JP2014165496A - アルミニウム前駆体と、それを用いた薄膜及びキャパシタの形成方法 - Google Patents
アルミニウム前駆体と、それを用いた薄膜及びキャパシタの形成方法 Download PDFInfo
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- JP2014165496A JP2014165496A JP2014031269A JP2014031269A JP2014165496A JP 2014165496 A JP2014165496 A JP 2014165496A JP 2014031269 A JP2014031269 A JP 2014031269A JP 2014031269 A JP2014031269 A JP 2014031269A JP 2014165496 A JP2014165496 A JP 2014165496A
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- Prior art keywords
- forming
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- film
- thin film
- lower electrode
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
Description
これによって、前記アルミニウム前駆体を用いて高い縦横比を有する開口内に薄膜を容易に形成することができ、これは、例えばキャパシタの誘電膜形成に好適に用いることができる。
本明細書に開示されている本発明の実施例に対して、特定の構造的ないし機能的説明は、単に本発明の実施例を説明するための目的で例示されたものであり、本発明の実施例は多様な形態で実施することができ、本明細書に説明された実施例に限定されるものではない。
例示的な実施例に係るアルミニウム前駆体は下記の式(1)と表示されて、低融点及び十分な揮発性を有しながらも熱安定性が高い特性を有するので、高温の蒸着温度を伴う化学気相蒸着工程或いは原子層蒸着工程を通じた薄膜形成時に蒸着ソースとして用いることができる。
アルゴンガスの雰囲気下において、脱水処理したトルエン115mlにトリメチルアルミニウム7.5gを溶解させた溶液を氷槽(ice bath)で撹はんして10℃付近まで冷却させた。次いで、前記冷却された溶液に脱水処理した(dehydrated)ジピバロイルメタン(dipivaloyl methane、DMP)19.2g及びトルエン30mlの混合溶液を3時間、ゆっくり添加し、反応中に発生したメタンガスはアルゴンガスを使って除去した。その後、前記混合物を室温で約15時間撹はんした後、100℃減圧下でトルエンを除去することによって液体残渣を得た。前記液体残渣を230Pa及び107℃の条件で減圧蒸留して塔頂温度78℃で流出することによって、無色透明の液体である、下記の式(4)と表されるアルミニウム前駆体を製造した。
アルゴンガスの雰囲気下で、脱水処理したトルエン1200gにトリメチルアルミニウム144gを溶解させた溶液を氷槽(ice bath)で撹はんして10℃付近まで冷却させた。次いで、前記冷却された溶液に脱水処理した第3ペンチルアルコール243gを3時間ゆっくり添加し、反応中に発生したメタンガスはアルゴンガスを使って除去した。その後、前記混合物を室温で約15時間撹はんした後、120℃減圧下でトルエンを除去することによって粘性の液体残渣を得た。前記液体残渣を50Pa及び107℃の条件で減圧蒸留して塔底温度78℃で流出することによって、白色の固体である、下記の式(5)と表されるアルミニウム前駆体を製造した。
発火性有無に係る安定性を評価するために、本発明の実施例1及び実施例2に係るアルミニウム前駆体と比較例1としてトリメチルアルミニウム、比較例2として下記の式(6)と表されるアルミニウム前駆体、及び比較例3として下記の式(7)と表されるアルミニウム前駆体を大気中に放置した結果を表1に表した。
化学気相蒸着工程或いは原子層蒸着工程の原料としての適合性を評価するために、前記実施例1乃至実施例2及び比較例2乃至比較例3について、微量融点測定装置で融点を測定した結果並びにTG−DTA(ThermoGravity_metric−Differential_Thermal_Analyser,示差熱・熱重量同時解析)測定装置でアルゴンの雰囲気下で加熱することによって試料重量が50重量%減少した時点の温度を測定した結果を表2に表した。
図1乃至図3は例示的な実施例に係る薄膜形成方法を説明するための断面図である。前記薄膜は例示的な実施例に係るアルミニウム前駆体を使う化学気相蒸着工程或いは原子層蒸着工程を通じて形成される。
2−メトキシエタノール(2−methoxyethanol)、2−エトキシエタノール(2−ethoxyethanol)、2−ブトキシエタノール(2−butoxyethanol)、2−(2−メトキシエトキシ)エタノール(2−(2−methoxyethoxy)ethanol)、2−メトキシ−1−メチルエタノール(2−methoxy−1−methylethanol)、2−メトキシ−1,1− ジメチルエタノール(2−methoxy−1,1−dimethylethanol)、2−エトキシ−1,1− ジメチルエタノール(2−ethoxy−1,1−dimethylethanol)、2−イソプロポキシ−1,1− ジメチルエタノール(2−isopropoxy−1,1−dimethylethanol)、2−ブトキシ−1,1− ジメチルエタノール(2−butoxy−1,1−dimethylethanol)、2−(2−メトキシエトキシ)−1,1− ジメチルエタノール(2−2(methoxyethoxy)−1,1−dimethylethanol)、2−プロポキシ−1,1−ジエチルエタノール(2−propoxy−1,1−diethylethanol)、2−2−ブトキシ−1,1−ジエチルエタノール(2−2−butoxy−1,1−diethylethanol)、3−メトキシ−1,1−ジメチルプロパノール(3−methoxy−1,1−dimethylpropanol)を含むエーテルアルコールと、を含む。
1,1,1−トリフルオロペンタン−2,4−ジオン(1,1,1−trifluoropentane−2,4−dione)、1,1,1−トリフルオロ−5,5−ジメチルヘキサン−2,4−ジオン(1,1,1−trifluoro−5,5−dimethylhexane−2,4−dione)、1,1,1,5,5,5−ヘキサフルオロペンタン−2,4−ジオン(1,1,1,5,5,5−hexafluoropentane−2,4−dione)、及び1,3−ジパーフルオロヘキシルプロパン−1,3−ジオン(1,3−diperfluorohexyl propane−1,3−dione)を含むふっ素置換アルキルβ−ジケトンと、
1,1,5,5−テトラメチル−1−メトキシヘクサン−2,4−ジオン(1,1,5,5−tetramethyl−1−methoxyhexane−2,4−dione)、2,2,6,6−テトラメチル−1−メトキシヘプタン−3,5−ジオン(2,2,6,6−tetramethyl−1−methoxyheptane−3,5−dione)、及び、2,2,6,6−テトラメチル−1−(2−メトキシエトキシ)ヘプタン−3,5−ジオン(2,2,6,6−tetramethyl−1−(2−methoxyethoxy)heptane−3,5−dione)を含むエーテル置換β−ジケトンと、を含む。
前記有機アミン化合物は、例えば、メチルアミン(methylamine)、エチルアミン(ethylamine)、プロピルアミン(propylamine)、イソプロピルアミン(isopropylamine)、ブチルアミン(butylamine)、第2ブチルアミン、第3ブチルアミン、イソブチルアミン(isobutylamine)、ジメチルアミン(dimethylamine)、ジエチルアミン(diethylamine)、ジプロピルアミン(dipropylamine)、ジイソプロピルアミン(diisopropylamine)、エチルメチルアミン(ethylmethylamine)、プロピルメチルアミン(propylmethylamine)、及びイソプロピルメチルアミン(isopropylmethylamine)を含む。
テトラヒドロフラン(tetrahydrofuran)、テトラヒドロピラン(tetrahydropyran)、エチレングリコールジメチルエーテル(ethylene glycol dimethyl ether)、ジエチルレングリコールジメチルエーテル(diethylene glycol dimethyl ether)、トリエチレングリコールジメチルエーテル(triethylene glycol dimethyl ether)、ジブチルエーテル(dibuthyl ether)、及び、ジオキサン(dioxane)を含むエーテル(ether)と、
メチルブチルケトン(methyl butyl ketone)、メチルイソブチルケトン(methyl isobutyl ketone)、エチルブチルケトン(ethyl butyl ketone)、ジプロピルケトン(dipropyl ketone)、ジイソブチルケトン(diisobutyl ketone)、メチルアミルケトン(methyl amyl ketone)、シクロヘキサノン(cyclohexanone)、及びメチルシクロヘキサノン(methylcyclohexanone)を含むケトン(ketone)と、
ヘキサン(hexane)、シクロヘキサン(cyclohexane),メチルシクロヘクサン(methylcyclohexane)、ジメチルシクロヘクサン(dimethylcyclohexane)、エチルシクロヘキサン(ethylcyclohexane)、ヘプタン(heptane)、オクタン(octane)、トルエン(toluene)、及びキシレン(xylene)を含む炭化水素と、
1−シアノプロパン(1−cyanopropane)、1−シアノブタン(1−cyanobutane)、1−シアノヘキサン(1−cyanohexane)、シアノシクロヘキサン(cyanocyclohexane)、シアノベンゼン(cyanobenzene)、1,3−ジシアノプロパン(1,3−dicyanopropane)、1,4−ジシアノブータン(1,4−dicyanobutane)、1,6−ジシアノヘキサン(1,6−dicyanohexane)、1,4−ジシアノシクロヘキサン(1,4−dicyanocyclohexane)、及び1,4−ジシアノベンゼン(1,4−dicyanobenzene)を含む、シアノ(cyano)基を有する炭化水素と、
ピリジン(pyridine)と、ルチジン(lutidine)と、及び/又は、これらの混合物と、を含む。
図4乃至図11は、本発明の例示的な実施例に係るキャパシタ形成方法を説明するための断面図である。
特に、本発明の例示的な実施例に係るアルミニウム前駆体は、低融点及び高い揮発性だけでなく、高温熱安定性を有するので、これを誘電膜形成のための蒸着ソースとして用いる場合、高い蒸着温度にあっても簡単に熱分解されないので、縦横比が大きい下部電極の表面に容易に誘電膜を形成できる。
110 蒸着ソース
115 薄膜
205 素子分離膜
210 ゲート絶縁膜
215 ゲート絶縁膜パターン
220 バッファ膜
225 バッファ膜パターン
230 ゲート導電膜
235 ゲート導電膜パターン
245 ゲート構造物
250 スペーサ
261 第1不純物領域
263 第2不純物領域
270 第1層間絶縁膜
281 第1コンタクトプラグ
283 第3コンタクトプラグ
290 第2層間絶縁膜
300 ビットラインコンタクト
310 ビットライン
320 第3層間絶縁膜
330 キャパシタコンタクト
340 エッチング阻止膜
350 モールド膜
360 第5導電膜
365 下部電極
370 誘電膜
380,430 上部電極
400 第1誘電膜
410 第2誘電膜
420 誘電膜構造物
Claims (10)
- 前記蒸着ソースは、シリコン前駆体又は有機金属前駆体をさらに含むことを特徴とする請求項2に記載の薄膜形成方法。
- 前記蒸着ソースは、不活性気体を含むキャリアガスとともに前記基板上に供給されることを特徴とする請求項2に記載の薄膜形成方法。
- 前記反応ガスは、酸化剤、還元剤又は窒化剤のうち、少なくとも1つを含むことを特徴とする請求項2に記載の薄膜形成方法。
- 前記基板上に前記下部電極を形成する前に、
前記基板上に層間絶縁膜を形成する段階と、
前記層間絶縁膜を貫通し、前記基板上面に接触するコンタクトプラグを形成する段階と、をさらに含み、
前記下部電極は前記コンタクトプラグ上に形成されて電気的に接続されることを特徴とする請求項6に記載のキャパシタ形成方法。 - 前記基板上に前記層間絶縁膜を形成する前に、
前記基板上にゲート構造物を形成する段階と、
前記ゲート構造物に隣接する前記基板の部分に不純物領域を形成する段階と、を含み、
前記コンタクトプラグは、前記不純物領域の上面に接触することを特徴とする請求項7に記載のキャパシタ形成方法。 - 前記基板上に前記ゲート構造物を形成する段階は、
前記基板上に順次に積層されたゲート絶縁膜パターン、バッファ膜パターン及びゲート導電膜パターンを形成する段階を含むことを特徴とする請求項8に記載のキャパシタ形成方法。 - 前記基板上に前記下部電極を形成する段階は、
前記層間絶縁膜上に前記コンタクトプラグの表面を露出させる開口を有するモールド膜を形成する段階と、
前記開口の内壁上に導電膜パターンを形成する段階と、
前記モールド膜を除去する段階と、を含むことを特徴とする請求項7に記載のキャパシタ形成方法。
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