JP2023545619A - 選択性付与剤を用いた領域選択的薄膜形成方法 - Google Patents
選択性付与剤を用いた領域選択的薄膜形成方法 Download PDFInfo
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- JP2023545619A JP2023545619A JP2023515391A JP2023515391A JP2023545619A JP 2023545619 A JP2023545619 A JP 2023545619A JP 2023515391 A JP2023515391 A JP 2023515391A JP 2023515391 A JP2023515391 A JP 2023515391A JP 2023545619 A JP2023545619 A JP 2023545619A
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- 238000000034 method Methods 0.000 title claims abstract description 43
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- 239000002243 precursor Substances 0.000 claims abstract description 27
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- 238000010926 purge Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000010408 film Substances 0.000 claims description 22
- 239000010955 niobium Substances 0.000 claims description 14
- 238000000231 atomic layer deposition Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 9
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Abstract
本発明の一実施例によれば,領域選択的薄膜形成方法は,選択性付与剤を基板が配置されたチャンバの内部に供給し,前記基板の非成長領域に吸着する選択性付与剤供給工程; 前記チャンバの内部をパージする工程; 前記チャンバの内部に前駆体を供給して基板の成長領域に吸着する前駆体供給工程; 前記チャンバの内部をパージする工程; 及び,前記チャンバの内部に反応物質を供給して吸着された前記前駆体と反応して薄膜を形成する薄膜形成工程を含む。
Description
本発明は薄膜形成方法に関し,特に選択性付与剤を用いた領域選択的薄膜形成方法に関する。
DRAMデバイスは革新的な技術開発によって微細化され,10nm時代を迎えるに至った。したがって,性能と信頼性を向上させるためにコンデンサのサイズが小さくなったとしても,高い静電容量と低い漏れ電流特性は十分に維持されなければならず,降伏電圧も高くなければならない。
従来のhigh-k材料の静電容量を高めるために様々な研究が進められており,その中でも誘電膜の結晶化を助けるためにシード層を用いる方法がある。
これにより,比較的低い温度でも高い誘電定数を有する結晶構造を形成することができるが,誘電膜が蒸着されてはならないところにもシード層が蒸着されてリーク電流が発生するという問題点がある。
発明の詳細な説明
技術的課題
本発明の目的は,高い静電容量を有する薄膜を形成する方法を提供することにある。
本発明の他の目的は,漏れ電流を最小限に抑えることができる薄膜形成方法を提供することにある。
技術的課題
本発明の目的は,高い静電容量を有する薄膜を形成する方法を提供することにある。
本発明の他の目的は,漏れ電流を最小限に抑えることができる薄膜形成方法を提供することにある。
本発明の他の目的は,領域に応じた選択が可能な薄膜形成方法を提供することにある。
本発明の他の目的は,以下の詳細な説明からより明らかになるであろう。
課題解決手段
本発明の一実施形態によれば,領域選択薄膜形成方法は,選択性付与剤を基板が配置されたチャンバの内部に供給し,前記基板の非成長領域に吸着する選択性付与剤供給工程; 前記チャンバの内部をパージする工程; 前記チャンバの内部に前駆体を供給して基板の成長領域に吸着する前駆体供給工程; 前記チャンバの内部をパージする工程; 及び
前記チャンバの内部に反応物質を供給して吸着された前記前駆体と反応して薄膜を形成する薄膜形成工程を含む。
本発明の一実施形態によれば,領域選択薄膜形成方法は,選択性付与剤を基板が配置されたチャンバの内部に供給し,前記基板の非成長領域に吸着する選択性付与剤供給工程; 前記チャンバの内部をパージする工程; 前記チャンバの内部に前駆体を供給して基板の成長領域に吸着する前駆体供給工程; 前記チャンバの内部をパージする工程; 及び
前記チャンバの内部に反応物質を供給して吸着された前記前駆体と反応して薄膜を形成する薄膜形成工程を含む。
前記成長領域はチタン窒化膜またはナイオブ窒化膜であり得る。
前記非成長領域はシリコン窒化膜であり得る。
前記シリコン窒化膜は,SiN,SiCN,C-ドープSiN,SiONのうちの少なくとも1つから選択されることができる。
選択性付与剤は,下記<化学式1>として表されることができる。
上記<化学式1>において,nはそれぞれ独立に0~8の整数であり,R1~R3は独立に炭素数が1~8のアルキル基であり,R4は水素,炭素数が1~8のアルキル基,炭素数1~8のアルコキシ基から選択される。
前記反応物質は,O3,O2,H2Oのいずれかであることができる。
前記前駆体は,Alを含む三価金属,ZrおよびHfを含む四価金属,NbおよびTaを含む五価金属のうちの少なくとも1つを含む化合物であり得る。
前記薄膜は,化学気相蒸着法(Metal Organic Chemical Vapor Deposition,MOCVD)または原子層蒸着法(Atomic layer Deposition,ALD)により形成されることができる。
発明の効果
本発明の一実施形態によれば,選択性付与剤が非成長領域に吸着した状態で後続的に供給される前駆体が非成長領域に吸着することを防止し,これにより非成長領域に薄膜が形成されることを防止できる。また,これにより漏れ電流を最小化することができる。
本発明の一実施形態によれば,選択性付与剤が非成長領域に吸着した状態で後続的に供給される前駆体が非成長領域に吸着することを防止し,これにより非成長領域に薄膜が形成されることを防止できる。また,これにより漏れ電流を最小化することができる。
以下,本発明の好ましい実施形態を添付の図1~図5を参照してさらに詳細に説明する。 本発明の実施形態は様々な形態に変更することができ,本発明の範囲は以下に説明する実施形態に限定されると解釈されるべきではない。本実施形態は,本発明が属する技術分野において通常の知識を有する者に本発明をさらに詳細に説明するために提供されるものである。したがって,図面に示される各要素の形状は,より明確な説明を強調するために誇張されてもよい。
本明細書全体において,ある部分がある構成要素を「含む」と言うとき,これは,特に反対の記載がない限り,他の構成要素を除外するのではなく,他の構成要素をさらに含み得ることを意味する。
本明細書全体で使用される程度の用語「約」,「実質的に」などは,言及された意味に固有の製造および物質許容誤差が提示されるとき,その数値またはその数値に近い意味で使用される。補助的に,正確なまたは絶対的な数値が,記載された開示を非良心的な侵害者が不当に使用するのを防ぐために使用される。
本明細書全体において,用語「アルキル」または「アルキル基」は,1~12個の炭素原子,1~10個の炭素原子,1~8個の炭素原子,1~5個の炭素原子,1~3個の炭素原子,3~8個の炭素原子,または3~5個の炭素原子を有する直鎖状または分枝状のアルキル基を含む。例えば,前記アルキル基としては,メチル基,エチル基,n-プロピル基(nPr),イソ-プロピル基(iPr),n-ブチル基(nBu),tert-ブチル基(tBu),イソ-ブチル基(iBu) ),sec-ブチル基( sBu),n-ペンチル基,tert-ペンチル基,iso-ペンチル基,sec-ペンチル基,ネオペンチル基,3-ペンチル基,ヘキシル基,イソヘキシル基,ヘプチル基,4 ,4-ジメチルペンチル基,オクチル基,2,2,4-トリメチルペンチル基,ノニル基,デシル基,ウンデシル基,ドデシル基,およびそれらの異性体などが挙げられるが,これらに限定されない。
本明細書全体において,用語「膜」は,「膜」または「薄膜」を含むものであり得るが,これらに限定されない。
従来の工程では,非成長領域,例えばシリコン窒化膜などの非金属薄膜に誘電膜が堆積されてリーク電流が発生する問題がある。しかしながら,以下に説明する選択性付与剤は,金属薄膜よりも非金属薄膜(例えばシリコン窒化膜)に高い密度で吸着され,選択性付与剤は後に投入される金属前駆体の吸着を防ぎ,金属薄膜のみにシード層を形成することができる。
図1は,本発明の一実施形態による薄膜形成方法を概略的に示すフローチャートであり,図2は,図1による供給周期を概略的に示すグラフである。図3は,図1による薄膜形成過程を概略的に示す図である。
基板はプロセスチャンバの内部にロードされ,以下のALDプロセス条件は調整される。ALDプロセス条件は,基板またはプロセスチャンバの温度,チャンバ圧力,ガス流量を含むことができ,温度は10~900℃である。
基板は,チャンバの内部に供給された選択性付与剤にさらされ,選択性付与剤は基板の非成長領域表面に吸着される。非成長領域は窒化シリコン膜であり得,SiN,SiCN,CドープされたSiN,SiONのうちの選択された1つ以上であり得る。選択性付与剤は,非成長領域の表面に高密度で吸着され,その後の工程で金属前駆体が吸着するのを妨げる。
選択性付与剤は,下記<化学式1>で表される。
上記<化学式1>において,nはそれぞれ独立に0~8の整数であり,R1~R3は独立に炭素数が1~8のアルキル基であり,R4は水素,炭素数が1~8のアルキル基,炭素数1~8のアルコキシ基から選択される。
その後,チャンバの内部にパージガス(例えば,Arなどの不活性ガス)を供給して,未吸着選択性付与剤または副生成物を除去または浄化する。
その後,基板はチャンバの内部に供給された金属前駆体にさらされ,金属前駆体は成長領域の表面に吸着され,非成長領域の表面には選択性付与剤のために吸着されない。 金属前駆体は,Alなどの3族を含んでもよく,Zr,Hfなどの4族を含んでもよく,Nb,Taなどの5族を含んでもよい。
その後,チャンバの内部にパージガス(例えば,Arなどの不活性ガス)を供給して,未吸着金属前駆体または副生成物を除去または浄化する。
その後,基板をチャンバの内部に供給された反応材料に露出させ,基板の表面に薄膜を形成する。反応物質は金属前駆体層と反応して薄膜を形成し,反応物質はO3,O2,H2Oガスであり,反応物質を介して金属酸化物膜を形成することができる。このとき,反応物質は吸着された表面保護物質を酸化させ,基板の表面から分離して除去する。
その後,チャンバの内部にパージガス(例えば,Arなどの不活性ガス)を供給して未反応物質または副生成物を除去または浄化する。
一方,先に選択性付与剤が金属前駆体の前に供給されると説明したが,これとは異なり,選択性付与剤は,金属前駆体の後に供給することができ,または金属前駆体を前後に供給することができる。
- 実施例1
選択性付与剤として,トリメチルオルトフォームを用いて金属薄膜(TiN)基板,非金属薄膜(SiN)基板上にそれぞれナイオビウム酸化膜を形成した。ALD工程によりナイオブ酸化膜を形成し,ALD工程温度は290℃,反応物質はO3ガスを用いた。
選択性付与剤として,トリメチルオルトフォームを用いて金属薄膜(TiN)基板,非金属薄膜(SiN)基板上にそれぞれナイオビウム酸化膜を形成した。ALD工程によりナイオブ酸化膜を形成し,ALD工程温度は290℃,反応物質はO3ガスを用いた。
ALD工程によるナイオブ酸化膜形成工程は以下の通りであり,以下の工程を1サイクルとして進行した(図1~3参照)。
1)反応室内に選択性付与剤を供給して基板に吸着
2)反応室内にArガスを供給して未吸着選択性付与剤又は副生成物を除去する
3)Arをキャリアガスとして,ナイオブ前駆体TBTDEN(Tert-butylimido tris(diethylamido)niobium)を反応室に供給し,基板にナイオブ前駆体を吸着
4)反応室内にArガスを供給して未吸着ナイオブ前駆体又は副生成物を除去する
5)O3ガスを反応室に供給してナイオブ酸化膜を形成する
6)反応室内にArガスを供給して未反応物質または副生成物を除去する
1)反応室内に選択性付与剤を供給して基板に吸着
2)反応室内にArガスを供給して未吸着選択性付与剤又は副生成物を除去する
3)Arをキャリアガスとして,ナイオブ前駆体TBTDEN(Tert-butylimido tris(diethylamido)niobium)を反応室に供給し,基板にナイオブ前駆体を吸着
4)反応室内にArガスを供給して未吸着ナイオブ前駆体又は副生成物を除去する
5)O3ガスを反応室に供給してナイオブ酸化膜を形成する
6)反応室内にArガスを供給して未反応物質または副生成物を除去する
- 比較例1
前述の選択性付与剤を用いずに金属薄膜(TiN)基板,非金属薄膜(SiN)基板上にそれぞれナイオビウム酸化膜を形成した。ALD工程によりナイオブ酸化膜を形成し,ALD工程温度は290℃,反応物質はO3ガスを用いた。
前述の選択性付与剤を用いずに金属薄膜(TiN)基板,非金属薄膜(SiN)基板上にそれぞれナイオビウム酸化膜を形成した。ALD工程によりナイオブ酸化膜を形成し,ALD工程温度は290℃,反応物質はO3ガスを用いた。
ALD工程によるナイオブ酸化膜形成工程は以下の通りであり,以下の工程を1サイクルとして進行した。
1)Arをキャリアガスとして,ナイオブ前駆体TBTDEN(Tert-butylimido tris(diethylamido)niobium)を反応室に供給し,ナイオビウム前駆体を基板に吸着
2)反応室内にArガスを供給して未吸着ナイオブ前駆体又は副生成物を除去する
3)O3ガスを反応室に供給してナイオブ酸化膜を形成する
4)反応室内にArガスを供給して未反応物質または副生成物を除去する
1)Arをキャリアガスとして,ナイオブ前駆体TBTDEN(Tert-butylimido tris(diethylamido)niobium)を反応室に供給し,ナイオビウム前駆体を基板に吸着
2)反応室内にArガスを供給して未吸着ナイオブ前駆体又は副生成物を除去する
3)O3ガスを反応室に供給してナイオブ酸化膜を形成する
4)反応室内にArガスを供給して未反応物質または副生成物を除去する
図4は,本発明の一実施例および比較例1によるXPS(X線光電子スペクトル分析)によるNb含有量を示すグラフである(30サイクル基準)。比較例1では,Nb含有量はSiN基板:TiN基板=1:1.2であったが,実施例1では,Nb含有量はSiN:TiN=1:3.2と選択性が増加した。このような結果は,選択性付与剤がSiN基板に吸着してナイオブ前駆体蒸着を抑制したものと解釈できる。
比較例1に基づいて,本発明の一実施例に対する厚み減少率を示す表である。図5に示すように,実施例1のナイオブ酸化膜は,TiN基板では厚さが42%減少したのに対し,SiN基板では厚さが82%減少し,選択性が増加したことが確認できる。実施例1において選択性付与剤が選択性を有する理由は,SiN基板と構造的に適合して吸着力が強化され,これによりSiN基板における金属薄膜の核成長を遅らせるものと解釈され,他の複合的な原因による結果として所望の選択性を得ることができる。
結論として,選択性付与剤は,非金属薄膜への選択的な吸着により高い厚さ減少効果を示し,これにより所望の基板の領域に誘電膜が堆積されるように選択性を付与することができるだけでなく,不要な領域に薄膜が形成されることを防ぐことにより漏れ電流を最小限に抑えることができる。
以上,本発明を,実施例に従って詳細に説明したが,他の形態の実施形態も可能である。したがって,以下に記載される特許請求の範囲の技術的思想および範囲は実施形態に限定されない。
本発明は,多様な形態の半導体の製造方法に応用される。
Claims (8)
- 選択性付与剤を基板が配置されたチャンバの内部に供給し,前記基板の非成長領域に吸着する選択性付与剤供給工程;
前記チャンバの内部をパージする工程;
前記チャンバの内部に前駆体を供給して基板の成長領域に吸着する前駆体供給工程;
前記チャンバの内部をパージする工程;及び
前記チャンバの内部に反応物質を供給して吸着された前記前駆体と反応して薄膜を形成する薄膜形成工程を含む,領域選択的薄膜形成方法。 - 前記成長領域はチタン窒化膜またはナイオブ窒化膜である請求項1記載の領域選択的薄膜形成方法。
- 前記非成長領域はシリコン窒化膜である請求項1記載の領域選択的薄膜形成方法。
- 前記シリコン窒化膜は,SiN,SiCN,C-ドープSiN,SiONのうちの少なくとも1つから選択される請求項3記載の領域選択的薄膜形成方法。
- 前記反応物質は,O3,O2,H2Oのいずれかである請求項1記載の領域選択的薄膜形成方法。
- 前記前駆体は,Alを含む三価金属,ZrおよびHfを含む四価金属,NbおよびTaを含む五価金属のうちの少なくとも1つを含む化合物である請求項1記載の領域選択的薄膜形成方法。
- 前記薄膜は,化学気相蒸着法(Metal Organic Chemical Vapor Deposition,MOCVD)または原子層蒸着法(Atomic layer Deposition,ALD)により形成される請求項1記載の蒸着方法。
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