プラズマ技術の最新パラダイム― その材料技術とのコラボレーションを目指して ―2006年5月発行
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目
第 １章 緒次

言 ······················································································································· 1

第 ２章 プラズマ―プラズマディスプレイの場 合 ································································· 4
２.１ 蛍 光 灯 の構 造 ···················································································································· 4
２.２ PDPの原 理 、構 造 ·············································································································· 4
２.３ ディスプレイの性 能 比 較 ····································································································· 5
２.４ PDPの今 後 ························································································································· 52.4.1 開 発 の体 制 ·················································································································· 52.4.2 市 場 の動 き ··················································································································· 6
2.4.3 技 術 開 発 最 新 状 況 の具 体 例 （N H K )·········································································

6

２.５ PDPに使 われる高 分 子 材 料 ······························································································· 7

第 ３章 表 面 改 質 のためのプラズマ源 ················································································· 8
３.１ プラズマ技 術 に関 する用 語 ································································································ 8
３.２ プラズマ電 源 ···················································································································· 11
３.３ プラズマ診 断 ···················································································································· 13
3.3.1 分 光 計 測 ···················································································································· 13
3.3.2 プラズマのパラメータと手 法 ························································································ 13
3.3.3 プラズマのパラメータと実 際 の装 置 ············································································· 14
3.3.4 プラズマシミュレーション ······························································································ 16
３.４ プラズマが高 分 子 材 料 に及 ぼす作 用 ·············································································· 18
３.５ 高 分 子 表 面 改 質 後 の評 価 ······························································································ 19
3.5.1 接 触 角 ························································································································ 19
3.5.2 ＸＰＳ（ＥＳＣＡ） ············································································································· 19
3.5.3 FT-IR ·························································································································· 20
3.5.4 電 子 顕 微 鏡 、AFM ······································································································ 20
3.5.5 表 面 物 性 ···················································································································· 20
3.5.6 ラマン分 光 ·················································································································· 21

第 ４章 大 気 圧 グロー放 電 プラズマ（大 気 圧 低 温 プラズマ、APG） ····························· 22
４.１ 大 気 圧 グロー放 電 プラズマの歴 史 ··················································································· 22
４.２ 大 気 圧 グロー放 電 プラズマの概 要 ··················································································· 24
4.2.1 従 来 の大 気 圧 グロー放 電 プラズマが、不 安 定 であった理 由 ······································ 24
4.2.2 大 気 圧 グロー放 電 の安 定 条 件 ··················································································· 24
4.2.3 大 気 圧 グロー放 電 安 定 の理 由 ··················································································· 24
4.2.4 従 来 の大 気 圧 プラズマとの違 い ················································································· 25
4.2.4.1 バリア誘 電 体 放 電 (D B D )との違 い ········································································· 25
4.2.4.2 コロナ放 電 との違 い ································································································· 25－i－４.３ 大 気 圧 グロー放 電 プラズマの研 究 進 捗 ··········································································· 25
4.3.1 大 気 圧 グロー放 電 プラズマの研 究 進 捗 （1 ） ······························································· 25
4.3.1.1 端 緒 となった研 究 ································································································· 26
4.3.1.2 A P G メカニズムの考 察 ·························································································· 27
4.3.1.2-1 放 電 電 流 の測 定 ······························································································· 27
4.3.1.2-2 発 光 スペクトルの測 定 ······················································································ 27
4.3.1.2-3 グロー放 電 開 始 、消 失 電 圧 の測 定 ·································································· 28
4.3.1.3 電 極 形 状 を変 えた場 合 のA P G ············································································· 28
4.3.1.4 H e 以 外 のガスによるA P G 他 ················································································· 29
4.3.1.5 A P G によるプラズマ重 合 膜 （低 圧 グロー放 電 法 との比 較 ） ·································· 31
4.3.1.6 A P G の応 用 ·········································································································· 34
4.3.2 大 気 圧 グロー放 電 プラズマの研 究 進 捗 （２） ······························································· 35
4.3.2.1 A P G とD B D との違 いの検 証 ················································································· 35
4.3.2.2 カーボンナノチューブ合 成 のためのA P G ······························································· 36
4.3.3 大 気 圧 グロー放 電 プラズマの研 究 進 捗 （３） ······························································· 37
4.3.3.1 名 古 屋 大 マイクロ波 励 起 大 気 圧 プラズマ装 置 ·················································· 37
4.3.3.2 東 北 大 の研 究 ······································································································ 38
4.3.3.3 埼 玉 大 導 電 セラミックスをトリガーとする大 気 圧 非 平 衡 プラズマ ······················· 38
4.3.4 大 気 圧 グロー放 電 プラズマの研 究 進 捗 （４） ······························································· 40
4.3.4.1 フランスUniversite Paul Sabatier のMassiners の研 究 ··········································· 40
4.3.4.2 英 国 University of Surrey のShenton の研 究 ························································· 40
4.3.4.3 国 際 ワークショップ ································································································ 41
４.４ 大 気 圧 グロー放 電 プラズマの実 用 化 状 況 ······································································· 41
4.4.1 大 気 圧 グロー放 電 プラズマの実 用 化 状 況 １（積 水 化 学 の状 況 ） ······························· 41
4.4.2 大 気 圧 グロー放 電 プラズマの実 用 化 状 況 ２（松 下 電 工 の状 況 ） ······························· 41
4.4.3 大 気 圧 グロー放 電 プラズマの実 用 化 状 況 ３（コニカミノルタの状 況 ） ·························· 42
4.4.4 大 気 圧 グロー放 電 プラズマの実 用 化 状 況 ４（国 内 研 究 機 関 、企 業 での状 況 ） ·········· 42
4.4.5 大 気 圧 グロー放 電 プラズマの実 用 化 状 況 ５（ダウコーニングの状 況 ） ························ 42
４.５ 大 気 圧 グロー放 電 プラズマの今 後 の展 望 ······································································· 43

第 ５章 マイクロプラズマ ········································································································· 44
５.１ マイクロプラズマの概 要 ···································································································· 44
5.1.1 マイクロプラズマの状 況 ······························································································ 44
5.1.1.1 マイクロプラズマ全 般 の状 況 ················································································ 44
5.1.1.2 PDP最 新 技 術 の状 況 ··························································································· 44
5.1.2 マイクロプラズマの実 例 ······························································································ 45
5.1.2.1 マイクロプラズマの実 例 ························································································ 45
5.1.2.2 極 微 細 プラズマ(ナノプラズマ)の実 例 ·································································· 46
5.1.3 マイクロプラズマの特 徴 と研 究 の方 向 ········································································ 47
５.２ マイクロプラズマの研 究 状 況 ···························································································· 48－ii－

5.2.1 マイクロプラズマの研 究 例 （１） ···················································································· 48
5.2.2 マイクロプラズマの研 究 例 （２） マイクロプラズマジェットによるシリコンナノコーンの生成 ··· 49
5.2.3 マイクロプラズマの研 究 例 （３） 液 滴 を用 いたマイクロプラズマ ································· 50

第 ６章 パルス変 調 プラズマ ·································································································· 52
６.１ 連 続 プラズマの問 題 解 決 としてのパルス変 調 プラズマ ···················································· 52
６.２ パルス変 調 プラズマのエッチング ······················································································ 54
6.2.1 パルス変 調 ECRプラズマの場 合 ················································································· 54
6.2.2 使 用 ガスを考 慮 したパルス変 調 ＩＣＰプラズマの場 合 ·················································· 55
６.３ パルス変 調 プラズマのCCD素 子 製 造 プラズマプロセスへの応 用 ····································· 56
６.４ パルス変 調 プラズマのCVDへの応 用 （１） ········································································· 58
６.５ パルス変 調 プラズマのCVDへの応 用 （２） ········································································· 58
６.６ パルス変 調 プラズマのCVDへの応 用 （３） ········································································· 59

第 ７章 中 性 粒 子 ビームとその応 用 ···················································································· 60
７.１ 装 置 と中 性 化 のメカニズム ······························································································· 60
７.２ 中 性 粒 子 ビームの応 用 （１）ゲート電 極 のエッチング ····················································· 62
７.３ 中 性 粒 子 ビームの応 用 （２）ゲート窒 化 膜 の改 質 ·························································· 63
７.４ 中 性 粒 子 ビームの応 用 （３）量 子 ドット ··········································································· 63
７.５ 中 性 粒 子 ビーム装 置 の関 連 特 許 と装 置 の開 発 ······························································ 64

第 ８章 プラズマイオン注 入 法 （PBII：Plasma Base Ion Implantation） ····················· 65
８.１ PBIIの概 要 ······················································································································· 65
８.２ RFパルスバイアス同 時 印 可 型 PBII ·················································································· 66
８.３ バイポーラパルスPBII ······································································································· 67
８.４ 同 軸 真 空 アークコーティング ····························································································· 69
８.５ 負 イオンビームのイオン注 入 ・イオンビーム蒸 着 法 への応 用 ··········································· 70
８.６ 極 低 エネルギーイオンビーム技 術 と材 料 開 発 への応 用 ·················································· 71
８.７ 配 管 内 壁 の処 理 ·············································································································· 73
８.８ コンビナトリアル手 法 による、イオン注 入 条 件 の設 定 (参 考 ) ············································ 74

第 ９章 高 周 波 プラズマとマイクロ波 プラズマの最 新 動 向(ICP、CCP、表 面 波 、ECRプラズマ、ヘリコン波 プラズマ) ······························ 75
９.１ 高 周 波 プラズマ最 新 動 向 ································································································· 75
9.1.1 選 択 的 運 動 量 制 御 型 プラズマ(茨 城 大 ) ·································································· 76
9.1.2 内 挿 アンテナICP（東 芝 ） ····························································································· 76
9.1.3 SLA-ICP（アネルバ) ·································································································· 77
9.1.4 ２周 波 重 畳 マグネトロンCCP（東 芝 ） ··········································································· 78
9.1.5 NLDプラズマ（アルバック） ··························································································· 79
9.1.6 ガスパフプラズマ（三 菱 電 機 ） ····················································································· 79－iii－

９.２ マイクロ波 帯 プラズマ最 新 動 向 ························································································ 80
9.2.1 表 面 波 プラズマ、R L S A マイクロ波 励 起 プラズマ ························································ 80
9.2.2 表 面 波 プラズマの例 ··································································································· 81
9.2.2.1 リングスロット型 アンテナによるマイクロ波 励 起 表 面 波 プラズマ ···························· 81
9.2.2.2 スロットアンテナのプラズマ源 （東 芝 ） ···································································· 81
9.2.3 体 積 波 プラズマ ··········································································································· 82
9.2.4 ギャップ放 電 によるマイクロ波 励 起 大 気 圧 プラズマ ···················································· 83
9.2.5 マイクロストリップラインを用 いたマイクロ波 励 起 大 気 圧 プラズマ ······························· 83
9.2.6 小 型 システムのマイクロ波 励 起 大 気 圧 プラズマ ························································· 84
９.３ ECR プラズマの最 新 動 向 ································································································· 84
9.3.1 EC R 装 置 の改 良 ········································································································· 84
9.3.2 UHF 帯 E C R プラズマ ···································································································· 85
9.3.3 EC R 装 置 のパルスバイアス ························································································ 85
９.４ ヘリコン波 プラズマの最 新 動 向 ························································································ 86
9.4.1 ヘリコン波 エッチングC V D 複 合 機 ··············································································· 86
9.4.2 大 容 量 へリコン波 励 起 の装 置 ···················································································· 86
９.５ 大 面 積 プラズマ ················································································································ 87
9.5.1 低 インダクタンス内 部 アンテナ方 式 ············································································· 87
9.5.2 ラダー型 電 極 方 式 ······································································································ 88

第 10章 電 子 ビーム励 起 プラズマ（EBEP:Electron Beam Excited Plasma） ············ 90
10.１ 中 部 地 域 コンソーシアムの研 究 開 発 ·············································································· 90
10.２ EBEPの装 置 (日 本 電 子 の装 置 ) ···················································································· 91
10.３ EBEP関 連 (名 古 屋 大 の研 究 ) ························································································· 91
10.3.1 パルス変 調 型 電 子 ビーム励 起 プラズマ ···································································· 91
10.3.2 コンパクトDCコントロール電 子 ビーム励 起 プラズマ ··················································· 92

第 11章 コロナ放 電 処 理 ········································································································ 93
11.１ パルスコロナ放 電 法 ········································································································ 93
11.２ 流 体 安 定 化 コロナ放 電 ··································································································· 94
11.３ コロナトーチ ····················································································································· 95
11.４ 櫛 形 電 極 によるコロナ放 電 処 理 ····················································································· 95

第 12章 熱 プラズマ ·················································································································· 96
12.１ 熱 プラズマについて ········································································································· 96
12.1.1 熱 プラズマの生 成 ····································································································· 96
12.1.2 熱 プラズマの特 徴 と応 用 ·························································································· 97
12.２ 熱 プラズマにおけるパルス変 調 （無 機 材 研 ） ··································································· 97
12.2.1 高 周 波 誘 導 プラズマの、エネルギー制 御 法 としての、パルス変 調 ··························· 97
12.2.2 金 沢 大 の研 究 ··········································································································· 98－iv－

12.2.3 無 機 材 研 （１）ZnO関 連 ·························································································· 99
12.３ 無 機 材 研 （２）電 池 関 連 ······························································································ 100
12.４ ナノ粒 子 合 成 （東 工 大 の研 究 ） ····················································································· 102
12.５ 高 周 波 誘 導 熱 プラズマの初 期 点 火 改 善 ······································································ 104
12.６ プラズマジェット 広 島 大 のプロジェクト ········································································· 105
12.７ 放 電 プラズマ焼 結 SPS ································································································ 106
12.7.1 放 電 プラズマ焼 結 装 置 ··························································································· 107
12.7.2 応 用 （１）傾 斜 機 能 材 料 ······················································································· 107
12.7.3 応 用 （２）MEMS分 野 への成 形 品 ·········································································· 108
12.８ プラズマ溶 射 ················································································································· 109
12.8.1 ハイブリッドプラズマによるプラズマ溶 射 ································································· 109
12.8.2 ツインハイブリッドプラズマスプレイシステム ···························································· 111

第 13章 高 分 子 材 料 のプラズマによる処 理 、改 質 ······················································· 112
13.１ プラズマ処 理 概 要 ········································································································· 112
13.1.1 化 学 変 化 と物 理 変 化 の分 離 ·················································································· 112
13.1.2 プラズマ中 の要 素 の分 離 （電 子 、イオン、ラジカルの分 離 ） ···································· 113
13.1.3 高 分 子 材 料 の組 成 の影 響 （ポリエステル３種 の比 較 ） ··········································· 113
13.1.4 プラズマの特 性 の影 響 リモートプラズマとダイレクトプラズマの比 較 ···················· 114
13.1.4.1 リモートプラズマの効 果 PTFEの場 合 ······························································ 114
13.1.4.2 リモートプラズマの効 果 液 晶 ポリマーの場 合 ·················································· 115
13.1.5 高 分 子 中 の特 定 部 位 の改 質 の例 （ETFE) ····························································· 116
13.1.6 パルスプラズマの効 果 ···························································································· 117
13.1.7 プラズマ処 理 の経 時 変 化 ······················································································· 118
13.２ 接 着 性 改 良 ·················································································································· 120
13.2.1 接 着 性 改 良 （１）半 導 体 MIRAIプロジェクト関 連 ··················································· 120
13.2.2 接 着 性 改 良 （２）フィルム（電 磁 遮 蔽 用 フィルム） ·················································· 122
13.2.3 接 着 性 改 良 （３）銀 塩 感 材 付 きフィルム ······························································· 123
13.2.4 接 着 性 改 良 （４）フィルム（ＰＰフィルムと銅 ） ························································· 123
13.2.5 接 着 性 改 良 （５）フィルム（ＰＥＴフィルムの印 刷 性 ） ·············································· 124
13.2.6 接 着 性 改 良 （６）フィルム（ＡＣＦ関 連 ） ··································································· 125
13.2.7 接 着 性 改 良 （７）フィルム ······················································································ 126
13.2.8 接 着 性 改 良 （８）ポリイミドフィルムと銅 ································································· 127
13.2.9 接 着 性 改 良 （９）フッ素 系 フィルムと銅 ·································································· 129
13.2.10 接 着 性 改 良 （１０）成 形 品 (レンズ) ······································································ 130
13.2.11 IOFのコート技 術 ··································································································· 130
13.2.12 エラストマーの処 理 ······························································································· 131
13.３ 親 水 化 ･撥 水 化 ･ぬれ性 ･官 能 基 付 与 ·········································································· 132
13.3.1 有 機 TFT関 連 自 己 整 合 プロセス ············································································ 132
13.3.2 親 水 化 （１）フィルム ······························································································ 133－v－

13.3.3 親 水 化 （２）フィルム ······························································································ 135
13.3.4 疎 水 化 フィルム ····································································································· 136
13.3.5 マイクロプラズマによる局 所 官 能 基 付 与（ポリエチレン表 面 の任 意 の場 所 にアミノ基 )························································

136

13.3.6 走 査 型 大 気 圧 マイクロラジカルジェット方 式 による局 所 親 水 化 処 理（ポリカーボネートのぬれ性 ） ··················································································· 137
13.3.7 ぬれ性 （ポリカーボネート） ······················································································· 138
13.3.8 親 水 性 （PTFE） ······································································································· 139
13.４ 医 薬 品 DDSへの表 面 溶 解 性 改 良 ················································································ 140
13.4.1 DDSに使 用 する高 分 子 の分 類 、選 別 ····································································· 140
13.4.2 プラズマ処 理 による乾 式 DDS ·················································································· 142
13.4.3 大 気 圧 グロー放 電 プラズマの応 用 ········································································· 144
13.５ チューブ内 面 処 理 ········································································································· 145
13.5.1 チューブ内 面 処 理 （１）軟 質 塩 ビチューブ ····························································· 145
13.5.2 チューブ内 面 処 理 （２）PETチューブの処 理 ·························································· 146
13.5.3 チューブ内 面 処 理 （３）PETチューブの処 理 （2） ···················································· 147
13.5.4 チューブ内 面 処 理 （４）PBIIによる処 理 ································································· 148
13.5.5 チューブ内 面 処 理 （５）PTFE、PSチューブの処 理 ················································· 149
13.６ 分 離 膜 の処 理 ··············································································································· 150
13.6.1 分 離 膜 の処 理 （１）PP膜 ······················································································· 150
13.6.2 分 離 膜 の処 理 （２）PAN膜 ···················································································· 151
13.6.3 分 離 膜 の処 理 （３）PSF、PAN膜 ··········································································· 151
13.７ 粉 末 ・繊 維 の改 質 ········································································································· 153
13.7.1 粉 末 のプラズマ処 理 例 ··························································································· 153
13.7.2 繊 維 のプラズマ処 理 例 ··························································································· 155
13.８ コロナ処 理 ····················································································································· 156
13.8.1 コロナとプラズマの比 較 （ポリオレフィンの処 理 ） ····················································· 156
13.8.2 超 高 分 子 量 ポリエチレン繊 維 とエポキシ樹 脂 の複 合 化 ········································· 157
13.8.3 パルスコロナ放 電 の利 用 （エレクトレットフィルタ） ··················································· 158
13.8.4 コロナトーチ （１）PETの処 理 ················································································· 158
13.8.5 コロナトーチ （２）PETの処 理 ················································································· 160
13.8.6 ナイロンとゴムのコロナ処 理 ···················································································· 162
13.8.7 生 分 解 性 プラスチックのコロナ処 理 ········································································ 163
13.8.8 ポリエチレンシートのコロナ処 理 ·············································································· 164
13.９ イオンビームによる処 理 具 体 例 ···················································································· 165
13.9.1 PBIIによる改 質 （１）PETのガスバリア性 ······························································· 165
13.9.2 PBIIによる改 質 （２）PSF表 面 へのヘパリン固 定 化 ··············································· 166
13.9.3 フィルムへのイオン注 入 ·························································································· 167
ⅰ．ポリイミド（電 気 特 性 、光 学 特 性 ） ·············································································· 168
ⅱ．シリコーンゴム、ポリスチレン（ぬれ性 ） ······································································· 168－vi－

ⅲ．セグメント化 ポリウレタン（細 胞 接 着 制 御 ） ································································· 168
ⅳ．コラーゲン（生 体 高 分 子 の一 種 ）（細 胞 と血 小 板 の接 着 性 を独 立 制 御 ） ·················· 168
13.9.4 PBIIによるゴム用 金 型 の表 面 改 質 ········································································· 170
13.10 プラスチック基 板 に関 連 したプラズマ処 理 ·································································· 171
13.10.1 常 温 結 晶 化 技 術 ·································································································· 171
13.10.1.1 技 術 の詳 細 ···································································································· 171
13.10.1.2 具 体 的 な応 用 状 況 ························································································· 173
13.10.1.3 コンソーシアム ································································································· 173
13.10.1.4 a-Si 薄 膜 の結 晶 化 ······················································································· 173
13.10.2 有 機 太 陽 電 池 用 ITO電 極 の酸 素 プラズマ処 理 効 果 ············································ 173
13.11 高 温 高 密 度 プラズマによる処 理 ·················································································· 175

第 14章 プラズマによる高 分 子 材 料 のエッチング、微 細 加 工 ···································· 176
14.１ エッチング ······················································································································ 176
14.1.1 Low-k膜 のエッチング
MIRAIプロジェクト、ポーラスシリカおよびプラズマ重 合 膜 のエッチング ··················· 176
14.1.2 ポーラスシリカの要 素 プロセス技 術 (MIRAIプロジェクト､2005) ······························· 178
14.1.3 NLDプラズマによるLow-k膜 のエッチング·····························································

179

14.1.4 層 間 絶 縁 膜 のエッチング ························································································ 180
14.1.5 ラジカル注 入 を用 いたECRエッチング装 置 によるSiLK

ＴＭのエッチング ····················· 181

14.1.6 有 機 Low-k材 エッチング用 N 2 /H 2 ２周 波 容 量 結 合 プラズマのモデリング ··············· 182
14.1.7 RLSAマイクロ波 励 起 プラズマ源 によるLowｰk膜 のエッチング ································ 184
14.２ 有 機 膜 、フィルムのエッチング ······················································································· 184
14.2.1 有 機 膜 のエッチング ································································································ 184
14.2.2 有 機 膜 エッチング用 大 気 圧 プラズマ ······································································· 186
14.2.3 使 用 ガスのポリマー堆 積 を抑 制 するシリコン酸 化 膜 のエッチング ·························· 187
14.2.4 高 分 子 フィルムのエッチング ··················································································· 188
14.３ レジスト関 連 ·················································································································· 190
14.3.1 レジスト材 開 発 の例 ································································································ 191
14.3.2 レジストの問 題 と対 策 の状 況 ·················································································· 193
14.3.2.1 レジストの問 題 と対 策 の状 況 （１）モデリングと、実 際 の比 較 ························· 193
14.3.2.2 レジストの問 題 と対 策 の状 況 （２）LER（Line Edge Roughness）関 連 ············· 196
14.3.2.3 レジストの問 題 と対 策 の状 況 （３）レジスト倒 れの問 題 と対 策 ························ 198
14.４ プラズマ技 術 による高 分 子 材 料 関 連 の微 細 加 工 ························································ 200
14.4.1 高 アスペクト比 の微 細 加 工 ····················································································· 200
14.4.1.1 高 アスペクト比 エッチング ·················································································· 200
14.4.1.2 Bosch法 ············································································································ 201
14.4.2 Bosch法 以 後 の発 展 MEMS関 連 ············································································ 202
14.4.2.1 デンソーの加 速 度 センサー（１） ········································································· 202
14.4.2.2 デンソーの加 速 度 センサー（２） ········································································· 204－vii－

14.4.2.3 大 日 本 印 刷 のボッシュ法 関 連 ·········································································· 205
14.4.2.4 サムコのボッシュ法 関 連 プラズマ装 置 ······························································ 206
14.4.2.5 アルバックMEMS関 連 プラズマ装 置 ·································································· 206
14.4.3 大 気 圧 マイクロプラズマジェット（熱 プラズマ）の微 細 加 工····································

207

14.4.4 バイオチップへの応 用 ····························································································· 208
14.4.5 ポリイミドへのビアホール加 工 ················································································· 209
14.4.6 デスミア・デスカム処 理 ···························································································· 210
14.５ プラズマ技 術 のナノ微 細 パターニング加 工 での利 用 ···················································· 211
14.5.1 ナノインプリントでのエッチング ················································································ 211
14.5.2 ポリマーのミクロ相 分 離 構 造 を利 用 したナノパターン加 工 と記 録 媒 体 への応 用 ···· 213
14.5.3 超 微 細 パターン凹 構 造 の形 成 方 法 ······································································· 216
14.６ 高 分 子 を一 部 含 む材 料 のエッチング ············································································ 217
14.6.1 ITO膜 のエッチング（１） ···························································································· 217
14.6.2 ITO膜 のエッチング（２）(参 考 ) ················································································· 218

第 15章 プラズマ技 術 による高 分 子 材 料 の洗 浄 、クリーニング、分 解 ···················· 220
15.１ 洗 浄 、クリーニング ········································································································ 220
15.1.1 洗 浄 、クリーニング（１）有 機 系 汚 染 物 質 想 定 ························································ 220
15.1.2 洗 浄 、クリーニング（２）洗 浄 専 用 装 置 の例 ···························································· 221
15.1.3 洗 浄 、クリーニング（３）金 メッキ工 程 でのNi化 合 物 のクリーニング ························· 222
15.1.4 洗 浄 、クリーニング（４）プラズマ洗 浄 のダメージ評 価 ·············································· 223
15.1.5 洗 浄 、クリーニング（５）廃 プラスチックの塗 膜 クリーニング ······································ 224
15.1.6 洗 浄 、クリーニングに関 する評 価 方 法 （エプソンメソッドによるガス削 減 ） ··············· 225
15.２ 分 解 、アッシング ············································································································ 227
15.2.1 ナノコピー技 術 ········································································································ 227
15.2.1.1 酸 化 チタン／ポリアクリル酸 から多 孔 性 チタニア膜 ·········································· 227
15.2.1.2 二 次 元 集 積 有 機 ナノ粒 子 を鋳 型 にしたチタニアナノカプセル ··························· 228
15.2.1.3 ケイ酸 ナトリウムとポリカチオンからシリカナノフィルム ······································ 228
15.2.1.4 チタニアをリソグラフィー（レジスト）して、ナノコピー ··········································· 228
15.2.1.5 チタニアへＤＮＡのナノコピー ············································································· 229
15.2.2 Low-k膜 のアッシング ······························································································ 229
15.2.3 分 解 、アッシング タイヤの分 解 処 理 ······································································ 230
15.2.4 分 解 、アッシング（市 販 装 置 ） ·················································································· 230

第 16章 プラズマ技 術 による高 分 子 材 料 への薄 膜 形 成（無 機 膜 、金 属 膜 、カーボン膜 など） ································································· 233
16.１ フレキシブルデバイス ···································································································· 234
16.1.1 フレキシブルTFT ······································································································· 234
16.1.1.1 プラスチック基 板 のa-Si TFT（１） ······································································ 234
16.1.1.2 プラスチック基 板 のa-Si TFT（２） ······································································ 235－viii－

16.1.1.3 PCVDによるポリシリコン成 膜 ············································································ 235
16.1.1.4 ZnO TFT ··········································································································· 237
16.1.1.4.1 東 北 大 の研 究 ···························································································· 237
16.1.1.4.2 高 知 工 大 の研 究 ························································································· 238
16.1.1.5 東 工 大 の研 究 ··································································································· 238
16.1.2 有 機 ELデバイス ······································································································ 239
16.1.2.1 有 機 ELデバイスの封 止 技 術 (山 形 大 、パイオニア、凸 版 印 刷 ) ······················ 240
16.1.2.2 有 機 ELデバイスの封 止 技 術 （豊 田 中 研 ） ························································· 241
16.1.2.3 有 機 ELデバイスの薄 膜 封 止 技 術 (大 日 本 印 刷 ) (参 考 ) ··································· 243
16.1.2.4 環 境 調 和 型 有 機 EL ·························································································· 244
16.1.2.5 有 機 ELディスプレイ（NHK) (参 考 ) ····································································· 244
16.1.3 フィルム基 板 太 陽 電 池 ··························································································· 245
16.1.3.1 フィルム基 板 太 陽 電 池 （１） ············································································ 245
16.1.3.2 フィルム基 板 太 陽 電 池 （２）CIS系 電 池 (参 考 ) ················································ 248
16.1.3.3 フィルム基 板 太 陽 電 池 （３）有 機 薄 膜 太 陽 電 池 (参 考 ) ·································· 248
16.1.4 フレキシブル基 板 米 国 の動 き ··············································································· 248
16.２ プラズマ技 術 による高 分 子 材 料 への金 属 、金 属 酸 化 膜 形 成 ······································ 249
16.2.1 高 分 子 基 板 上 に透 明 導 電 膜 ITO膜 （１） ······························································ 249
16.2.2 高 分 子 基 板 上 に透 明 導 電 膜 ITO膜 （２） ······························································ 250
16.2.3 イオンプレーティングによるITO膜 ············································································ 251
16.2.4 アルバック ITO膜 ··································································································· 252
16.2.5 ECRプラズマスパッタ法 によるITO膜 ······································································· 253
16.2.6 高 分 子 基 板 上 に透 明 導 電 膜 ZnO膜 ···································································· 254
16.2.6.1 高 知 工 大 の研 究 ······························································································· 254
16.2.6.2 アークプラズマ蒸 着 法 によるZnO透 明 導 電 膜 ·················································· 256
16.2.7 反 応 性 スパッタリング法 によるZnO透 明 導 電 膜 ····················································· 258
16.2.8 高 分 子 材 料 上 に金 属 膜 量 産 ················································································· 259
16.2.9 IVD法 によるPIフィルムへ銅 薄 膜 成 膜 ···································································· 260
16.2.10 チューブ内 面 コーティング処 理 ·············································································· 262
16.2.10.1 走 査 ミラー磁 界 型 同 期 ECRプラズマ装 置 による細 管 内 面 コーティング ·········· 262
16.2.10.2 同 軸 型 マグネトロンパルスプラズマによる細 管 内 面 コーティング ···················· 263
16.３ プラズマ技 術 による高 分 子 材 料 への無 機 膜 形 成 ························································ 265
16.3.1 次 世 代 DVDナノガラス薄 膜 (酸 化 コバルト膜 ) ························································ 265
16.3.2 シリカ膜 ··················································································································· 266
16.3.2.1 シリカ膜 （１） ······································································································ 266
16.3.2.2 シリカ膜 （２） ······································································································ 267
16.3.2.3 シリカ膜 などの大 気 圧 ＣＶＤ ·············································································· 268
16.3.2.4 セラミック膜 ／ポリマー膜 の交 互 ナノ多 層 薄 膜 （層 数 は10～30層 ） ·················· 268
16.3.2.5 反 射 防 止 コート光 学 フィルム ············································································ 269
16.3.3 シリコン窒 化 膜 、シリコン酸 窒 化 膜 ········································································· 269－ix－

16.3.4 シリコンカーバイド膜 ······························································································· 270
16.４ プラズマ技 術 による高 分 子 材 料 へのカーボン膜 の付 着 ··············································· 271
16.4.1 ペットボトル用 DLCコーティング（三 菱 重 工 ） ···························································· 273
16.4.2 変 調 RFプラズマCVDによる高 分 子 基 材 へのDLC膜 作 製 （日 新 電 機 ） ··················· 274
16.4.3 樹 脂 基 材 へのフレキシブルDLC膜 ·········································································· 275
16.4.4 パルス放 電 プラズマCVDによるDLC膜 ···································································· 276
16.4.5 真 空 アーク法 による柔 軟 DLC膜 のゴムへの成 膜 で
摩 擦 特 性 の向 上 （豊 橋 技 術 科 学 大 ） ······································································ 277
16.4.6 セグメント構 造 DLC、ナノパルスCVD ······································································· 278
16.4.6.1 セグメント構 造 DLC ···························································································· 278
16.4.6.2 ナノパルスCVDによるDLC膜 ············································································ 279
16.4.7 パルスバイアス電 圧 によるプラズマCVD法 のDLC膜 ·············································· 280
16.4.8 DLC膜 の剥 離 欠 陥 とその改 善 方 法 ········································································ 281
16.4.9 大 面 積 透 明 DLC成 膜 装 置 ····················································································· 281
16.4.10 ハイブリッド型 パルス･プラズマ･コーティング（ＨＰＰＣ）システム ···························· 282
16.4.11 ハイブリッド重 畳 方 式 プラズマイオン注 入 によるDLC膜 ········································ 282
16.4.12 量 産 型 パルスDCプラズマCVD装 置 ······································································ 283

第 17章 プラズマ技 術 による高 分 子 膜 の形 成（プラズマ重 合 、PCVD） ························································································ 284
17.１ Low-k膜 ························································································································ 284
17.1.1 Low-k膜 （１）NEC p-BCB膜 （プラズマ重 合 膜 ） ··················································· 284
17.1.2 Low-k膜 （２）半 導 体 MIRAIプロジェクトのDVS-BCB ··········································· 286
17.1.3 Low-k膜 （３）MIRAIプロジェクト2005＜17.1.2以 後 ＞ ············································ 288
17.1.4 Low-k膜 （４）分 子 内 細 孔 法 （NEC） ······································································ 289
17.1.5 Low-k膜 （５）NCSによるポーラスシリカ膜 （富 士 通 ）（参 考 ） ································· 290
17.1.6 Low-k膜 （６）RLSAマイクロ波 プラズマ装 置 による、C 5 F 8 の成 膜 ·························· 291
17.1.7 Low-k膜 （７）フルオロカーボン系 ·········································································· 292
17.1.8 Low-k膜 （８）ボラジン ··························································································· 292
17.1.9 Low-k膜 （９）溶 媒 処 理 との組 み合 わせ ······························································· 293
17.２ センサーへの応 用 ········································································································· 294
17.2.1 センサーへの応 用 （１）化 学 センサー ···································································· 294
17.2.2 センサーへの応 用 （２）バイオセンシングシステム ················································· 296
17.2.2.1 QCM上 にプラズマ重 合 膜 を成 膜 し、膜 厚 測 定 と制 御 をする ···························· 296
17.2.2.2 免 疫 センサーの基 体 用 抗 体 固 定 化 高 分 子 としてのプラズマ重 合 膜 ··············· 296
17.2.2.3 マイクロプラズマ重 合 によるバイオセンサーへの応 用 ······································· 297
17.2.3 センサーへの応 用 （３）バイオセンサー ·································································· 298
17.2.4 センサーへの応 用 （４）ガスセンサー ····································································· 300
17.2.5 センサーへの応 用 （５）ガスセンサー ····································································· 301
17.３ 撥 水 性 ・親 水 性 付 与 ····································································································· 301－x－17.3.1 PCVDによる超 撥 水 性 ・超 親 水 性 薄 膜 とそのマイクロパターン ······························· 301
17.3.2 撥 水 性 、親 水 性 材 料 シリコン系 のプラズマ重 合 （１） ············································ 303
17.3.3 撥 水 性 、親 水 性 材 料 シリコン系 のプラズマ重 合 （２） ············································ 304
17.４ 有 機 無 機 複 合 膜 ··········································································································· 304
17.５ 大 気 圧 プラズマ重 合 による高 分 子 材 料 の表 面 処 理 ···················································· 305
17.5.1 大 気 圧 プラズマ重 合 （１） ······················································································ 306
17.5.2 大 気 圧 プラズマ重 合 （２） ······················································································ 306
17.5.3 大 気 圧 プラズマ重 合 （３）粘 着 テープの剥 離 剤 ···················································· 307
17.5.3.1 大 気 圧 プラズマ重 合 （３）粘 着 テープの剥 離 剤 （1） ········································ 307
17.5.3.2 大 気 圧 プラズマ重 合 （３）粘 着 テープの剥 離 剤 （2） ········································ 308
17.６ フッ素 系 イオン交 換 膜 への応 用 ···················································································· 309
17.７ 電 池 への応 用 ··············································································································· 310
17.7.1 リチウム二 次 電 池 用 傾 斜 特 性 電 解 質 への応 用 ···················································· 311
17.7.2 メタノール型 燃 料 電 池 ····························································································· 313
17.８ 光 ファイバー 増 幅 器 への応 用 （プラズマ開 始 重 合 ） ··················································· 314
17.９ CNx:H フィルム ············································································································· 315

第 18章 湿 式 法 の前 処 理 としてのプラズマ技 術 ···························································· 317
18.１ 細 孔 フィリング膜 (プラズマ処 理 グラフト重 合 法 による機 能 膜 )····································

317

18.２ 中 空 糸 表 面 のプラズマ処 理 とプラズマ開 始 グラフト重 合 法 による改 質 （１） ················· 319
18.３ 中 空 糸 表 面 のプラズマ処 理 とプラズマ開 始 グラフト重 合 法 による改 質 （２） ················· 320
18.４ 血 液 循 環 ポンプの抗 血 栓 性 表 面 処 理 ········································································· 321
18.５ シリコン／アパタイト経 皮 材 料 のコロナグラフト重 合 ····················································· 321
18.６ コンタクトレンズ表 面 のプラズマグラフト重 合 法 ····························································· 323
18.6.1 コンタクトレンズ表 面 のプラズマグラフト重 合 法 （１） ················································ 323
18.6.2 コンタクトレンズ表 面 のプラズマグラフト重 合 法 （２） ················································ 323
18.７ マイクロ波 プラズマを用 いた綿 織 物 のグラフト重 合 ······················································· 323
18.８ PE繊 維 のグラフト重 合 ·································································································· 325
18.９ スチレンのグラフト重 合 ································································································· 326

第 19章 プラズマ技 術 の高 分 子 材 料 関 連 への応 用 その他 ······································· 327
19.１ 滅 菌 ・殺 菌 ····················································································································· 327
19.1.1 大 気 圧 無 声 放 電 による殺 菌 ··················································································· 327
19.1.2 大 容 積 マイクロ波 プラズマによる低 温 殺 菌 ····························································· 328
19.1.3 低 温 表 面 波 空 気 プラズマによる殺 菌 ····································································· 328
19.1.4 大 気 圧 同 軸 マイクロ波 プラズマの殺 菌 滅 菌 ・殺 菌 ················································· 329
19.1.5 殺 菌 に対 する、表 面 波 マイクロプラズマのパルス変 調 の影 響 ································ 329
19.1.6 パルス変 調 体 積 波 プラズマによる殺 菌 ·································································· 330
19.1.7 PBIIによる滅 菌 ······································································································· 331
19.２ 環 境 改 善 のための処 理 ································································································· 331－xi－

19.2.1 アスベストの処 理 ···································································································· 332
19.2.2 PCBの処 理 ············································································································· 332
19.2.3 放 射 能 廃 棄 物 の処 理 ····························································································· 333
19.2.4 水 中 難 分 解 物 質 の処 理 ························································································· 334
19.2.5 CO 2 の分 解 ·············································································································· 334
19.2.6 NOxの分 解 ············································································································· 335
19.2.7 CF 4 の分 解 ·············································································································· 336
19.2.8 大 気 圧 プラズマ触 媒 による有 害 ガス対 策 技 術 ······················································· 336
19.2.9 ナノ材 料 の安 全 性 ·································································································· 337
19.３ 分 析 関 連 ······················································································································ 338
19.3.1 分 析 関 連 （１）マイクロ波 ビーム重 畳 法 を応 用 したプラズマ発 生 分 光 分 析 方 法 ·· 338
19.3.2 分 析 関 連 （２）微少試料内全元素分析用パルス同期マルチガスプラズマ分析装置 ········ 339
19.3.3 分 析 関 連 （３）マイクロ化学分析システム（µTAS：Micro Total Analysis System) ·········· 339
19.４ マイクロプラズマの新 規 な利 用 ····················································································· 340
19.4.1 マイクロプラズマを、プラズマリアクタとして使 う（１） ················································· 340
19.4.2 マイクロプラズマを、プラズマリアクタとして使 う（２） ················································· 341
19.4.3 液 中 環 境 下 マイクロプラズマ合 成 法 ······································································ 342
19.５ 液 体 プラズマ電 極 ········································································································· 342
19.5.1 液 体 プラズマ電 極 を用 いたマイクロ元 素 分 析 器 ···················································· 342
19.5.2 液 体 中 プラズマ ······································································································· 343
19.5.3 超 臨 界 流 体 プラズマの生 成 ··················································································· 344
19.６ これからのプラズマ技 術 例 ···························································································· 345
19.6.1 高 精 度 プラズマ制 御 技 術 （自 律 型 ナノ製 造 システム） ············································ 345
19.6.2 プラズマプロセスでの壁 の影 響 ··············································································· 346

第 20章 終言 ····················································································································· 348

略 語 表 ·································································································································· 349
参 考 文 献 ·································································································································· 352－xii－