CN116768631A - 高电阻高耐腐蚀陶瓷材料及晶片载放台 - Google Patents

高电阻高耐腐蚀陶瓷材料及晶片载放台 Download PDF

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CN116768631A
CN116768631A CN202211703929.1A CN202211703929A CN116768631A CN 116768631 A CN116768631 A CN 116768631A CN 202211703929 A CN202211703929 A CN 202211703929A CN 116768631 A CN116768631 A CN 116768631A
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ceramic
ceramic material
wafer
resistance
substrate
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服部亮誉
上田晃司
西尾仁志
沟口智久
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NGK Insulators Ltd
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Abstract

本发明涉及高电阻高耐腐蚀陶瓷材料及晶片载放台。所要解决的课题是,在高温下具有充分的耐腐蚀性、并且提高高温下的体积电阻率。本发明的高电阻高耐腐蚀陶瓷材料含有镁‑铝氮氧化物,碳含有率为0.005~0.275质量%。

Description

高电阻高耐腐蚀陶瓷材料及晶片载放台
技术领域
本发明涉及高电阻高耐腐蚀陶瓷材料及晶片载放台。
背景技术
在半导体制造中的干式工艺、等离子体涂敷等中使用的半导体制造装置中,作为蚀刻用、清洗用,使用反应性高的F、Cl等卤素系等离子体。因此,对组装于这种半导体制造装置的部件要求高耐腐蚀性。作为具有高耐腐蚀性的材料,如专利文献1所示,已知有以镁-铝氮氧化物相为主相的陶瓷材料。该陶瓷材料能够长期耐受在半导体制造工艺中使用的反应性高的卤素系等离子体。
现有技术文献
专利文献
专利文献1:日本专利第5680645号公报
发明内容
近年来,为了生成高品质的膜,工艺温度高温化(500℃以上)。因此,不仅要求在高温下具有充分的耐腐蚀性,还要求能够在高温下静电吸附晶片。
本发明是为了解决这样的课题而提出的,主要目的在于在高温下具有充分的耐腐蚀性、并且提高高温下的体积电阻率。
本发明的高电阻高耐腐蚀陶瓷材料是含有镁-铝氮氧化物的陶瓷材料,其中,碳含有率为0.005~0.275质量%。
根据该陶瓷材料,由于以适当的范围含有碳,因此在高温下具有充分的耐腐蚀性、并且能够提高高温下的体积电阻率。
本发明的晶片载放台具备:陶瓷基体,其由上述的陶瓷材料形成、并能够在上表面载放晶片;和电极,其配置于所述陶瓷基体的内部,
或者,本发明的晶片载放台具备:陶瓷基体,其由上述的陶瓷材料形成、并能够在上表面载放晶片;高热传导基体,其设置在所述陶瓷基体的下表面、且热传导率比所述陶瓷基体高;电极,其配置于所述陶瓷基体的内部、所述高热传导基体的内部或所述陶瓷基体和所述高热传导基体之间;和电阻发热体,其配置于所述高热传导基体的基体内部且比所述电极更靠下方。
根据这样的晶片载放台,由于陶瓷基体由上述的陶瓷材料形成,因此在高温下具有充分的耐腐蚀性、并且能够提高高温下的体积电阻率。在此,“电极”例如可以是静电电极,也可以是加热器电极(电阻发热体),还可以是等离子体产生用的高频(RF)电极。
附图说明
图1是晶片载放台10的纵截面图。
图2是晶片载放台20的纵截面图。
图3是晶片载放台30的纵截面图。
图4是晶片载放台40的纵截面图。
图5为实验例3的XRD图。
图6为实验例5的XRD图。
图7是表示C含有率与500℃下的体积电阻率的关系的曲线图。
符号说明
10晶片载放台、12陶瓷基体、12a晶片载放面、14静电电极、16电阻发热体、18轴、20晶片载放台、22陶瓷基体、22a晶片载放面、23高热传导基体、24静电电极、26电阻发热体、28轴、30,40晶片载放台。
具体实施方式
以下,参照附图对本发明的优选实施方式进行说明。图1~图4是晶片载放台10~40的纵截面图。需要说明的是,在本说明书中,“上”、“下”并非表示绝对的位置关系,而是表示相对的位置关系。因此,根据晶片载放台10~40的朝向,“上”“下”成为“下”“上”、或成为“左”“右”、或成为“前”“后”。另外,在本说明书中,表示数值范围的“~”作为包含在其前后记载的数值作为下限值和上限值的含义来使用。
本实施方式的高电阻高耐腐蚀陶瓷材料含有镁-铝氮氧化物,碳含量为0.005~0.275质量%。如果碳含有率在该范围,则能够在高温下具有充分的耐腐蚀性、并且能够提高高温下的体积电阻率。例如,在将该陶瓷材料用于具有晶片载放面的、内置有静电电极的陶瓷基体的情况下,能够在高温下静电吸附晶片、或抑制在高温下处理晶片时在晶片与电极之间流动有漏电流。另外,在将该陶瓷材料用于内置有加热器电极(电阻发热体)或RF电极的陶瓷基体的情况下,能够抑制在高温下处理晶片时在晶片与电极之间流动有漏电流。在碳含有率小于0.005质量%的情况下或超过0.275质量%的情况下,500℃下的体积电阻率变低。碳含有率优选为0.005~0.21质量%。本实施方式的陶瓷材料优选含有镁-铝氮氧化物作为主相。在此,主相是指整体所占的相中包含最多的相。
本实施方式的陶瓷材料优选在500℃下的体积电阻率为1×109Ωcm以上。如果500℃下的体积电阻率为1×109Ωcm以上,则在将该陶瓷材料用作具有晶片载放面的、内置有电极的陶瓷基体的情况下,能够充分抑制在高温下处理晶片时在晶片与电极之间流动有漏电流。另外,在将该陶瓷材料用于静电卡盘的情况下,能够在高温下利用约翰逊拉别克力可靠地静电吸附晶片。另外,500℃下的体积电阻率优选为5×1011Ωcm以下。如此,在将该陶瓷材料用于静电卡盘的情况下,能够使晶片的吸脱附响应性良好。
本实施方式的陶瓷材料可以含有钛。通过含有钛,能够使陶瓷材料的颜色为黑色。因此,能够使陶瓷材料的颜色不均变得不明显。钛的含有率设定为耐腐蚀性不降低、500℃下的体积电阻率不脱离上述范围即可,例如,以氧化物换算设定在0.1~1质量%的范围即可。
本实施方式的陶瓷材料优选将使用CuKα射线时的XRD峰至少出现在2θ=47~50°(优选为47~49°)的镁-铝氮氧化物相作为主相。这样的陶瓷材料对卤化等离子体的耐腐蚀性与尖晶石同等或比尖晶石高,因此优选。该主相优选与专利文献1(日本专利第5680645号)所涉及的镁-铝氮氧化物的峰一致。需要说明的是,专利文献1所涉及的镁-铝氮氧化物的峰例如与参考文献1(J.Am.Ceram.Soc.,93[2]322-325(2010))、参考文献2(日本特开2008-115065)所示的MgAlON(或氮氧化铝镁)的峰不一致。一般而言,已知这些MgAlON为尖晶石中固溶了N成分的物质,可认为具有与专利文献1所涉及的镁-铝氮氧化物不同的晶体结构。
接着,对本实施方式的陶瓷材料的制造例进行说明。本实施方式的陶瓷材料可以通过将氧化镁、氧化铝、氮化铝和碳源的混合粉末成型后烧成来制造。例如,可以按照氧化镁为5质量%以上60质量%以下、氧化铝为60质量%以下、氮化铝为90质量%以下的方式进行称量,进而在其中添加碳源进行混合,对所得到的粉末进行成型后,进行烧成。作为碳源,可以添加有机粘合剂、有机分散剂,也可以添加碳粉末。碳源的添加量设定为烧成后的陶瓷材料中所含的碳含量为0.005~0.2质量%即可。或者,也可以通过在烧成前的阶段进行脱脂,按照烧成后的陶瓷材料中含有的碳含量为0.005~0.2质量%的方式进行调整。该情况下,可以通过脱脂温度来调整碳含量。脱脂温度例如优选设定在300~600℃的范围。对于成型而言,例如可以在对混合粉末的浆料进行造粒而制成颗粒后对该颗粒进行粉末压制,也可以使用刮刀法将混合粉末的浆料制成生片。成型时的压力并没有特别限制,适当设定为能够保持形状的压力即可。烧成温度优选为1750℃以上,更优选为1800~1950℃。另外,烧成优选采用热压烧成,热压烧成时的压制压力优选设定为50~300kgf/cm2。烧成时的气氛优选为不影响氧化物原料的烧成的气氛,例如优选为氮气氛、氩气氛、氦气氛等非活性气氛。成型时的压力并没有特别限制,适当设定为能够保持形状的压力即可。
接着,参照附图,对晶片载放台10~40进行说明。
如图1所示,晶片载放台10为静电卡盘加热器,具备:静电电极14,其配置于陶瓷基体12的内部;和电阻发热体16,其配置于陶瓷基体12的内部且比静电电极14更靠下方。
陶瓷基体12是将上述陶瓷材料形成为圆板状而得到的,具有在上表面能够载放晶片的晶片载放面12a。
静电电极14为圆板状的金属板或金属网,与晶片载放面12a平行地设置。除了圆板的金属板、网以外,静电电极14还可以采用箔、冲孔金属、印刷电极等形态。需要说明的是,对于“平行”而言,除了完全平行的情况之外,即使不完全平行但在允许的误差(例如公差)的范围内就视为平行。陶瓷基体12中比静电电极14更靠上侧的部分作为介电层发挥功能。当向静电电极14施加直流电压时,载放于晶片载放面12a的晶片因约翰逊拉别克力(静电力)而吸附于晶片载放面12a。作为用于静电电极14的材料,可以举出例如W、Mo、W-Mo合金或它们的碳化物。
电阻发热体16在从上方观察陶瓷基体12时按一笔画的要领遍及整体地从一端配线至另一端,通过在一端与另一端之间流过电流而发热。电阻发热体16例如能够使用将线状的导体弯曲并加工成卷绕体而得到的部件。电阻发热体16的线径优选为0.3mm~0.5mm左右,在为线圈形状的情况下,卷径优选为2mm~4mm左右,间距优选为1mm~7mm左右。在此,“卷径”是指构成电阻发热体16的线圈的内径。作为电阻发热体16的形状,除了线圈形状之外,还可以采用带状、网状、螺旋弹簧状、片状、印刷电极等各种形态。作为用于电阻发热体16的材料,可以举出例如W、Mo、W-Mo合金或它们的碳化物。
在晶片载放台10的下表面接合有圆筒状的轴18。接合例如可以通过烧结来进行,也可以使用接合剂(例如无机接合剂)来进行。轴18优选使用与陶瓷基体12的线热膨胀系数相同或相近的部件。作为轴18的材料,优选使用AlN-YAG。YAG是钇铝石榴石(Y3Al5O12)的简称。AlN-YAG可以含有钛,其含有率例如可以以氧化物换算为0.1~1质量%。若添加钛,则AlN-YAG的颜色会变黑,因此能够使AlN-YAG的颜色不均变得不明显。
根据以上所说明的晶片载放台10,陶瓷基体12由上述的陶瓷材料形成,因此具有与上述陶瓷材料相同的效果,例如在高温下具有充分的耐腐蚀性、并能够提高高温下的体积电阻率。另外,能够在高温下静电吸附晶片、或在高温下处理晶片时抑制在晶片和静电电极14之间流动有漏电流。进而,能够抑制在高温下处理晶片时在晶片和电阻发热体16之间流动有漏电流。
图2所示的晶片载放台20是在内置有静电电极24的陶瓷基体22的下表面接合内置有电阻发热体26的高热传导基体23而成的静电卡盘加热器。接合例如可以通过烧结来进行,也可以使用接合剂(例如无机接合剂)来进行。
陶瓷基体22是将上述陶瓷材料形成为圆板状而得到的,具有在上表面能载放晶片的晶片载放面22a。静电电极24与上述静电电极14相同,因此省略说明。
高热传导基体23采用热传导率比陶瓷基体22高、且线热膨胀系数与陶瓷基体12相同或相近的部件。AlN-YAG可以含有钛,其含有率例如可以以氧化物换算为0.1~1质量%。若添加钛,则AlN-YAG的颜色会变黑,因此能够使AlN-YAG的颜色不均变得不明显。
电阻发热体26与上述电阻发热体16相同,因此省略说明。
在晶片载放台20的下表面接合有圆筒状的轴28。轴28与上述轴18相同,因此省略说明。
根据以上所说明的晶片载放台20,陶瓷基体22由上述的陶瓷材料形成,因此具有与上述陶瓷材料相同的效果,例如在高温下具有充分的耐腐蚀性、并能够提高高温下的体积电阻率。另外,能够在高温下静电吸附晶片、或在高温下处理晶片时抑制在晶片和静电电极14之间流动有漏电流。
另外,在晶片载放台20中,在陶瓷基体22的下表面接合有高热传导基体23,因此与晶片载放台10相比,容易使载放于晶片载放面22a的晶片的温度均匀。
进一步,高热传导基体23的热膨胀系数与陶瓷基体22的热膨胀系数相同或接近,因此即使反复进行升温和降温,也难以从陶瓷基体22剥离。
除了将静电电极24配置于陶瓷基体22与高热传导基体23的界面以外,图3所示的晶片载放台30与晶片载放台20相同。晶片载放台30也能够得到与晶片载放台20同样的效果。
除了将静电电极24内置于高热传导基体23而非陶瓷基体22以外,图4所示的晶片载放台40与晶片载放台20相同。电阻发热体26配置于比静电电极24更靠下方的位置。晶片载放台40也能够得到与晶片载放台20同样的效果。但是,在晶片载放台40中,电介质层(比静电电极24更靠上侧的部分)由陶瓷基体22和高热传导基体23构成,因此电介质层仅由陶瓷基体22构成的晶片载放台10~30更容易调整晶片的吸附力。
需要说明的是,本发明并不限于上述的实施方式,只要属于本发明的技术范围,当然可以以各种方式实施。
例如,作为晶片载放台10~40,示例了内置有静电电极14、24的情况,但也可以不内置静电电极14、24。在该情况下,也能够抑制在晶片与电阻发热体16、26之间流动有漏电流。另外,可以代替静电电极14、24而内置RF电极或者在静电电极14、24之外还内置RF电极,也可以将静电电极14、24兼用作RF电极。
另外,也能够将高热传导基体23的外周(上表面、侧面、下表面)用上述的陶瓷材料包裹。由此,能够提高侧面、底面的耐腐蚀性。
实施例
以下,对本发明的实施例进行说明。实验例2~6、9~11、13~15、17~19相当于本发明的实施例。需要说明的是,以下的实施例并不限定本发明。
[实验例1~7]
·调合
在实验例1中,按照达到表1所示的质量%的方式称量MgO原料、Al2O3原料以及AlN原料,以异丙醇为溶剂,使用尼龙制的罐、直径5mm的氧化铝球石湿式混合4小时。混合后取出浆料,在氮气流中以110℃干燥。之后通过30目的筛,制成调合粉末。
在实验例2中,按照达到表1所示的质量%的方式称量MgO原料、Al2O3原料和AlN原料,以异丙醇为溶剂,添加丙烯酸系粘合剂1.0质量%和聚羧酸系分散剂0.1质量%,在滚筒筛中使用氧化铝球石湿式混合4小时,制作原料浆料。使用喷雾干燥机对所得到的原料浆料进行喷雾干燥,制作了颗粒。进而,将所得到的颗粒在大气中以500℃加热24小时,制作部分脱脂的颗粒。
在实验例3中,在大气中以500℃加热5小时而进行部分脱脂,除此之外,与实验例2同样地制作了颗粒。
在实验例4中,添加丙烯酸系粘合剂1.5质量%和聚羧酸系分散剂0.5质量%并在大气中以450℃加热5小时而进行部分脱脂,除此之外,与实验例2同样地制作了颗粒。
在实验例5中,未进行脱脂,除此之外,与实验例4同样地制作了颗粒。
在实验例6中,按照达到表1所示的质量%的方式称量MgO原料、Al2O3原料和AlN原料,以异丙醇为溶剂,添加0.3质量%的碳粉末,使用尼龙制的罐、直径5mm的氧化铝球石湿式混合4小时。混合后取出浆料,在氮气流中以110℃干燥。之后通过30目的筛,制成调合粉末。
在实验例7中,添加0.42质量%的碳粉末,除此之外,与实验例6同样地制作了颗粒。
·成型
在100kgf/cm2的压力下,对调合粉末或颗粒进行单轴加压成型,制作了直径35mm、厚度10mm左右的圆板状成型体,收纳在烧成用石墨模中。
·烧成
通过对圆板状成型体进行热压烧成而得到陶瓷基体。在热压烧成中,将压制压力设为200kgf/cm2,并以表1所示的烧成温度(最高温度)进行烧成。气氛到烧成结束为止设为N2气氛。烧成温度下的保持时间设为4小时。
[评价]
(1)结晶相评价
在研钵中将实验例1~7得到的陶瓷基体粉碎,利用X射线衍射装置鉴定结晶相。测定条件为CuKα、40kV、40mA、2θ5-70°,使用封入管式X射线衍射装置(Bruker AXS制D8ADVANCE)。结果,在实验例1~7中的任一者中,主相均为镁-铝氮氧化物(在2θ=47~49°存在峰)。该主相与专利文献1所鉴定的镁-铝氮氧化物的峰一致。图5以及图6示出了代表例(实验例3、5)的XRD图。
(2)碳(C)含有率
C含有率根据JIS R1616:2007中记载的总碳量的测定方法来测定。具体而言,在氧气流中利用高频加热使试样与助燃剂一起燃烧,将生成的二氧化碳(和一氧化碳)与氧一起送入红外线分析仪,测定红外线吸收量的变化,求出C含有率。表1中示出了实验例1~7得到的陶瓷基体的C含有率。C含有率在实验例1、7中分别为0.002质量%、0.30质量%,而在实验例2~6中为0.005~0.21质量%。实验例1是专利文献1的实施品,实验例1的C含有率是未积极地添加碳源时的值(作为杂质而含有的C含有率)。
(3)体积电阻率(500℃)
体积电阻率通过基于JIS-C2141的方法,在大气中以500℃进行测定。试验片形状为直径50mm×(0.5~1mm),按照主电极的直径为20mm、保护电极的内径为30mm且外径为40mm、外加电极的直径为40mm的方式用银形成各电极。外加电压为500V/mm,读取施加电压后3分钟时的电流值,由该电流值算出室温体积电阻率。实验例1~7得到的陶瓷基体的体积电阻率示于表2。在表2的体积电阻率中,[E8]表示108,[E10]表示1010。对于500℃下的体积电阻率而言,在实验例2~6中为1×109Ωcm以上,但在实验例1、7中为比其低的值。将表示C含有率与500℃下的体积电阻率的关系的图示于图7。由图7的曲线图可知,500℃下的体积电阻率为1×109Ωcm以上的C含有率为0.005~0.275质量%。另外,若为0.011~0.19质量%,则达到5×109Ωcm以上,更好。
(4)热传导率(室温)
热传导率通过激光闪光法测定。将由实验例2、3、5、6中得到的陶瓷基体在室温下的热传导率示于表2。
(5)平均线热膨胀系数(40~1000℃)
1000℃下的平均线热膨胀系数使用膨胀计(Bruker AXS制),在氮气氛中,以40~1000℃进行测定。将由实验例2、3、5、6得到的陶瓷基体在室温下的平均线热膨胀系数示于表2。
(6)蚀刻速率
将实验例1、3、5、6得到的陶瓷基体的蚀刻速率示于表2。具体而言,对各材料的表面进行镜面研磨,使用ICP等离子体耐腐蚀试验装置进行下述条件的耐腐蚀试验。然后,用由台阶仪测定的掩模面与暴露面的阶梯差除以试验时间,由此算出各材料的蚀刻速率。结果可知,实验例3、5、6与实验例1(耐腐蚀性与尖晶石同等或更高的专利文献1的实施品)相比,具有同等或更高的耐腐蚀性。
ICP:800W,偏置:300W,导入气体:NF3/Ar=75/100sccm 13Pa,暴露时间:5小时,试样温度:550℃
[表1]
[表2]
※Mg-Al-O-N:镁-铝氮氧化物(XRD:在2θ=47-49°存在峰)
[实验例8~19]
在实验例8~19中,按照达到表1所示的质量%的方式称量MgO原料、Al2O3原料及AlN原料,基于实验例1~7,制作调合粉末或颗粒,进行成型及烧成,得到陶瓷基体。所得到的陶瓷基体的C含有率如表1所示。另外,实验例8、12、16的C含有率是未积极地添加碳源时的值(作为杂质而含有的C含有率)。
[实验例20]
实验例20是AlN-YAG制的高热传导基体的一例。首先,按照分别达到74.5质量%、15质量%、10质量%、0.5质量%的方式称量AlN原料、Y2O3原料、Al2O3原料和TiO2原料,以异丙醇为溶剂,使用尼龙制的罐、直径5mm的氧化铝球石湿式混合4小时。混合后取出浆料,在氮气流中在110℃下进行干燥。之后通过30目的筛,制成调合粉末。使用该调合粉末,与实验例1同样地进行成型及烧成,从而得到圆板状的高热传导基体。对该高热传导基体的XRD光谱进行解析,结果,主相为AlN-YAG。另外,高热传导基体的颜色为黑色。所得到的高热传导基体在500℃下的体积电阻率为5×109Ωcm,在室温下的热传导率为81W/m·K,在40~1000℃下的热膨胀系数为6.1×10-6/K。即,热传导率是实验例2、3、5、6的约10倍,热膨胀系数与实验例2、3、5、6同等。实验例20可以用作上述晶片载放台10~40的轴28或晶片载放台20~40的高热传导基体23。

Claims (8)

1.一种高电阻高耐腐蚀陶瓷材料,是含有镁-铝氮氧化物的陶瓷材料,其中,
碳含有率为0.005~0.275质量%。
2.根据权利要求1所述的陶瓷材料,其中,
500℃下的体积电阻率为1×109Ωcm以上。
3.根据权利要求1或2所述的陶瓷材料,其中,
所述陶瓷材料含有钛。
4.根据权利要求1~3中任一项所述的陶瓷材料,其中,
以使用CuKα射线时的XRD峰至少出现在2θ=47~50°的镁-铝氮氧化物相作为主相。
5.一种晶片载放台,具备:
陶瓷基体,所述陶瓷基体由权利要求1~4中任一项所述的陶瓷材料形成、并能够在上表面载放晶片;和
电极,所述电极配置于所述陶瓷基体的内部。
6.一种晶片载放台,具备:
陶瓷基体,所述陶瓷基体由权利要求1~4中任一项所述的陶瓷材料形成、并能够在上表面载放晶片;
高热传导基体,所述高热传导基体设置在所述陶瓷基体的下表面、且热传导率比所述陶瓷基体的热传导率高;
电极,所述电极配置于所述陶瓷基体的内部、所述高热传导基体的内部、或所述陶瓷基体和所述高热传导基体之间;和
电阻发热体,所述电阻发热体配置于所述高热传导基体的基体内部且比所述电极更靠下方。
7.根据权利要求6所述的晶片载放台,其中,
所述高热传导基体包含AlN和YAG。
8.根据权利要求7所述的晶片载放台,其中,
所述高热传导基体包含钛。
CN202211703929.1A 2022-03-17 2022-12-29 高电阻高耐腐蚀陶瓷材料及晶片载放台 Pending CN116768631A (zh)

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TW486452B (en) * 1999-12-16 2002-05-11 Tokuyama Corp Joining body of crystalized glass and nitrogen oxide sintering body, and the preparation thereof
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