TWI783000B - 半導體製造裝置用加熱器 - Google Patents

半導體製造裝置用加熱器 Download PDF

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TWI783000B
TWI783000B TW107122751A TW107122751A TWI783000B TW I783000 B TWI783000 B TW I783000B TW 107122751 A TW107122751 A TW 107122751A TW 107122751 A TW107122751 A TW 107122751A TW I783000 B TWI783000 B TW I783000B
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heater
aln
aln ceramic
mass ratio
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山名啓太
曻和宏
鳥居謙悟
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日商日本碍子股份有限公司
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Abstract

本發明之半導體製造裝置用加熱器為於AlN陶瓷基體之內部埋設發熱體的半導體製造裝置用加熱器，其特徵為：AlN陶瓷基體含有O、C、Ti、Ca、Y作為雜質元素，Ti／Ca的質量比為0.13以上，無法藉由XRD側面圖來確認TiN相。

Description

半導體製造裝置用加熱器
本發明是關於一種半導體製造裝置用加熱器。
一般半導體製造裝置用加熱器，已知如專利文獻1所示，具備AlN陶瓷基體以及埋設於該AlN陶瓷基體之內部的發熱體。此種半導體製造裝置用加熱器用來對載置於AlN陶瓷基體之表面的晶圓加熱。又，一般半導體製造裝置用加熱器，已知如專利文獻2所示，於AlN陶瓷基體之內部埋設發熱體與靜電電極。
另一方面，在專利文獻3及4中，揭示一種AlN陶瓷基體，其分配原料比例燒結CaO、TiO2 等而成。例如，在文獻3中，揭示一例，其分配原料比例燒結2重量％的CaO與0.5重量％的TiO2 （Ti／Ca質量比為0.21），在文獻4中，揭示一例，其分配原料比例燒結1重量％的CaO與0.2重量％的TiO2 （Ti／Ca質量比為0.15）。 ［先前技術文獻］ ［專利文獻］
［專利文獻1］日本特開2008-153194號公報 ［專利文獻2］日本特開2005-281046號公報 ［專利文獻3］日本特開平8-157261號公報 ［專利文獻4］日本特開平8-157262號公報
［發明所欲解決之課題］
在專利文獻1及2的半導體製造裝置用加熱器中，若電流從發熱體到晶圓之間產生洩漏情況或從靜電電極到晶圓之間產生洩漏情況，晶圓會受到損壞。因此，AlN陶瓷基體的體積電阻率宜控制在較高的值（例如7×108 Ωcm以上）。不過，AlN陶瓷基體的體積電阻率有時會隨著雜質的影響而產生變動，於是變得難以控制體積電阻率。特別是，AlN陶瓷基體含有O、C、Ti、Ca、Y作為雜質元素，但這些元素會對體積電阻率造成怎樣的影響，目前為止仍不得而知。
又，專利文獻3及4的AlN陶瓷基體含有Ti、Ca等，但Ti的分配量過多，所以，燒結時產生體積電阻率極低（2～6×10-5 Ωcm）的TiN相，於是有整個AlN陶瓷基體的體積電阻率下降的問題。
本發明為解決此種問題的發明，主要目的為，在使用AlN陶瓷基體的半導體製造裝置用加熱器中，AlN陶瓷基體即使含有O、C、Ti、Ca、Y作為雜質元素，也可在高溫下具有高的體積電阻率。 ［用以解決課題之手段］
本發明之半導體製造裝置用加熱器為於AlN陶瓷基體之內部埋設發熱體的半導體製造裝置用加熱器，其特徵為：上述AlN陶瓷基體含有O、C、Ti、Ca、Y作為雜質元素，並含有釔鋁酸鹽相作為結晶相，Ti／Ca的質量比為0.13以上，無法藉由使用CuKα射線測定之後的XRD側面圖來確認TiN相。
在此半導體製造裝置用加熱器中，即使所使用的AlN陶瓷基體含有O、C、Ti、Ca、Y作為雜質元素，也能在高溫下具有高的體積電阻率。其理由可以下列方式來探討。當Ca固溶於釔鋁酸鹽相（例如Y4 Al2 O9 （YAM）、YAlO3 （YAL）等）時，二價的Ca置換三價的Y，所以，由於價數平衡的關係導致氧的缺損，氧離子傳導路徑增加，體積電阻率下降。另一方面，當Ti固溶於釔鋁酸鹽相時，四價的Ti置換三價的Al，所以，由於價數平衡的關係導致氧的缺損被填補，氧離子傳導路徑減少。若Ti／Ca的質量比為0.13以上，Ca可使氧離子傳導路徑的增加被Ti適切地抑制，所以，可知AlN陶瓷基體在高溫下的體積電阻率會變高。
又，當AlN陶瓷基體中的Ti過多時，會有TiN生成。TiN在室溫的體積電阻率為2～6×10-5 Ωcm、600℃時，約為原來的1.1倍（文獻1：日本陶瓷協會學術論文誌，99卷4號，pp286-291（1991）文獻2：電學論A，114卷12號，pp886-891（1994））亦即，TiN無論在室溫下或高溫下都是體積電阻率極低的化合物。因此，為了使AlN陶瓷基體在高溫下具有高的體積電阻率，宜不含有TiN相。又，若TiN生成，絕緣破壞容易發生，耐蝕性也會下降，所以，從這種觀點來看，AlN陶瓷基體也宜不含有TiN相。TiN相的XRD側面圖被揭露於JCPDS38-1420。若在AlN陶瓷基體的XRD側面圖中無法確認TiN相，TiN會導致的體積電阻率的下降會被抑制，所以，可提高AlN陶瓷基體在高溫下的體積電阻率，並且抑制TiN會導致的絕緣破壞、耐蝕性下降等。此外，XRD側面圖是使用CuKα射線來測定的（更詳細地說，使用CuKα射線在管電壓40kv、管電流40mA下測定的）。
此外，TiN相有可能作為Al固溶在TiN的相存在，但即使在此情況下，體積電阻率也是極低，可能導致絕緣破壞、耐蝕性下降等。
在AlN陶瓷基體中，Ti／Ca的質量比宜為0.13以上、0.5以下。AlN陶瓷基體的Ti含有率宜為18質量ppm以上、95質量ppm以下。AlN陶瓷基體宜含有YAM及YAL，在此情況下，YAM／YAL的質量比宜為2.8以上、5.3以下。在AlN陶瓷基體中，O／C的質量比宜為48以上、65以下。
本發明之半導體製造裝置用加熱器可使用含有O、C、Ti、Ca作為雜質元素的AlN原料粉末與作為燒結助劑的Y2 O3 粉末這兩種粉末的混合粉末，藉由於內部埋設發熱體而成形來製作成形體，再藉由燒成此成形體而製作完成。在AlN原料粉末中，O／C的質量比宜為20～30，Ti／Ca的質量比宜為0.13以上。如此，將Y2 O3 粉末作為燒結助劑使用來燒成AlN原料粉末之後的AlN陶瓷基體容易形成上述的AlN陶瓷基體。此種AlN原料粉末可根據需要對含有O、C、Ti、Ca之Al2 O3 粉末適量添加C、TiO2 、CaO再氮化、氧化此混合粉末而得。在AlN原料粉末中，宜含有0.70～0.75質量％的O、220～380質量ppm的C、18～95質量ppm的Ti、150～250質量ppm的Ca。
在本發明之半導體製造裝置用加熱器中，AlN陶瓷基體在540℃的體積電阻率宜為1.0×109 Ωcm以上。如此，可充分減少從發熱體到載置於AlN陶瓷基體上之晶圓之間的漏電流。
本發明之半導體製造裝置用加熱器中，AlN陶瓷基體的彎曲強度宜為300MPa以上，310Mpa以上則更好。如此，可充分具有作為使用於半導體製造裝置之構造元件所被要求的強度。
在本發明之半導體製造裝置用加熱器中，AlN陶瓷基體的熱傳導率宜為170W／m•K以上。如此，載置於AlN陶瓷基體的晶圓的均熱性會變高。
以下將一邊參照圖面，一邊說明本發明的最佳實施型態。圖1為概略表示靜電吸盤加熱器10之構造的垂直剖面圖。
靜電吸盤加熱器10為本發明之半導體製造裝置用加熱器之一例，具備陶瓷基體12、發熱體14及靜電電極16。
陶瓷基體12為AlN製的圓盤元件，直徑可為例如200～450mm。陶瓷基體12的上面成為用來載置晶圓W的晶圓載置面12a。陶瓷基體12是以AlN為主成分的基體，但含有O、C、Ti、Ca、Y作為雜質元素，並含有釔鋁酸鹽相作為結晶相，Ti／Ca的質量比為0.13以上，無法在XRD側面圖中確認TiN相。關於是否可在XRD側面圖中確認TiN相，可藉由對照陶瓷基體12的XRD側面圖與TiN相的全峰值來決定。在陶瓷基體12中，Ti／Ca的質量比宜為0.13以上、0.5以下。陶瓷基體12的Ti含有率宜為18質量ppm以上、95質量ppm以下。陶瓷基體12宜含有YAM及YAL作為釔鋁酸鹽相，在此情況下，YAM／YAL的質量比宜為2.8以上、5.3以下。在陶瓷基體12中，O／C的質量比宜為48以上、65以下。
發熱體14埋設於陶瓷基體12的內部。發熱體14以一氣呵成的要領橫跨整個晶圓載置面12a來配置金屬線圈，使其成為所制定的圖樣。發熱體14不受金屬線圈限定，例如可採用緞帶狀、網眼狀、片狀等各種型態。作為發熱體的材料，宜採用Mo、W、Nb等高熔點導電材料。
靜電電極16埋設於陶瓷基體12的內部。靜電電極16配置於晶圓載置面12a與發熱體14之間。靜電電極16的形狀不受特別限定，例如除了可採用平面狀、網眼狀之外，也可採用沖壓金屬。作為靜電電極16的材料，宜採用Mo、W、Nb等高熔點導電材料。
接著，將說明靜電吸盤加熱器10的使用例。首先，靜電吸盤加熱器10設置於未圖示出的腔室內。然後，在靜電吸盤加熱器10的晶圓載置面12a上載置晶圓W，對靜電電極16施加電壓以在靜電電極16與晶圓W之間產生約翰森•拉別克效應（Johnson Rahbek effect）之類的靜電吸著力，藉此，將晶圓W吸著固定於晶圓載置面12a上。又，作為發熱體14的金屬線圈上連接有外部端子並施加電壓使發熱體14發熱，藉此，將晶圓W加熱至既定溫度。在此狀態下，進行各種在晶圓W上製作半導體晶片所需要的各種處理。處理完畢後，結束對靜電電極16的電壓施加或對發熱體14的電壓施加，將晶圓W從載置面12a上取下。
接著，說明靜電吸盤加熱器10的製造例。首先，準備含有O、C、Ti、Ca作為雜質元素的AlN原料粉末。在AlN原料粉末中，O／C的質量比宜為20～30，Ti／Ca的質量比宜為0.13以上。此種AlN原料粉末可根據需要對含有O、C、Ti、Ca之Al2 O3 粉末適量添加C、TiO2 、CaO再氮化、氧化此混合粉末而得。在AlN原料粉末中，宜含有0.70～0.75質量％的O、220～380質量ppm的C、18～95質量ppm的Ti、150～250質量ppm的Ca。
接著，對準備好的AlN原料粉末添加Y2 O3 粉末作為燒結助劑並混合在一起變成混合粉末，再將其噴霧乾燥成顆粒。Y2 O3 對整個混合粉末添加的量為4.5～5.5質量％。作為混合方法，可採用使用有機溶劑的濕式混合，亦可採用例示於球磨、震動磨、乾式袋混合等技術的乾式混合。
接著，將發熱體14及靜電電極16埋設於內部並使用混合粉末的顆粒成形，藉此，製作成形體。然後，藉由燒成此成形體來得到AlN燒結體。藉此，得到靜電吸盤加熱器10。燒成方法不受特別限定，例如亦可採用熱壓燒成等技術。在進行熱壓燒成技術的情況下，燒成時的最高溫度（燒成溫度）宜為1700～1900℃，在燒成溫度下的維持時間宜為0.5～100小時，熱壓壓力宜為5～50MP，環境氣體宜為氮氣或真空（例如0.13～133.3Pa）。
根據以上所說明的本實施型態之靜電吸盤加熱器10，O／C的質量比、Ti／Ca的質量比及YAM／YAL的質量比皆在適當的數值範圍內，所以，陶瓷基體12的體積電阻率變高，於是可減少從發熱體14或靜電電極16到載置於陶瓷基體12之晶圓載置面12a的晶圓之間的漏電流。
此外，本發明不受上述實施型態的任何限定，只要屬於本發明的技術範圍內，可以各種型態實施本發明。
例如，在上述的實施型態中，作為本發明之半導體製造裝置用加熱器，例示了靜電吸盤加熱器10，但亦可省略靜電電極16，將靜電電極16置換為RF電極。 ［實施例］
［實施例1～11］已針對各實施例，準備好表1所示的AlN原料粉末。AlN原料粉末所含有的雜質元素的質量以下面的方式來測定。雜質元素的質量分析是根據JIS R1675來實施。具體而言，氧在鎳囊中取樣約0.05g，投入石墨坩堝並對其加熱、燃燒，再作為CO來抽出，使用非分散紅外線檢測器定量。碳取樣約0.5g，添加助燃劑（Sn等）之後對其加熱、燃燒，使用非分散紅外線檢測器定量所產生的CO＋CO2 。金屬雜質取樣約1g，加熱既定量的硝酸、鹽酸、過氧化氫水，使用ICP發光分析法測定加熱溶解後的溶液。
對準備好的AlN原料粉末添加Y2 O3 粉末作為燒結助劑並藉由球磨技術混合，變成混合粉末，再將其噴霧乾燥成顆粒。Y2 O3 對整個混合粉末的添加量為5質量％。接著，使用混合粉末的顆粒製作圓盤形狀的成形體。然後，藉由熱壓燒成技術將此成形體製作成AlN燒結體。在熱壓燒成技術中，燒成時的最高溫度（燒成溫度）為1850～1890℃，在燒成溫度下的維持時間為2小時，熱壓壓力為20MPa，環境氣體為氮氣。測定好所得到的AlN燒結體所含有的雜質元素的質量、YAM的質量及YAL的質量。
AlN燒結體中的雜質元素的質量採用與AlN原料粉末中的雜質元素的質量相同的方法來測定。YAM及YAL的質量以下面的方式來測定。首先，使用粉末X射線繞射技術精密測定至10deg～120deg以上的高角度，取得XRD側面圖，使用所取得的XRD側面圖進行結晶相的鑑定，推測所鑑定出的結晶相並進行特沃爾德解析（Rietveld解析），算出各結晶相的定量值。AlN燒結體在540℃的體積電阻率以下面的方式來測定。將使用銀漿印刷電極部的樣本（50mm×50mm×1mm）加熱至540℃之後，測定施加1kV的電壓時1分鐘後的電流值，藉此，求到體積電阻率。彎曲強度藉由以JIS R1601為根據的四點彎曲測試來測定。熱傳導率根據JIS R1611，使用雷射閃光測定法在室溫下進行測定。這些結果表示於表2。又，O／C質量比與體積電阻率的關係表示於圖2，Ti／Ca質量比與體積電阻率的關係表示於圖3，YAM／YAL質量比與體積電阻率的關係表示於圖4。
X射線繞射藉由Bruker AXS製的D8 ADVANCE測定0.5g的粉末。測定條件為CuKα射線光源、管電壓40kV、管電流40mA。採用特沃爾德解析來解析測定結果，進行結晶相的鑑定與定量。這些結果表示於圖5、圖6及表2。圖5及圖6為表示實驗例1、7之XRD側面圖的圖表。從實驗例1、7之XRD側面圖鑑定出的結晶相為AlN、YAM、YAL，無法確認TiN。關於實驗例2～6、8、9，雖然省略XRD側面圖的圖示，亦得到相同的結果。
［表1］
Figure 107122751-A0304-0001
［表2］
Figure 107122751-A0304-0002
 ※１　燒成條件為燒成時最高溫度（燒成溫度）1850℃(但在實驗例9中為1890℃）、維持時間為2hr、熱壓壓力為20MPa。
實驗例1～9的AlN燒結體含有O、C、Ti、Ca、Y作為雜質元素，並含有YAM及YAL作為結晶相，Ti／Ca的質量比為0.13以上，無法在XRD側面圖中確認TiN相。這些AlN燒結體在540℃的體積電阻率皆達1.0×109 （＝1.0E＋09）［Ωcm］以上之高。因此，在作為圖1所示之靜電吸盤加熱器10的陶瓷基體12來使用的情況下，可減少從發熱體14或靜電電極16到載置於晶圓載置面12a之晶圓W之間的漏電流。此外，在實驗例1～9的AlN燒結體中，Ti／Ca的質量比皆為0.13以上、0.5以下，Ti含有率皆為18質量ppm以上、95質量ppm以下，YAM／YAL的質量比皆為2.8以上、5.3以下，O／C的質量比皆為48以上、65以下。
相對於此，實驗例10、11的AlN燒結體於540℃的體積電阻率為4.5×108 ［Ωcm］以下的低值。在實驗例10、11中，特別是Ti／Ca的質量比在適當範圍外可能是體積電阻率下降的原因。換言之，在實驗例10、11中，Ti／Ca的質量比為0.08、0.07之低，所以可知，Ca固溶於YAM、YAL而導致氧離子傳導路徑增加的情況勝過Ti固溶於YAM、YAL而導致氧離子傳導路徑減少的情況，於是體積電阻率下降。在實驗例10中，可知Ti含有率在適當範圍外這一點、YAM／YAL的質量比在適當範圍內這一點以及O／C的質量比在適當範圍外這一點等，也是體積電阻率下降的原因。在實驗例11中，可知Ti含有率在適當範圍外這一點以及O／C的質量比在適當範圍外這一點等，也是體積電阻率下降的原因。
又，實驗例10、11的AlN燒結體的彎曲強度達353Mpa、328MPa之高，但實驗例1～9的AlN燒結體的彎曲強度也在300MPa以上（更詳細地說，是310MPa以上），與實驗例10、11差不多高。再者，實驗例10、11的AlN燒結體的熱傳導率有190W／m•K、180W／m•K之高，但實驗例1～9的AlN燒結體的熱傳導率也有170～180W／m•K，與實驗例10、11差不多高。
在上述實驗例1～11之中，實驗例1～9與本發明的實施例相當，實驗例10、11與比較例相當。
本申請是以2018年2月8日所申請的日本專利申請第2018-20637號作為優先權主張的基礎，藉由引用，所有其內容皆包含在本說明書內。 ［產業上可利性］
本發明可應用於靜電吸盤加熱器、陶瓷加熱器等半導體製造裝置用加熱器。
10‧‧‧靜電吸盤加熱器12‧‧‧陶瓷基體12a‧‧‧晶圓載置面14‧‧‧發熱體16‧‧‧靜電電極W‧‧‧晶圓
［圖1］為概略表示靜電吸盤加熱器10之構造的垂直剖面圖。 ［圖2］為表示O／C質量比與體積電阻率之關係的圖表。 ［圖3］為表示Ti／Ca質量比與體積電阻率之關係的圖表。 ［圖4］為表示YAM／YAL質量比與體積電阻率之關係的圖表。 ［圖5］為表示實驗例1之AlN燒結體之XRD側面圖的圖表。 ［圖6］為表示實驗例7之AlN燒結體之XRD側面圖的圖表。
10‧‧‧靜電吸盤加熱器
12‧‧‧陶瓷基體
12a‧‧‧晶圓載置面
14‧‧‧發熱體
16‧‧‧靜電電極
W‧‧‧晶圓

Claims (7)

  1. 一種半導體製造裝置用加熱器，其為於AlN陶瓷基體之內部埋設發熱體的半導體製造裝置用加熱器，其特徵為：上述AlN陶瓷基體含有O、C、Ti、Ca、Y作為雜質元素，並含有釔鋁酸鹽相作為結晶相，Ti/Ca的質量比為0.13以上，無法藉由使用CuKα射線測定之後的XRD側面圖來確認TiN相，其中，上述AlN陶瓷基體的Ti含有率為18質量ppm以上、95質量ppm以下。
  2. 如申請專利範圍第1項之半導體製造裝置用加熱器，其中，上述Ti/Ca的質量比為0.5以下。
  3. 如申請專利範圍第1或2項之半導體製造裝置用加熱器，其中，上述AlN陶瓷基體含有Y4Al2O9(YAM)及YAlO3(YAL)，YAM/YAL的質量比為2.8以上、5.3以下。
  4. 如申請專利範圍第1或2項之半導體製造裝置用加熱器，其中，上述AlN陶瓷基體中的O/C的質量比為48以上、65以下。
  5. 如申請專利範圍第1或2項之半導體製造裝置用加熱器，其中，上述AlN陶瓷基體在540℃的體積電阻率為1.0×109Ωcm以上。
  6. 如申請專利範圍第1或2項之半導體製造裝置用加熱器，其中，上述AlN陶瓷基體的彎曲強度為300MPa以上。
  7. 如申請專利範圍第1或2項之半導體製造裝置用加熱器，其中，上述AlN陶瓷基體的熱傳導率為170W/m‧K以上。
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