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TWI753835B - 靜電吸盤用介電質 - Google Patents

靜電吸盤用介電質 Download PDF

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TWI753835B
TWI753835B TW110119161A TW110119161A TWI753835B TW I753835 B TWI753835 B TW I753835B TW 110119161 A TW110119161 A TW 110119161A TW 110119161 A TW110119161 A TW 110119161A TW I753835 B TWI753835 B TW I753835B
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Abstract

本發明的課題在於提供可確保約翰森-拉赫貝克(Johnsen-Rahbeck)型靜電吸盤用介電質所要求的體積固有電阻率等基本特性，同時可確保充分硬度的靜電吸盤用介電質。 [解決手段]一種靜電吸盤用介電質，主結晶相由剛玉構成，其他結晶相包含Al 5BO 9，根據粉末X線繞射之Al 5BO 9的(021面)峰強度I A與剛玉的(012面)峰強度I B之比I A/I B為0.04以上0.4以下。

Description

靜電吸盤用介電質
本發明係關於使用在高精度地定位而固定矽晶圓等半導體晶圓或LCD基板玻璃等各種基板的靜電吸盤的介電質。
例如，於半導體製造裝置，為了以形成電路為目的在矽晶圓上曝光/成膜，蝕刻矽晶圓，有必要保持作為對象的晶圓的平坦度，而且以晶圓沒有溫度分布的方式保持晶圓。作為這樣的晶圓的保持手段，被提出了機械方式、真空吸附方式、靜電吸附方式。這些保持手段之中，靜電吸附方式是藉由靜電吸盤保持晶圓的方式，因為可在真空氛圍下使用所以被大量使用。
靜電吸盤，依吸附力可分為利用庫侖力之型(庫侖型)，與利用約翰森-拉赫貝克(Johnsen-Rahbeck)力之型(約翰森-拉赫貝克型)。後者之約翰森-拉赫貝克力是在介電質與晶圓之界面的小間隙流通微小電流，藉由帶電分極使感應而產生的力，在介電質的體積固有電阻率為10 12～10 13Ω•cm以下時會發生。接著，使用約翰森-拉赫貝克力作為靜電吸盤為了確保必要的吸附力，介電質的體積固有電阻率在10 9～10 13Ω•cm的範圍內為其要件。
從前，作為約翰森-拉赫貝克型的靜電吸盤用介電質，已知有在氧化鋁添加過渡金屬元素之陶瓷，例如Al 2O 3-TiO 2系等(例如參照專利文獻1)。 [先前技術文獻] [專利文獻]
[專利文獻1]日本專利第4354138號公報
[發明所欲解決之課題]
本案發明人等把專利文獻1之Al 2O 3-TiO 2系的介電質使用於蝕刻裝置的靜電吸盤時，發現耐用性並不充分。亦即，可知在蝕刻裝置，靜電吸盤在電漿氛圍下使用時，專利文獻1之Al 2O 3-TiO 2系的介電質硬度不充分所以耐電漿性降低，結果無法得到充分的耐用性。
於是，本發明所要解決的課題在於提供可確保約翰森-拉赫貝克(Johnsen-Rahbeck)型靜電吸盤用介電質所要求的體積固有電阻率等基本特性，同時可確保充分硬度的靜電吸盤用介電質。 [供解決課題之手段]
為了解決前述課題，本案發明人等反覆試驗及研究的結果，得知於主結晶相為剛玉所構成的靜電吸盤用介電質，藉著其他的結晶相適量地含有Al 5BO 9，可以確保約翰森-拉赫貝克(Johnsen-Rahbeck)型靜電吸盤用介電質所要求的體積固有電阻率等基本特性，同時可確保充分硬度。
亦即，根據本發明，提供以下1～3之靜電吸盤用介電質。 1. 一種靜電吸盤用介電質，主結晶相由剛玉構成，其他結晶相包含Al 5BO 9，根據粉末X線繞射之Al 5BO 9的(021面)峰強度：I A與剛玉的(012面)峰強度：I B之比：I A/I B為0.04以上0.4以下。 2. 如前述1之靜電吸盤用介電質，維氏硬度為16GPa以上。 3. 如前述1或2之靜電吸盤用介電質，把含有氧化鈦0.8質量%以上3質量%以下，碳化硼0.2質量%以上1質量%以下，餘部主要為氧化鋁原料構成的配合物予以混合、成形、燒成(firing)而得。 [發明之效果]
根據本發明，可確保約翰森-拉赫貝克(Johnsen-Rahbeck)型靜電吸盤用介電質所要求的體積固有電阻率等基本特性，同時可確保充分的硬度。
本發明之靜電吸盤用介電質，主結晶相由剛玉構成，其他結晶相包含Al 5BO 9。而且根據粉末X線繞射之Al 5BO 9的(021面)峰強度為I A、根據粉末X線繞射之剛玉的(012面)峰強度為I B，其峰強度比(I A/I B)為0.04以上0.4以下。 I A/I B未滿0.04的話，無法確保充分的硬度。 另一方面，I A/I B超過0.4的話，在粒界生成大量Al 5BO 9因而使體積固有電阻率增加，吸附力降低。亦即，約翰森-拉赫貝克型靜電吸盤用介電質，藉著在粒界形成低電阻的粒界相以確保適度的導電性，並使體積固有電阻率降低，但在粒界生成大量Al 5BO 9的話，Al 5BO 9會阻礙低電阻的粒界相的導電性，結果使體積固有電阻率增加。
本發明之靜電吸盤用介電質的硬度，可在維氏硬度16GPa以上。亦即，「維氏硬度16GPa以上」是確保充分硬度的基準之一。由確保更加充分的硬度之點而言，本發明之靜電吸盤用介電質的硬度，亦可在維氏硬度18GPa以上。為了確保維氏硬度在18GPa以上，I A/I B最好是0.18以上0.4以下。
這樣的本發明之靜電吸盤用介電質，可以藉著把含有氧化鈦0.8質量%以上3質量%以下，碳化硼0.2質量%以上1質量%以下，餘部主要為氧化鋁原料構成的配合物予以混合、成形、燒成來製造。 配合物中含氧化鈦率未滿0.8質量%的話，有Ti 3+的生成量變少而增加體積固有電阻率，吸附力降低之疑慮。亦即，氧化鈦(TiO 2)係固溶在氧化鋁(Al 2O 3)原料粒子的粒界相使體積固有電阻率降低。具體而言，在燒成中TiO 2的Ti 4+的一部分被還原為Ti 3+，並藉著把該Ti 3+置換固溶在Al 2O 3的Al 3+的位置而形成低電阻的粒界相((Al、Ti) 2O 3)。因此，配合物中含氧化鈦率未滿0.8質量%的話，有Ti 3+的生成量變少而增加體積固有電阻率，吸附力降低之疑慮。 另一方面，配合物中含氧化鈦率超過3質量%的話，則有體積固有電阻率變得過低且洩漏電流增加，對晶圓的電路等產生不利影響之疑慮。
配合物中含碳化硼(B 4C)率未滿0.2質量%的話，可能無法確保充分的硬度。特別是靜電吸盤在電漿氛圍下被使用之情況，無法確保充分的硬度的話，則有劣化變快耐用性降低之疑慮。此外，配合物中含碳化硼率未滿0.2質量%的話，可能靜電吸盤黑色化不充分，且髒污變得明顯。 另一方面，配合物中含碳化硼率超過1質量%的話，可能在粒界生成大量Al 5BO 9因而使體積固有電阻率增加，吸附力降低。 由確保更加充分的硬度之點而言，配合物中含碳化硼率最好是0.4質量%以上1質量%以下。
本發明之靜電吸盤用介電質，係如前述，在將氧化鈦、碳化硼及氧化鋁原料予以特定量混合後，藉著壓製成形、CIP (冷均壓：Cold Isostatic Pressing)成形、刮刀成形等成形為特定形狀，因應需要進行脫脂之後，加以燒成而得到。 燒成可以藉通常的常壓燒結來進行，但密度容易變得相對較低，因而最好是進行熱壓、HIP、氣壓燒成等的加壓燒結。燒成氛圍可以是氬等的惰性氣體氛圍或氫等的還原氣體氛圍(亦即非氧化性氛圍)，或者是真空中。燒結溫度可以為1200℃以上1700℃以下。 又，本發明之配合物中氧化鈦及碳化硼以外的餘部主要為氧化鋁原料構成，但這餘部除了氧化鋁原料之外，得以包含作為助燒結劑之氧化鎂(MgO)、二氧化矽(SiO 2)、氧化鑭(La 2O 3)、氧化釔(Y 2O 3)、氧化鈣(CaO)、氧化鈰(Ce 2O 3)等。但是，這些的含有率以合計3質量%以下(包含0)為較佳。 [實施例]
將氧化鈦、碳化硼及氧化鋁原料配合成為表1所示之各例的含有率而得到配合物，並將各例的配合物分別進行混合、成形、燒成，得到各例的靜電吸盤用介電質。 針對得到之各例的靜電吸盤用介電質，利用Cu-Kα線之粉末X線繞射評估Al 5BO 9的(021面)峰強度：I A與剛玉的(012面)峰強度：I B之比：I A/I B，同時評估維氏硬度、體積固有電阻率及吸附力，並進行色調判定。
Figure 02_image001
圖1係顯示作為粉末X線繞射之一例之，本發明例之實施例1的粉末X線繞射強度數據。根據那樣的粉末X線繞射強度數據，進行評估Al 5BO 9的(021面)峰強度：I A與剛玉(Al 2O 3)的(012面)峰強度：I B之比：I A/I B。又，各例的峰強度比(I A/I B)，主要藉著調整配合物中的含碳化硼率來調整。
維氏硬度係根據日本工業標準JIS Z2244來測定(加壓力1kgf)。評估係以維氏硬度18GPa以上為◎(優)，16GPa以上且未滿18GPa為○(良)，未滿16GPa為×(不良)。
體積固有電阻率係以三端子法測定(施加電壓500V、室溫)。評估係以體積固有電阻率9.7×10 9Ω•cm以上且3.8×10 10Ω•cm以下為◎(優)，超過3.8×10 10Ω•cm且1.3×10 11Ω•cm以下或3.8×10 9Ω•cm以上且未滿9.7×10 9Ω•cm為○(良)，超過1.3×10 11Ω•cm或未滿3.8×10 9Ω•cm為×(不良)。 又，表1中，○(良)之中將超過3.8×10 10Ω•cm且1.3×10 11Ω•cm以下標記為○(H)，將3.8×10 9Ω•cm以上且未滿9.7×10 9Ω•cm標記為○(L)，此外，×(不良)之中將超過1.3×10 11Ω•cm標記為×(H)，將未滿3.8×10 9Ω•cm標記為×(L)。
吸附力係將各例的介電質組入圖2所示那樣的約翰森-拉赫貝克型靜電吸盤而測定。亦即，如圖2所示，在介電質1的單方的表面濺鍍Ti，賦予作為導體層3之電極。在這上面以把導體層3夾在中間的方式用環氧系接著劑4接著絕緣體基板2(氧化鋁)。此時，預先於絕緣體基板2的中心開孔作為導線電極用，最後將介電質1研削到2mm的厚度，包裹加工，並附上導線電極5而製作出靜電吸盤。然後，在此靜電吸盤真空中利用電源7施加300V的直流電壓60秒鐘，並測定真空中吸附矽晶圓6時之吸附力。評估以吸附力40g/cm 2以上為◎(優)，以20g/cm 2以上且未滿40g/cm 2為○(良)，以未滿20g/cm 2為×(不良)。
色調判定係以目視來進行。
表1中，實施例1～7係本發明範圍內之介電質，各評估為◎(優)或○(良)是良好的，色調判定為黑或藍色也是良好的。其中，峰強度比(I A/I B)為0.18以上0.4以下之實施例1,3,4,6,7，其維氏硬度18GPa以上(◎(優))特別良好，色調判定為黑也特別良好。
相對地，比較例1係峰強度比(I A/I B)太小之例，其維氏硬度未滿16GPa(×(不良))，無法得到充分的硬度。此外，色調判定為綠色是不良的。 另一方面，比較例2係峰強度比(I A/I B)過大之例，體積固有電阻率升高到超過1.3×10 11Ω•cm，吸附力降低。
1:介電質 2:絕緣體基板 3:導體層(電極) 4:環氧系接著劑 5:導線電極 6:矽晶圓 7:電源
[圖1]係本發明例之實施例1的粉末X線繞射強度數據。 [圖2]係約翰森-拉赫貝克(Johnsen-Rahbeck)型靜電吸盤之一例的概念剖面圖。

Claims (3)

  1. 一種靜電吸盤用介電質，主結晶相由剛玉構成，其他結晶相包含Al 5BO 9，根據粉末X線繞射之Al 5BO 9的(021面)峰強度I A與剛玉的(012面)峰強度I B之比I A/I B為0.04以上0.4以下。
  2. 如請求項1之靜電吸盤用介電質，維氏硬度為16GPa以上。
  3. 如請求項1或2之靜電吸盤用介電質，把含有氧化鈦0.8質量%以上3質量%以下，碳化硼0.2質量%以上1質量%以下，餘部主要為氧化鋁原料構成的配合物予以混合、成形、燒成(firing)而得。
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