CN104710178A - 具有可控电阻率的耐等离子体腐蚀陶瓷 - Google Patents
具有可控电阻率的耐等离子体腐蚀陶瓷 Download PDFInfo
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- CN104710178A CN104710178A CN201510093578.0A CN201510093578A CN104710178A CN 104710178 A CN104710178 A CN 104710178A CN 201510093578 A CN201510093578 A CN 201510093578A CN 104710178 A CN104710178 A CN 104710178A
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- 239000000919 ceramic Substances 0.000 title claims description 74
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 57
- 230000003628 erosive effect Effects 0.000 claims abstract description 34
- 239000004065 semiconductor Substances 0.000 claims abstract description 34
- 238000012545 processing Methods 0.000 claims abstract description 31
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- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 60
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 30
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 18
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- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 12
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000006104 solid solution Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 8
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 claims description 7
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 7
- 229940075624 ytterbium oxide Drugs 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000010891 electric arc Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 12
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- 229910052782 aluminium Inorganic materials 0.000 description 6
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
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- 238000002048 anodisation reaction Methods 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 229910052747 lanthanoid Inorganic materials 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了在采用腐蚀/侵蚀性等离子体的半导体处理条件下抵抗腐蚀/侵蚀的特种陶瓷材料。腐蚀性等离子体可为含卤素等离子体。对所述特种陶瓷材料已经改性以提供抑制等离子体电弧放电可能的可控电阻率。
Description
本申请是申请日为2007年9月29日,发明名称为“具有可控电阻率的耐等离子体腐蚀陶瓷”的申请的分案申请。
本申请涉及与本申请具有共同发明者的一系列申请。以下列出的所有申请涉及包含氧化钇的陶瓷的使用以提供用于半导体处理装置的耐等离子体表面。相关的申请包括由Sun等人在2007年4月27日提交的题目为“Method ofReducing The Erosion Rate Of Semiconductor Processing Apparatus Exposed ToHalogen-Containing Plasmas”的目前未诀的美国申请第11/796,210号;Sun等人在2007年4月27日提交的题目为Method And Apparatus Which ReduceThe Erosion Rate Of Surfaces Exposed To Halogen-Containing Plasmas”的目前未诀的美国申请第11/796,211号;Sun等人在2004年7月22日提交的题目为“Clean Dense Yttrium Oxide Coating Protecting Semiconductor Apparatus”的目前未诀的美国申请第10/898,113号;Sun等人在2004年8月13日提交的题目为“Gas Distribution Plate Fabricated From A Solid Yttrium Oxide-ComprisingSubstrate”目前未诀的美国申请第10/918,232号;以及Sun等人在2002年2月14日提交的题目为“Yttrium Oxide Based Surface Coating For SemiconductorIC Processing Vacuum Chambers”的美国专利申请第10/075,967号,所述美国专利申请在2004年8月14日授予美国专利第6,776,873号。以上列出的申请的分案和接续申请的所提交的其它相关申请包括:Wang等人在2006年11月10提交的题目为“Cleaning Method Used In Removing Contaminants From TheSurface Of An Oxide or Fluoride Comprising a Group III Metal”的美国申请第11/595,484号,目前未诀且为美国申请第10/898,113号的分案申请;以及Wang等人在2006年11月3日提交的题目为“Cleaning Method Used InRemoving Contaminants From A Solid Yttrium Oxide-Containing Substrate”的美国申请第11/592,905号,目前未诀且为美国申请第10/918,232号的接续申请。在此引入这些专利和申请的所有主题作为参考。
技术领域
本发明的实施方式涉及主要由高度抗存在于半导体处理装置中的等离子体腐蚀的固溶体陶瓷组成的特种含氧化钇陶瓷。
背景技术
该部分描述涉及本发明所公开的实施方式的背景主题。并没有意图表示或暗指在该部分讨论的背景技术组成现有技术。
抗侵蚀(包括腐蚀)性是在存在侵蚀性环境的半导体处理腔室中使用的装置组件和衬垫的关键属性。尽管侵蚀等离子体存在于多数半导体处理环境中,包括等离子体增强化学气相沉积(PECVD)和物理气相沉积(PVD),但是侵蚀性最强的等离子体环境是用于处理装置清洗和用于蚀刻半导体衬底的等离子体。这里尤其会有高能量等离子体存在并结合有化学反应以与存在于环境中的组件表面反应。当侵蚀性气体,即使在不存在等离子体,与处理装置表面接触时,装置组件表面或工艺腔室衬垫表面的还原化学反应是重要的属性。
存在于用于制造电子器件和微电子机械系统(MEMS)的处理腔室内的工艺腔室衬垫和组成装置通常由铝和铝合金构成。工艺腔室和组成装置(存在于腔室内)的表面通常阳极化以提供对侵蚀性环境的一定程度的隔离。然而,铝或铝合金中的杂质可能破坏阳极化层的完整性,从而侵蚀较早地开始,缩短了保护涂层的有效期限。与其它陶瓷材料相比,铝氧化物的耐等离子体属性并不积极。因此,各种组分的陶瓷涂层已经用于替代以上所提及的铝氧化物层;以及,在一些例子中,已经用在阳极化层的表面上以改善下层铝基材料的保护。
氧化钇是很有希望用于保护暴露于制造半导体器件中使用类型的含卤素等离子体的铝和铝合金表面的陶瓷材料。氧化钇涂层已经用于并施加在高纯度铝合金工艺腔室表面的阳极化表面上,或者工艺组件表面上,以产生良好的侵蚀保护(例如,以上提及的Sun等人的美国专利第6,777,873号)。可使用诸如喷涂、物理气相沉积(PVD)、化学气相沉积(CVD)等方法施加保护涂层。
A12O3、或A12O3和Y2O3膜已经形成于处理腔室的内壁表面上以及需要高度耐侵蚀性和绝缘属性的腔室内的构件的暴露表面上。在一个示例性应用中,腔室的基材可以为陶瓷材料(A12O3、SiO2、AlN等)、铝或不锈钢,或在基材之上具有喷涂膜的其它金属或金属合金。所述膜可以由周期表的III-B元素的化合物诸如Y2O3制成。所述膜可主要包含A12O3和Y2O3。钇-铝-石榴石(YAG)的喷涂膜也在以上提到过。喷涂膜厚度的实施例从50μm到300μm之间变化。
发明内容
已经研发了在采用含卤素等离子体的半导体处理条件下耐侵蚀的特种烧结陶瓷材料。已经改性特种材料以具有与以前用于半导体处理装置的烧结陶瓷材料相比的改善的耐等离子体腐蚀性和适合的机械属性。已经调整烧结陶瓷材料的电属性,从而材料的电阻率属性(所述电阻率属性在等离子体材料腔室中具有影响)满足特定腔室组件的需要。这些电阻率属性要求之前仅通过具有低耐等离子体腐蚀性质的材料满足。本发明的特种材料(所述特种材料具有耐等离子体腐蚀性、机械性能和电阻率性能的各种结合)与之前所用的半导体处理装置的材料充分相似。这种相似的电属性的一个优点在于不需要改变目前在半导体器件加工中使用的工艺菜单或通用的处理条件。
用于制造半导体材料腔室组件的特种烧结陶瓷材料可使用例如热/火焰喷涂或等离子体喷涂、物理气相沉积(诸如来自由特种烧结陶瓷材料组成的靶的溅射)或化学气相沉积等而施加到下层材料之上。在可选实施例中,烧结的陶瓷材料可使用成型工艺而用于制造整体组件,例如,当这对于涂层的使用有利的时候。
讨论的烧结陶瓷材料包含氧化钇基的固溶体。在一个实施方式中,改变烧结的含氧化钇陶瓷材料的电阻率。在一个示例性实施方式技术中,将其它氧化物添加到氧化钇中,并且烧结这种混合物。其它氧化物的阳离子具有与Y3+离子不同的化合价,以形成Y空位,导致电阻率降低。所述其它氧化物的实施例包括CeO2、TiO2、ZrO2、HfO2和Nb2O5等,仅以示例方式而并不限制于此。在可选示例性实施方式技术中,其它氧化物添加到氧化钇中并烧结所述混合物。其它氧化物的阳离子具有与Y3+离子相同的化合价,但是具有与Y3+离子显著不同的离子半径。在还原气氛中烧结先驱混合物。这产生O空位,也降低了电阻率。具有与Y3+离子相同化合价但是具有显著不同的离子半径的氧化物的实施例包括Nd2O3、Sm2O3、Sc2O3、Yb2O3、Er2O3、Ho2O3和Dy2O3,仅以示例方式而并不限制于此。
在通常与含钇烧结陶瓷相比需要较低电阻率的半导体处理腔室中的主要组件中的一种是静电夹盘。静电夹盘设计者建议在半导体处理条件下静电夹盘的介电表面的电阻率在从约109到1011Ω·cm的范围内,以减小在静电夹盘处形成等离子体电弧的可能。电阻率范围与在约10-9到10-7S/m范围内的电导率等价。这是比体Si3N4显著低的电阻率,例如,所述体Si3N4具有电导率10-13S/m。对于等离子体电弧可能产生不利影响的其它耐侵蚀表面,诸如升降杆,在需静电夹盘需要的那个范围内的电阻率是有益的。对于耐侵蚀表面诸如工艺腔室衬垫,电阻率较高,可能与1014Ω·cm一样高或者高于1014Ω·cm,并仍然可接受。
至少一种固溶体形成有效用作电改性的耐侵蚀材料的烧结陶瓷材料的主要摩尔分数。当存在用于形成固溶体的两者氧化物时,这些氧化物通常包含氧化钇结合其它氧化物,所述其它氧化物通常选自氧化锆、氧化铈、氧化铪、氧化铌及上述物质的组合。其它氧化物诸如氧化钪、氧化钕、氧化钐、氧化镱、氧化铒和氧化铈(以及其它镧系列元素氧化物)可考虑用于这些实施例中。
当存在用于形成一种或多种固溶体的多于两种的氧化物时,这些氧化物通常包含氧化钇、氧化锆和至少一种其它氧化物,所述氧化物通常选自氧化铪、氧化钪、氧化钕、氧化铌、氧化钐、氧化镱、氧化铒、氧化铈及上述氧化物的组合物。在特别实施例中还可能使用其它镧系元素。当烧结陶瓷包含多个固溶相时,通常有两个相或三个相。除了至少一个固溶相,可能在烧结陶瓷内存在化合物或元素金属的其它相。
通过示例方式,而并不限制于此,关于使用两种先驱物氧化物的烧结陶瓷,已经通过试验确定包含固溶体的烧结陶瓷,所述固溶体中存在约40%摩尔分数到小于100%摩尔分数范围内的氧化钇,并存在从大约0%摩尔分数到约60%摩尔分数范围内的氧化锆,产生具有在从约350℃至室温范围内的温度下从约107到约1015Ω·cm范围内的电阻率。预期可由其中存在大于0%摩尔分数到小于100%摩尔分数范围内的氧化钇和大于0%摩尔分数至小于100%摩尔分数的氧化铈的先驱氧化物的组合得到相同范围内的电阻率。还预期可由其中存在大于0%摩尔分数到小于100%摩尔分数范围内的氧化钇和大于0%摩尔分数至小于100%摩尔分数的氧化铪的先驱氧化物组合得到从约109到约1011Ω·cm范围内的电阻率。还预期可由其中存在从约48%摩尔分数到小于100%摩尔分数范围内的氧化钇和大于0%摩尔分数至约52%摩尔分数范围内的氧化铌的先驱氧化物组合得到具有约109到约1011Ω·cm范围内电阻率的陶瓷。
用于实施例,并不限制于此,关于使用多于两种先驱氧化物的烧结陶瓷,在一个实施方式中,当烧结陶瓷包含固溶体并且其中烧结陶瓷材料由以下氧化物形成时,其中:存在从约40%摩尔分数至小于100%摩尔分数范围内的氧化钇;存在从大于0%摩尔分数至约50%摩尔分数范围内的氧化锆;以及存在大于约0%摩尔分数到小于100%摩尔分数范围内的氧化钐,烧结陶瓷具有从约107到约1015Ω·cm范围内的电阻率。
在另一实施方式中,当烧结的陶瓷包含固溶体并且烧结陶瓷材料由以下氧化物制成时:存在从约40%摩尔分数至小于100%摩尔分数范围内的氧化钇;存在从大于0%摩尔分数至约50%摩尔分数范围内的氧化锆;以及存在大于约0%摩尔分数到小于100%摩尔分数范围内的氧化铪,烧结陶瓷将具有在约107到约1015Ω·cm范围内的电阻率。
在又一实施方式中,当烧结的陶瓷包含固溶体并且烧结陶瓷材料由以下氧化物制成时:存在从约40%摩尔分数至小于100%摩尔分数范围内的氧化钇;存在从大于0%摩尔分数至约45%摩尔分数范围内的氧化锆;以及存在大于约0%摩尔分数到小于80%摩尔分数范围内的氧化铌时,烧结陶瓷将具有在约107到约1015Ω·cm范围内的电阻率。
在一个实施方式中,烧结的陶瓷材料包含三个相,所述三个相包括:包含Y2O3-ZrO2-Nb2O5并占烧结陶瓷材料的从约60%摩尔分数到约90%摩尔分数范围内的第一固溶相;占烧结陶瓷材料的从约5%摩尔分数到约30%摩尔分数范围内的Y3NbO7第二相;以及占烧结陶瓷材料的从约1%摩尔分数到约10%摩尔分数范围内的Nb元素形式的第三相。
包含三个相的烧结陶瓷材料的另一实施方式中,氧化钇在从约60%摩尔分数至小于约75%摩尔分数范围内;氧化锆在从大于约15%摩尔分数至约25%摩尔分数范围内;以及氧化铌在大于约5%摩尔分数到小于15%摩尔分数范围内。
在由以上所述类型的Y2O3-ZrO2-MxOy形成的烧结陶瓷测量样品中,在其中M是钐、铪、铌或钕的实施方式中,在暴露于CF4/CHF3等离子体76小时之后,已经证明侵蚀速度是0.16μ/小时或更低。预期当M是铈、钐、铒或其它镧系元素时具有类似的侵蚀速度。等离子体形成于可从Applied Materials有限公司购得的Enabler for Trench Etch等离子体处理腔室中,等离子体源功率高达2000W,工艺腔室压力为10-500m托(Torr),并且衬底温度为40℃。所述0.16μ/小时或更低的侵蚀速度等价于纯Y2O3的侵蚀速度。因此,用于提供较低电阻率烧结陶瓷的烧结陶瓷改性不影响烧结陶瓷的侵蚀速度。
虽然以上所述的陶瓷材料是由利用本领域公知的烧结技术形成的烧结陶瓷,但是在其它实施方式中,以上列出的起始材料成分可用于利用涂覆技术形成陶瓷涂层于各种金属和陶瓷衬底的表面上,所述起始材料成分包括但是不限于铝、铝合金、不锈钢、氧化铝、铝氮化物和石英。所述涂覆技术包括等离子体喷涂、热/火焰喷涂;从由烧结氧化物形成的溅射靶的物理气相沉积;或者化学气相沉积,作为示例但是并不限制于此。
附图说明
为了有助于理解以上所述的实施方式,可参照附图更加详细地描述以上所述的特定实施方式。然而,应该注意到,附图仅示出了部分典型实施方式并因此不用于现在在此所述的本发明的范围。本发明包括其它等效的实施方式。
图1是示出了对于多种材料,在空气环境中施加电压为1000V下,电阻率与温度的函数关系图表100;
图2是Y2O3-ZrO2-Al2O3相图200。所述相图示出了除了其它成分之外,特种材料的组成,在此在相图上标记为区域“A”用于参考。类型“A”陶瓷材料是对卤素等离子体侵蚀具有良好耐腐蚀性的陶瓷成分;
图3是Y2O3-ZrO2-Nb2O5相图300。所述相图示出除了其它成分外,特种材料的组成,在此在相图上标记为区域“B”,用于参考。类型“B”陶瓷材料为不仅对卤素等离子体侵蚀具有良好耐腐蚀性而且还具有例如与“A”类型陶瓷材料相比的可控的、较低电阻率的陶瓷成分;
图4是示出对于多种材料的电阻率与施加的电压的函数关系图表400,其中测量可在室温(约27℃)空气中下进行;
图5是柱形图500,示出了暴露于由CF4和CHF3源气体产生的等离子体的多种烧结陶瓷材料相对于纯氧化钇的标准化平均示例性侵蚀速度。
具体实施方式
作为详细描述的绪言,应该注意到,如在该说明书和附图中所用的,单数形式“一(a)”、“一(an)”和“所述(the)”包括复数指代,文中清晰指出数目的除外。
当在此使用词“about”时,意欲指所指的标称值准确地在±10%内。
在此所述地为在采用含卤素等离子体的半导体器件处理条件下研发的抵抗侵蚀的特种陶瓷材料。在特定实施方式中,已经改性特种材料以具有与之前研发的类似陶瓷材料相比减小的电阻率以提供耐等离子体腐蚀性。减小的电阻率有益于减小在半导体处理腔室内的各种组件处等离子体电弧放电(arcing)的可能性,尤其在等离子体放电成问题的静电夹盘的表面或衬底升降杆上,用于举例但不限于此。在过去,组件或至少组件表面由铝氮化物或铝氧化物制造,可对所述铝氮化物或铝氧化物掺杂以提供电属性。虽然所述材料提供所需的电属性,但是侵蚀/腐蚀速度相对快,限制了特定组件的有效寿命,并需要更多的停工时间用于组成部件的修理及替换。
另外,用作等离子体处理半导体装置内的工艺腔室衬垫和功能组件的各种材料的电属性影响等离子体的行为。等离子体行为中的变化影响等离子体处理属性,并且当影响显著时,需要改变其它工艺变量以适应等离子体行为的变化。胜于返工用于器件制造的处理变量,发展具有适合电属性的耐腐蚀陶瓷材料更实用。仅改性部分具有适合等离子体腐蚀/侵蚀属性的陶瓷材料以控制电阻率性能在对于与等离子体接触的组件有效的所需范围内。当选择氧化物的组合以形成陶瓷材料时,本领域且读取本发明的普通技术人员将能相对成功地确定本发明。
为了便利,具有所需电属性的适合耐卤等离子体腐蚀/侵蚀陶瓷材料的发展通过使用烧结陶瓷实施。所烧结的陶瓷通过本领域的众所周知的技术生产。在其它实施方式中,相同的一般组分的适合耐卤等离子体腐蚀/侵蚀的陶瓷材料可例如,使用热/火焰喷镀或等离子体喷镀应用为在下层诸如铝或铝合金的材料之上的涂层。在可选实施方式中,所烧结的陶瓷材料可用于制造可用于通过物理气相沉积在下层材料之上施加陶瓷材料,特别地当上面待施加保护陶瓷材料的装置较大时,所述装置诸如工艺腔室衬垫。
如之前所述,讨论的所烧结陶瓷材料包括氧化钇。可改变所烧结的含钇陶瓷材料的电阻率。在一个示例性技术中,至少一种其它氧化物添加到氧化钇中并烧结所述混合物。至少一种其它氧化物的阳离子具有不同于Y3+离子的化合价,以形成Y空位,导致电阻率降低。所述氧化物的实施例包括CeO2、TiO2、ZrO2、HfO2和Nb2O5,仅用于示例而并不限制于此。在另一示例性技术中,至少一种其它氧化物添加到氧化钇中,并在还原气氛中烧结所述混合物;然而,至少一种其它氧化物的阳离子具有与Y3+离子相同的化合价,但是展示出与Y3+离子显著不同的离子半径。这样导致O空位产生,这也降低了电阻率。具有与Y3+离子相同化合价但是具有显著不同的离子半径的氧化铝实施例包括Nd2O3、Sm2O3、Sc2O3、Yb2O3、Er2O3、Ho2O3和Dy2O3,仅用于示例而并不限制于此。
至今已经研究了多种示例性烧结陶瓷材料的属性,并且以下的表格提供了所制造并评估的部分烧结陶瓷材料。随后将描述这些材料的评估。
实施例:
表格
*N/A=无效
**c-ss指立方氧化钇型固溶体。
实施例一
图1是示出各种陶瓷材料的电阻率的图表100,陶瓷材料包括根据本发明的示例性实施方式制造的A型和B型材料。电阻率在轴104上示出,作为在轴102上示出的温度的函数。可在空气环境下在1000V下测量电阻率,使用根据ASTM D 1829-或JIS C2141的标准测试条件。
在图1中示出的曲线106在表中描述为样品#4的含Nb2O5烧结陶瓷材料。对于含Nb2O5烧结陶瓷材料,如图3中通过相图所示,还可通过添加额外的成分得到适合的电阻率值。烧结陶瓷材料包含三个相,所述三个相包括包含Y2O3-ZxO2-Nb2O5的第一固溶相,占烧结陶瓷材料的约60%到约90%摩尔分数;第二相Y3NbO7,占烧结陶瓷材料的从约5%到约30%的摩尔分数;以及元素形式的Nb第三相,占烧结陶瓷材料的约1%到约10%摩尔分数。当需要低电阻率以防止电弧放电时,所述材料特别有效。电阻率在室温下低于约1011Ω·cm并在200℃为约108Ω·cm,以及在典型半导体处理条件下可能具有在109Ω·cm范围内的电阻率。
在图1中示出的含Nb2O5的烧结陶瓷材料的一个实施方式称为Nb2O5-ZrO2-Y2O3。参照图3,相图的一个区域标记为“B”。所述标记表示烧结陶瓷材料的固溶相成分在从约55%摩尔分数到约80%摩尔分数之间的浓度下包含Y2O3,并且在从约5%摩尔分数到约25%摩尔分数之间的浓度下包含添加剂诸如Nb2O5、HfO2、Nd2O3、或Sc2O3。
实施例二
在图1中示出的曲线108表示根据本发明制造的含HfO2烧结陶瓷材料,所述含HfO2烧结陶瓷材料还在表格中描述为样品#1。所述陶瓷材料显示出比含Nb2O5材料高的电阻率,但是对制造与静电夹盘或衬底升降杆相比电弧放电不主要的半导体处理装置组件有效。
实施例三
在图1中示出的曲线110表示根据本发明实施方式制造的含Sc2O3烧结陶瓷材料,所述含Sc2O3烧结陶瓷材料还在表格中描述为样品#2。同样,所述材料可用于需要1011Ω·cm电阻率的应用中。
实施例四(对比实施例)
在图1中示出曲线112表示在图2的相图中示出的Y2O3-ZrO2-A12O3材料。描述所述材料仅用于可控电阻率陶瓷材料的比较实施例的目的。所述烧结陶瓷材料包含由Y2O3和ZrO2形成的固溶体,以及由Y2O3和Al2O3氧化物形成的合成物。典型的烧结陶瓷材料由在从约60%摩尔分数到约65%摩尔分数之间的浓度下的Y2O3;在从约20%摩尔分数到约25%摩尔分数之间的浓度下的ZrO2;以及在从约10%摩尔分数到约15%摩尔分数之间的浓度下的Al2O3形成。在相图图2中示为区域“A”并通过曲线表示为在图1中示出的Y2O3-ZrO2-A12O3的中心陶瓷材料的一个实施方式,包含:具有立方氧化钇型晶体结构的约60%摩尔分数固溶体,所述固溶体中c-Y2O3是溶剂,Zr2O3是溶质;具有萤石型晶体结构的约2%摩尔分数的固溶体,所述固溶体中是ZrO2溶剂,Y2O3是溶质;以及约38%摩尔分数的YAM(Y4Al2O9)化合物。
实施例五(对比实施例)
图1的曲线114表示含Nd2O3的烧结陶瓷材料,所述含Nd2O3的烧结陶瓷材料在表格中描述为样品#3。但是所述材料难以满足需要防止放电的需要,并且认为不是弥补本发明的部分单一材料的比较实施例。
实施例六(对比实施例)
图1的曲线116表示纯Y2O3烧结陶瓷的电阻率属性。所述材料也是对比实施例,上述对比实施例用作基线,原因在于许多半导体装置组件已由纯Y2O3制造。纯Y2O3电阻率的比较示出由本发明得到的电阻率的显著改善。
曲线120也在图1中示出,所述曲线120表示通常用于制造静电夹盘的掺杂铝氮化物,曲线122表示也用于制造静电夹盘和需要低电阻率的其它半导体处理装置的第二掺杂的铝氮化物。
实施例七
图4是示出对于许多烧结陶瓷测试样本在电阻率测试期间电阻率与所施加的电压的函数关系图400。在轴404上示出电阻率,并且电压在轴402上示出。测试温度是室温(约27℃)。该图的目的是为了示出受控以降低电阻率的本发明的耐侵蚀陶瓷实施方式和目前使用的掺杂铝氮化物陶瓷之间在电阻率上的区别。虽然掺杂的铝氮化物陶瓷具有稍微低的电阻率,但它们的侵蚀速度至少比已经改性以降低电阻率的含氧化钇陶瓷的侵蚀速度高2倍。
特别地,图4的曲线422表示目前用于制造静电夹盘的掺杂的铝氮化物陶瓷。曲线420表示用于制造静电夹盘和其它较低电阻率组件的另一种掺杂的铝氮化物陶瓷。
图4的曲线406表示含Nb2O5的烧结陶瓷材料,所述含Nb2O5的烧结陶瓷材料在表格中表示为样品#4。已经改性以降低电阻率的含氧化钇材料具有与表示为AlN-1的掺杂的铝氮化物非常接近的电阻率。然而,掺杂的铝氮化物的侵蚀速度比由曲线406示出的含氧化钇材料的侵蚀速度高10倍,如通过图5中的柱状图500示出。
在图4中的曲线408表示含HfO2的烧结陶瓷材料,所述含HfO2的烧结陶瓷材料在表格中表示为样品#1。所述陶瓷材料表现出比含Nb2O5材料高的电阻率,并且在室温下表现出等离子体电弧放电更可能发生的组件的推荐范围之外的电阻率。然而,在200℃下,所述200℃在部分半导体处理期间存在的温度,电阻率落入可接受范围内,如图1中通过曲线108所示。
图4的曲线410表示含Sc2O3的烧结陶瓷材料,所述含Sc2O3的烧结陶瓷材料在表格中表示为样品#2。再次,当处理温度为200℃时,所述材料可用于需要1011Ω·cm电阻率的应用中。
为了比较目的(关于包含含氧化钇固溶体的电阻率可控的陶瓷),图4的曲线412示出了包含在图2中示出的Y2O3、ZrO2和Al2O3的“A”型陶瓷材料。所述“A”型材料的一个实施方式,在图1中示出,包含具有c-Y2O3为溶剂以及Zr2O3为溶质的约60%摩尔分数的立方氧化钇型结构;具有ZrO2为溶剂以及Y2O3为溶质的约2%摩尔分数的萤石型结构固溶体;以及,约38%摩尔分数YAM(Y4Al2O9)化合物。虽然A型HPM材料表示出适合的耐侵蚀性能和优良的机械性能,但电阻率显著高于所需范围最大值1011Ω·cm。即使在200℃下也是这种情况,如图1中的曲线112所示。所述材料并不包括于电阻率改性的耐侵蚀陶瓷的实施方式中。
为了比较目的,图4的曲线414表示含Nd2O3的烧结陶瓷材料,所述含Nd2O3的烧结陶瓷材料在表格中表示为样品#3。所述材料难以满足防止电弧放电的需要,并认为是不构成本发明的单一陶瓷材料部分的比较实施例。
为了比较目的,图4的曲线416示出了纯Y2O3的烧结陶瓷的电阻率属性。所述材料也是比较实施例,所述比较实施例用作基准,原因在于大部分半导体装置组件已经由纯Y2O3制造。纯Y2O3的电阻率的比较示出了由本发明所得到的电阻率有非常显著的改善。
实施例八
图5示出了表示对于多种暴露于等离子体的烧结陶瓷材料标准化为纯Y2O3的示例性侵蚀速度的柱状图500。等离子体由CF4和CHF3源气产生。等离子体处理腔室是可从Applied Materials有限公司购得的Enabler for TrenchEtch。等离子体源功率高达2000W,工艺腔室压力为10-500mTorr,并且衬底温度为约40℃,76小时的时间周期。轴502示出了测试耐侵蚀性的多种材料。表示为Y2O3-10ZrO2的测试样本表示通过烧结100重量份数的Y2O3以及10重量份数的ZrO2形成。表示为含Nb2O5-或HfO2-或Nd2O3-或Sc2O3-的测量样本表示描述为含蚀刻这些材料的化合物。如在轴504上所示的侵蚀速度的比较表示所改性的电阻率的侵蚀速度,含氧化钇的烧结陶瓷材料基本与纯氧化钇的侵蚀速度相同。另外,所改性的电阻率的侵蚀速度,含氧化钇的烧结陶瓷基本比Al2O3、AlN、ZrO2、石英、W/ZrC、B4C和SiC更佳,用于提供半导体处理腔室衬垫和在半导体处理装置内部组件上的耐卤素等离子体腐蚀材料。
基于在提供以上所述的实施例的实验期间所得到的结果,以及来自其它参考源的数据,已经进行了提供在等离子体漏电流中的UV辐射效果评估的计算。等离子体环境中(用于等离子体处理中的类型)的UV辐射不影响含电阻率改性的氧化钇的烧结陶瓷材料的漏电流。
193nmUV辐射(在部分半导体处理操作中采用)对在Nb2O5-B型烧结陶瓷材料和HfO2-B型烧结陶瓷材料中的漏电流的影响的研究表示这些材料的电性能不应用受这些UV辐射影响。
用作与等离子体接触的半导体处理装置的含陶瓷颗粒的制品包括盖子、衬垫、喷嘴、气体分配板、喷头、静电夹盘组件、阴影框架、衬底容纳框架、处理套件和腔室衬垫,仅作为示例性并且不限于此。
以上所述的示例性实施方式不意欲限制本发明的范围,由于本发明的公开内容,本发明的普通技术人员能解释与本发明所要求保护的主题对应的实施方式。
Claims (32)
1.一种含陶瓷制品,能抵抗半导体处理中使用的含卤素等离子体的侵蚀,并且所述含陶瓷制品在从约350℃至室温范围内的温度下呈现在约107到1015Ω-cm范围内的可控电阻率,所述陶瓷制品具有表面,所述表面包含至少一种固溶体,所述至少一种固溶体包含氧化钇,并且其中包含氧化钇的至少一种固溶体还包含选自由氧化锆、氧化铪、氧化钪、氧化铌、氧化钐、氧化镱、氧化铒、氧化铈及上述氧化物的组合组成的组的一种或多种氧化物。
2.根据权利要求1所述的含陶瓷制品,其中其它镧系元素氧化物包括于所述陶瓷制品中。
3.根据权利要求1所述的含陶瓷制品,其中两种氧化物用于形成所述至少一种固溶体,所述至少一种固溶体包含氧化钇和其它氧化物,以及其中所述其它氧化物选自由氧化锆、氧化铈、氧化铪和氧化铌组成的组。
4.根据权利要求3所述的含陶瓷制品,其中氧化钪、氧化钐、氧化镱、氧化铒或其它镧系元素氧化物包括于所述陶瓷制品中。
5.根据权利要求1所述的含陶瓷制品,其中多于两种的前驱物氧化物用于形成包含氧化钇的所述固溶体,以及其中所述前驱物氧化物包括氧化锆以及选自由氧化铪、氧化钪、氧化铌、氧化钐、氧化镱、氧化铒、氧化铈及上述氧化物组合组成的组的其它氧化物。
6.根据权利要求5所述的含陶瓷制品,其中其它镧系元素包括于所述含陶瓷制品中。
7.根据权利要求3所述的含陶瓷制品,其中所述陶瓷由在从约40%摩尔分数到小于100%摩尔分数范围内的浓度下的氧化钇,和在从高于0%摩尔分数到约60%摩尔分数范围内的浓度下的氧化锆形成。
8.根据权利要求3所述的含陶瓷制品,其中所述陶瓷由在从约40%摩尔分数到小于100%摩尔分数范围内的浓度下的氧化钇,和在从高于0%摩尔分数到约60%摩尔分数范围内的浓度下的氧化铈形成。
9.根据权利要求3所述的含陶瓷制品,其中所述陶瓷由在从约40%摩尔分数到小于100%摩尔分数范围内的浓度下的氧化钇,和在从高于0%摩尔分数到约60%摩尔分数范围内的浓度下的氧化铪形成。
10.根据权利要求3所述的含陶瓷制品,其中所述陶瓷由在从约40%摩尔分数到小于100%摩尔分数范围内的浓度下的氧化钇,和在从高于0%摩尔分数到约60%摩尔分数范围内的浓度下的氧化铌形成。
11.根据权利要求5所述的含陶瓷制品,其中所述氧化钇存在从约40%摩尔分数到小于100%摩尔分数范围内的浓度,以及氧化锆存在从高于0%摩尔分数到约20%摩尔分数范围内的浓度,以及氧化钪存在从高于0%摩尔分数到小于100%摩尔分数范围内的浓度。
12.根据权利要求5所述的含陶瓷制品,其中所述氧化钇存在从约70%摩尔分数到小于100%摩尔分数范围内的浓度,以及氧化锆存在从高于0%摩尔分数到约17%摩尔分数范围内的浓度,以及氧化铪存在从高于0%摩尔分数到约27%摩尔分数范围内的浓度。
13.根据权利要求5所述的含陶瓷制品,其中所述制品由三相烧结陶瓷形成,所述三相烧结陶瓷包括包含Y2O3-ZrO2-Nb2O5的第一相固溶体,占所述烧结陶瓷材料的约60%到约90%之间的摩尔分数;第二相Y3NbO7,占所述烧结陶瓷材料的约5%到约30%之间的摩尔分数;以及元素形式的第三相Nb,占所述烧结陶瓷材料的约1%到约10%之间的摩尔分数。
14.根据权利要求1所述的含陶瓷制品,其中所述制品为静电夹盘或衬底升降杆外形或其它制品形式,所述制品需要从约350℃到室温范围内的温度下从约107到1015Ω-cm范围内电阻率。
15.根据权利要求1所述的含陶瓷制品,其中所述制品为在半导体处理腔室内部使用的内部组件或衬垫形式,以及其中所述陶瓷制品的所述电阻率是在约350℃至室温下约107到1015Ω-cm范围内。
16.根据权利要求1所述的含陶瓷制品,其中所述制品为固体烧结陶瓷制品。
17.根据权利要求1所述的含陶瓷制品,其中所述制品选自由静电夹盘、盖子、衬垫、喷嘴、气体分配板、喷头、静电夹盘组件、阴影框架、衬底容纳框架、处理套件和腔室衬垫组成的组。
18.根据权利要求1所述的含陶瓷制品,其中所述制品的所述表面涂覆有所述陶瓷。
19.一种降低采用静电夹盘、衬垫、或具有与等离子体接触表面的内部组件的半导体处理腔室内的等离子体电弧放电的方法,所述表面包含陶瓷材料,所述方法包含:
a)选择氧化物以由氧化钇和至少一种其它氧化物组成所述陶瓷材料,其中所述其它氧化物的阳离子具有与Y3+离子显著不同的化合价,以形成Y空位,导致所述陶瓷材料的电阻率降低;
b)烧结所述氧化物以形成至少一种结晶固溶体;以及
c)将所述陶瓷材料暴露于等离子体。
20.根据权利要求19所述的方法,其中具有与所述Y3+离子不同的化合价的所述氧化物选自由CeO2、TiO2、ZrO2、HfO2、Nb2O5及上述氧化物的组合组成的组。
21.一种减少采用静电夹盘、衬垫或具有接触等离子体的表面的内部组件的半导体处理腔室内的等离子体电弧放电的方法,所述表面包含陶瓷材料,所述方法包含:
a)选择氧化物以由氧化钇和至少一种其它氧化物组成所述陶瓷材料,其中所述其它氧化物的阳离子展示出与Y3+离子相同的化合价,但具有与Y3+离子显著不同的离子半径,导致所述陶瓷材料的电阻率降低;
b)在还原气氛中烧结所述氧化物;以及
c)将所述陶瓷材料暴露于等离子体。
22.根据权利要求21所述的方法,其中具有显著不同的离子半径的所述氧化物选自由Nd2O3、Sm2O3、Sc2O3、Yb2O3、Er2O3、Ho2O3、Dy2O3及上述氧化物的组合组成的组。
23.一种含陶瓷制品,能抵抗半导体处理中使用的含卤素等离子体的侵蚀并提供可控电阻率,所述可控电阻率有益于减小在半导体处理腔室内的各种组件处等离子体电弧放电的可能性,其中所述含陶瓷制品的表面在从约350℃至室温范围内的温度下呈现在约107到1015Ω-cm范围内的电阻率,所述表面包含至少一种固溶体,所述至少一种固溶体包含在40%摩尔分数或更高浓度下的氧化钇,并且所述至少一种固溶体还包含选自由氧化锆、氧化铪、氧化钪、氧化铌、氧化钐、氧化镱、氧化铒、氧化铈及上述氧化物的组合组成的组的至少一种或多种氧化物。
24.根据权利要求23所述的含陶瓷制品,其中两种氧化物用于形成所述至少一种固溶体,所述至少一种固溶体包含氧化钇和其它氧化物,其中所述其它氧化物选自由氧化锆、氧化铈、氧化铪和氧化铌组成的组。
25.根据权利要求23所述的含陶瓷制品,其中多于两种的前驱物氧化物用于形成包含氧化钇的所述固溶体,以及其中所述前驱物氧化物包括氧化锆以及选自由氧化铪、氧化钪、氧化铌、氧化钐、氧化镱、氧化铒、氧化铈及上述氧化物组合组成的组的其它氧化物。
26.根据权利要求25所述的含陶瓷制品,其中氧化钇存在从约40%摩尔分数到小于100%摩尔分数范围内的浓度,氧化锆存在从高于0%摩尔分数到约27%摩尔分数范围内的浓度,以及氧化钪存在高于0%摩尔分数到小于60%摩尔分数。
27.根据权利要求25所述的含陶瓷制品,其中氧化钇存在从约70%摩尔分数到小于100%摩尔分数范围内的浓度,氧化锆存在从高于0%摩尔分数到约17%摩尔分数范围内,以及氧化铪存在从高于0%摩尔分数到约27%摩尔分数范围内。
28.根据权利要求23所述的含陶瓷制品,其中所述制品为静电夹盘或衬底升降杆形式,所述制品需要从约255℃到室温范围内的温度下从约107到1011Ω-cm范围内的电阻率。
29.根据权利要求23所述的含陶瓷制品,其中所述制品为在半导体处理腔室内部使用的内部组件或衬垫形式,以及其中所述陶瓷制品的所述电阻率是在约250℃下约107Ω-cm到在室温下约1015Ω-cm范围内。
30.根据权利要求23所述的含陶瓷制品,其中所述制品为固体烧结陶瓷制品。
31.根据权利要求23所述的含陶瓷制品,其中所述制品选自由静电夹盘、盖子、衬垫、喷嘴、气体分配板、喷头、静电夹盘组件、阴影框架、衬底容纳框架、处理套件和腔室衬垫组成的组。
32.一种含陶瓷制品,能抵抗半导体处理中使用的含卤素等离子体的侵蚀,并呈现在250℃的温度下小于约107Ω-cm和上达在室温下约1011Ω-cm的电阻率,所述含陶瓷制品具有固溶体陶瓷表面,所述固溶体陶瓷表面由前驱物氧化物形成,所述前驱物氧化物形成三相烧结陶瓷,所述三相烧结陶瓷包括包含Y2O3-ZrO2-Nb2O5的第一相固溶体,占所述烧结陶瓷材料的约60%到约90%之间的摩尔分数;第二相Y3NbO7,占所述烧结陶瓷材料的约5%到约30%之间的摩尔分数;以及元素形式的第三相Nb,占所述烧结陶瓷材料的约1%到约10%之间的摩尔分数。
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US8871312B2 (en) | 2014-10-28 |
US20090036292A1 (en) | 2009-02-05 |
EP2030961A2 (en) | 2009-03-04 |
TW200906759A (en) | 2009-02-16 |
JP2009035469A (ja) | 2009-02-19 |
TWI361177B (en) | 2012-04-01 |
US8367227B2 (en) | 2013-02-05 |
KR20090013645A (ko) | 2009-02-05 |
CN101357846A (zh) | 2009-02-04 |
KR100934516B1 (ko) | 2009-12-31 |
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