于静电卡盘1,在上述真空室内,对静电吸附用电极3施加规定的电压,使被加工物在试样保持面上吸附保持30分钟,然后,停止对上述电极3的电压施加,将该循环重复1000次,然后,通过与上述初始残留吸附相同的方法进行测定。
在此,在使用测力计测定完全未施加电压时的吸附力时,为0.2kPa左右的值,因此在测定值为0.2kPa以下的情况下,判断为没有残留吸附力。
另外,对于试样1和3以外的所有试样,通过以下方法评价介电损耗角正切。在残留吸附评价结束后,从陶瓷基体2中的静电吸附用电极3的正下方的部位切出60mm见方、厚度1mm,按照JISC2141测定1MHz下的介电损耗角正切(tanδ)。将其结果示于表1。
[表1]
如表1所示,氧化铝粒子10不含镁原子和锆原子的试样1和3产生0.9kPa以上的残留吸附力的初始值。与此相对,对于包含镁原子和锆原子的、试样2和试样4~11,能够将残留吸附力的初始值降低至0.2kPa以下。这样,在本公开的一例的静电卡盘1中,能够减少残留吸附力的产生,提高试样保持面上的试样的脱离性。
另外,如表1所示,我们认为:C2/C1摩尔比小于1的试样4由于氧化锆的固溶量少,所以如果长期使用,则空穴会缓慢蓄积于试样保持面而发生残留吸附。
另一方面,在试样2和试样5~11中,即使长期使用氧化锆的固溶量仍多,因此能够进一步使空穴消失,能够降低1000次循环后的残留吸附力。这是因为较多地包含含有镁原子和锆原子的氧化铝粒子10。这样,在本公开的一例的静电卡盘1中,通过使C2/C1摩尔比为1以上,而能够降低经时的残留吸附力的产生,更有效地提高试样保持面的试样的脱离性。
另外,如表1所示,C2/C3摩尔比为0.01以上的试样9、10的介电损耗角正切的值为5.6×10-4以上。另一方面,C2/C3摩尔比为0.01以下的试样2和试样4~8的介电损耗角正切的值为2.0×10-4以下。这样,根据本公开的静电卡盘1,通过使C2/C3摩尔比为0.01以下,能够降低介电损耗角正切的增加,提高耐久性。
此外,在C2/C3摩尔比为0.01以下的试样11中,虽然陶瓷基板中的氧化铝的含量低至90.6质量%,但介电损耗角正切的值为3.6×10-4以下。这样,氧化铝的含量低的陶瓷基体2有可能因空洞、空隙的影响而导致介电损耗角正切增加,但通过使C2/C3摩尔比为0.01以下,而能够降低介电损耗角正切的增加。
另外,在上述试样2和试样4~11的TEM、EDS、EELS解析时,在氧化铝粒子10中,确认了具有镁原子和锆原子的粒子的存在,这些原子以图3所示的形态存在。即,锆原子存在于氧化铝的晶界附近。镁原子存在于氧化铝晶粒内,或者与锆原子同样地存在于晶界附近。
因此,由不完全尖晶石引起的空穴h·在晶界移动时,被来自于锆原子的自由电子e’电固定,其结果是,残留吸附得到抑制。
附图标记说明
1:静电卡盘
2:陶瓷基体
3:静电吸附用电极
4:周壁
5:气体流路
6:凸部
7:气体导入孔
8:导线
9:直流电源
10:氧化铝粒子
11:锆原子存在区域
12:镁原子存在区域
21:上表面侧区域
22:下表面侧区域
Claims (4)
1.一种静电卡盘,其具备陶瓷基体和静电吸附用电极,所述陶瓷基体为板状,在一个主面具有试样保持面,所述静电吸附用电极设置于该陶瓷基体的内部或另一个主面,所述陶瓷基体包含主成分为氧化铝的多个粒子,该多个粒子包含具有镁原子和锆原子的粒子。
2.根据权利要求1所述的静电卡盘,其中,所述陶瓷基体中,锆的含量C2相对于镁的含量C1之比C2/C1为1以上,其中C1和C2的单位为mol。
3.根据权利要求2所述的静电卡盘,其中,所述陶瓷基体中,所述C2相对于铝的含量C3之比C2/C3为0.01以下,其中C2和C3的单位为mol。
4.一种静电卡盘用基板的制造方法,其特征在于,包括如下工序:
通过溶胶-凝胶法制作氧化铝-氧化锆粉末的工序;
将所述氧化铝-氧化锆粉末与氧化铝粉末混合来制作陶瓷材料的工序;以及
将所述陶瓷材料烧成的工序。
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