JP2019212776A - 成膜用組成物および成膜装置 - Google Patents
成膜用組成物および成膜装置 Download PDFInfo
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Abstract
Description
本発明の実施形態に係る成膜用組成物は、互いに重合して含窒素カルボニル化合物を生成する第1成分と第2成分とを有し、含窒素カルボニル化合物の生成エネルギーに対して、第1成分および第2成分の少なくともいずれかの脱離エネルギーが2倍以上である。
本実施形態の成膜用組成物において、第1成分と第2成分と重合して生成される含窒素カルボニル化合物は、炭素−酸素の二重結合と窒素を含有する重合体である。含窒素カルボニル化合物は、第1成分と第2成分と重合により成膜された膜の成分を構成する。含窒素カルボニル化合物は、このような重合体の膜として、例えば、ウエハの特定の部位がエッチングされることを防ぐための保護膜となり得る。
本実施形態の成膜用組成物に含まれる第1成分は、第2成分と重合して含窒素カルボニル化合物を生成し得るもモノマーである。このような第1成分は、特に限定されないが、例えば、イソシアネート、アミン、酸無水物、カルボン酸、アルコール等が挙げられる。これらの第1成分は、本発明に係る成膜用組成物に含まれる第1成分の一例である。
本実施形態の成膜用組成物に含まれる第2成分は、第1成分と重合して含窒素カルボニル化合物を生成し得るモノマーである。このような第2成分は、特に限定されないが、例えば、イソシアネート、アミン、酸無水物、カルボン酸、アルコール等が挙げられる。これらの第2成分は、本発明に係る成膜用組成物に含まれる第2成分の一例である。
次に、本発明の実施形態に係る成膜装置1について、図1の断面図を参照しながら説明する。本実施形態の成膜装置1は、真空雰囲気が形成される処理容器11と、処理容器11内に設けられた、基板(ウエハW)を載置する載置部(載置台21)と、上述の成膜用組成物(成膜ガス)を処理容器11内に供給する供給部(ガスノズル41)とを有する。なお、成膜装置1は、本発明に係る成膜装置の一例である。
図8に示す成膜装置101を用いて、重合体の膜を成膜した。具体的には、処理容器11内のウエハWの温度を所定の温度に調整し、成膜ガス(第1成分M1と第2成分M2)を供給してウエハWに重合体の膜を成膜した。成膜は4枚のウエハWに対して同時に行った。ウエハWには、直径300mmのシリコンウエハを用いた。なお、ウエハWの温度を成膜温度とし、成膜ガスの供給開始から供給終了までの時間を成膜時間とした。
光学式薄膜及びスキャトロメトリ(OCD)測定装置(装置名「n&k Analyser」、n&k Technology社製)を用いて、ウエハWに成膜した重合体の膜の膜厚を測定した。測定は、成膜したウエハWの面内49か所について行い、その平均膜厚を算出した。
平均膜厚と成膜時間から、成膜速度を算出した。
成膜温度を140℃に調整し、第1成分M1として1,12−ジアミノドデカン(DAD)(脱離エネルギー73kJ/mol)を供給し、第2成分M2として4,4´−ジフェニルメタンジイソシアネート(MDI)(脱離エネルギー101kJ/mol)を供給して、ウエハWに重合体の膜を成膜した。DADとMDIとが重合反応して生成される含窒素カルボニル化合物(ポリウレア)の生成エネルギー(DADの反応エネルギーおよびMDIの反応エネルギー)は、10kJ/molである。DAD、MDIは、いずれも脱離エネルギーが反応エネルギーの2倍以上である。実施例1について、成膜された重合体の膜成膜速度を評価した。結果を表1に示す。
成膜温度を100℃に調整し、第2成分M2としてMDIに替えて1,3−ビス(イソシアナトメチル)シクロヘキサン(H6XDI)(脱離エネルギー66kJ/mol)を供給した以外は、実施例1と同様に成膜し、評価した。結果を表1に示す。
成膜温度を70℃に調整し、第1成分M1としてDADに替えて1,3−ビス(アミノメチル)シクロヘキサン(H6XDA)(脱離エネルギー63kJ/mol)を供給した以外は、実施例2と同様に成膜し、評価した。結果を表1に示す。
成膜温度を40℃に調整し、第1成分M1としてDADに替えて1,6−ジアミノヘキサン(HMDA)(脱離エネルギー58kJ/mol)を供給した以外は、実施例2と同様に成膜し、評価した。結果を表1に示す。
成膜温度を調整せず(室温)、第1成分M1としてヘキサメチレンジオール(HMDO)(脱離エネルギー90kJ/mol)を供給し、第2成分M2としてヘキサメチレンジイソシアネート(HMDI)(脱離エネルギー69kJ/mol)を供給して、ウエハWに重合体の膜を成膜した。HMDOとHMDIとが重合反応して生成される含窒素カルボニル化合物(ポリウレタン)の生成エネルギー(HMDOの反応エネルギーおよびHMDIの反応エネルギー)は、80kJ/molである。HMDO、HMDIは、いずれも脱離エネルギーが反応エネルギーの2倍未満である。比較例1について、成膜された重合体の膜成膜速度を評価した。結果を表1に示す。
1 成膜装置
11 処理容器
21 載置台
20 ステージヒーター
31 排気口
41 ガスノズル
60 配管ヒーター
Claims (9)
- 互いに重合して含窒素カルボニル化合物を生成する第1成分と第2成分とを有し、
前記含窒素カルボニル化合物の生成エネルギーに対して、前記第1成分および前記第2成分の少なくともいずれかの脱離エネルギーが2倍以上である、成膜用組成物。 - 前記含窒素カルボニル化合物は、ポリウレア、ポリウレタン、ポリアミド、ポリイミドから選ばれる少なくとも1種である、請求項1に記載の成膜用組成物。
- 前記第1成分および前記第2成分の少なくともいずれかは、イソシアネート、アミン、酸無水物、カルボン酸、およびアルコールのいずれか1種である、請求項1または2に記載の成膜用組成物。
- 前記第1成分および前記第2成分の少なくともいずれかは、芳香族化合物、キシレン系化合物、脂環族化合物、脂肪族化合物から選ばれる少なくとも1種である、請求項3に記載の成膜用組成物。
- 前記第1成分および前記第2成分の少なくともいずれかは、1官能性化合物または2官能性化合物である、請求項3または4に記載の成膜用組成物。
- 前記第1成分および前記第2成分のいずれか一方がアミンであり、
前記第1成分および前記第2成分のいずれか他方がイソシアネートである、請求項3乃至5のいずれか1項に記載の成膜用組成物。 - 前記アミンは、2官能性脂肪族化合物または2官能性脂環族化合物である、請求項6に記載の成膜用組成物。
- 前記イソシアネートは、2官能性芳香族化合物または2官能性脂環族化合物である、請求項6または7に記載の成膜用組成物。
- 真空雰囲気が形成される処理容器と、
前記処理容器内に設けられた、基板を載置する載置部と、
請求項1乃至8のいずれか1項に記載の成膜用組成物を前記処理容器内に供給する供給部とを有する、成膜装置。
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