電子部品用感光性材料の最新動向Ⅲ― 半導体・電子基板・ディスプレイ分野の開発状況 ―2006年7月発行
定価104,500円（消費税込み）
住ベリサーチの調査研究レポート
住ベリサーチ株式会社
技術調査部〒140-0002 品川区東品川2-5-8
天王洲パークサイドビル16F
TEL 03-5462-7036
FAX 03-5462-7040

目
第１章

次

緒言 ············································································································································ 1

第２章 電子部品用感光性材料の概要 ························································································· 3
２.１ 感光性材料に関する最近の研究 ······················································································ 3
２.１.１

ハイパーブランチ型感光性樹脂 ························································································ 3

２.１.２

連鎖硬化ポリマーからなる高フィラー含有感光性材料 ················································· 5２.１.３

環状オリゴマーからなる高性能光機能性材料 ································································· 6２.１.４

酸素硬化阻害のないチオール／エン型感光性樹脂 ························································· 6２.１.５

酸素硬化阻害のない水酸基を持つモノマーからなる感光性樹脂 ·································· 7

２.１.６

感光性材料の光開始剤の安定化方法 ················································································ 8２.２

電子部品用感光性材料の最新動向 ·················································································· 8２.２.１

半導体用フォトレジスト ··································································································· 8２.２.２電子基板用フォトレジスト ································································································ 9２.２.３

フラットパネルディスプレイ用フォトレジスト ··························································· 10

２.３

電子部品用感光性材料市場の最新動向 ······································································· 10

２.３.１

電子工業界の市場動向 ····································································································· 10

２.３.２

感光性材料の市場動向 ····································································································· 11２.３.３

電子部品用感光性材料メーカーの世界シェア ······························································· 12

２.４

感光性材料メーカーの最新動向 ···················································································· 13

２.４.１

旭化成エレクトロニクス ································································································· 13

２.４.２

荒川化学工業 ····················································································································· 13

２.４.３

AZ エレクトロニックマテリアルズ(AZEM) ································································ 14

２.４.４

NTT ····································································································································· 14

２.４.５

京セラケミカル ················································································································· 14

２.４.６

JSR ····································································································································· 15

２.４.７

シャープ ····························································································································· 16

２.４.８

昭和電工 ····························································································································· 16

２.４.９

住友化学 ····························································································································· 17

２.４.10住友ベークライト ············································································································· 18

２.４.11

ダイセル化学工業 ············································································································· 18

２.４.12

大日本印刷 ························································································································· 18

２.４.13

太陽インキ製造 ················································································································· 19

２.４.14

タムラ化研 ························································································································· 20

２.４.15デュポン MRC ドライフィルム ······················································································· 20

２.４.16

デュポン・ジャパン ········································································································· 20

２.４.17

東京応化工業 ····················································································································· 21

２.４.18

東洋合成工業 ····················································································································· 22

２.４.19東洋インキ製造 ················································································································· 22

２.４.20

東レ ···································································································································· 23

２.４.21

凸版印刷 ····························································································································· 24

２.４.22日本合成化学工業 ············································································································· 24

２.４.23

日立化成工業 ····················································································································· 25

２.４.24

富士フイルム ····················································································································· 25

２.４.25松下電器産業 ····················································································································· 26

２.４.26丸善石油化学 ····················································································································· 26

２.４.27三井化学 ····························································································································· 27

２.４.28三菱化学 ····························································································································· 27

２.４.29

ローム・アンド・ハース(旧シプレイ) ········································································· 27

２.４.30その他 ································································································································ 27
APDC、大阪府立産業技術総合研究所、大阪有機化学工業、関西ペイント、新日鉄化学、
セマテック、セリート、セントラル硝子、ダイソー、東亞合成、東ソー、日東電工、
日本油脂、パイオニア

第３章 半導体リソグラフィー用フォトレジストの最新動向 ········································ 30
３.１ 半導体リソグラフィー用フォトレジストの開発最前線の概要 ·························· 30
３.１.１

次世代は光学式か電子線方式か ······················································································ 30

３.１.２

次々世代は EUV か F2 か ································································································· 31

３.１.３

主要レジストメーカーの動き ·························································································· 32

３.２

KrF 用フォトレジストの技術開発動向 ······································································· 34

３.２.１

KrF 用フォトレジスト ······································································································ 34

３.２.２

KrF 用ポジ型フォトレジストの開発 ··············································································· 35[１]LAER 型レジストと HAER 型レジスト ·········································································· 35[２]水系現像型レジスト ········································································································· 36[３]溶解阻止型レジスト ········································································································· 36

３.２.３

KrF 用ネガ型フォトレジストの開発 ··············································································· 37

３.２.４

KrF 用フォトレジストの研究課題 ··················································································· 37

３.３

ArF ドライ用フォトレジストの技術開発動向 ·························································· 37

３.３.１

ArF 用ポジ型フォトレジストの開発 ··············································································· 37[１]アクリル系ポジ型レジストの開発 ·················································································· 38[２]

ノルボルネン系ポジ型レジストの開発 ·········································································· 40[３]その他ポジ型レジストの開発 ·························································································· 43

３.３.２

ArF 用ネガ型フォトレジストの開発 ··············································································· 45[１]ヒドロキシ(OH)基樹脂系ネガ型レジストの開発 ························································· 46[２]脂環式エポキシ樹脂系ネガ型レジストの開発 ······························································· 47[３]その他樹脂系ネガ型レジストの開発 ·············································································· 47

３.３.３

ArF 用フォトレジスト成分材料の開発 ··········································································· 49[１]

高感度なアルキルスルホニウム塩感光剤の開発 ··························································· 49[２]

高透明なナフタレン環含有感光剤の開発 ······································································· 50[３]エッチング耐性の良いレジスト樹脂の開発 ··································································· 52[４]

密着性の良いレジスト樹脂の開発 ·················································································· 54

３.３.４

ArF 用プロセス材料と技術の開発 ··················································································· 55[１]プロセス材料の開発 ········································································································· 55[２]

プロセス技術の開発 ········································································································· 56

３.３.５

ArF 用フォトレジストの今後の研究課題 ······································································· 60

３.４

ArF 液浸用フォトレジストの技術開発動向 ······························································ 61

３.４.１

ArF 液浸リソグラフィー技術 ·························································································· 61

３.４.２

ArF 液浸リソグラフィー用レジストの開発 ··································································· 62

３.４.３

トップコート(カバーコート)の開発 ··············································································· 62

３.４.４

高屈折率液体の開発 ········································································································· 64

３.４.５

液浸露光装置の開発 ········································································································· 65

３.５

F2 用フォトレジストの技術開発動向 ········································································· 66

３.５.１

F2 用フォトレジスト ········································································································ 66

３.５.２

F2 用フォトレジストの開発 ···························································································· 66[１]

Selete の研究開発状況 ····································································································· 66[２]F2 用レジストポリマーの開発 ························································································ 68

３.５.３

F2 リソグラフィー技術の開発中止 ················································································ 72

３.６

X 線用フォトレジストの技術開発動向 ······································································· 72

３.６.１

X 線用フォトレジスト ······································································································ 72

３.６.２

X 線用フォトレジストポリマーの開発 ··········································································· 73３.６.３

X 線用フォトレジストの今後の研究課題 ······································································· 76３.７

電子線用フォトレジストの技術開発動向 ·································································· 76３.７.１

電子線用フォトレジスト ································································································· 76３.７.２

電子線用フォトレジストの開発 ······················································································ 77[１]電子線用フォトレジストの組成 ······················································································ 77[２]電子線用フォトレジストの開発 ······················································································ 78

３.８

その他のリソグラフィー微細化技術の開発動向 ····················································· 90

３.８.１

ナノパターニング技術の開発 ·························································································· 90

３.８.２

可視光リソグラフィー技術の開発 ·················································································· 92

３.８.３

レジストパターン縮小化技術の開発 ·············································································· 93

第４章 半導体用感光性材料の最新動向 ·················································································· 95
４.１ 半導体用表面保護コーティング材料(ポリイミド系) ·········································· 95
４.１.１

表面保護コーティング材料の概要 ·················································································· 95[１]

表面保護コーティング材料の必要性 ·············································································· 95[２]

表面保護コーティング材料の種類 ·················································································· 95[３]

表面保護コーティング用感光性ポリイミドの種類 ······················································· 96

４.１.２

ネガ型感光性ポリイミドの開発 ······················································································ 98[１]

ネガ型感光性ポリイミドの構造とその特性 ··································································· 98[２]

低温硬化可能なネガ型感光性ポリイミド ······································································· 99[３]アルカリ水溶液現像が可能なネガ型感光性ポリイミド ············································· 102[４]高耐熱性のネガ型感光性ポリイミド ············································································ 104[５]低熱膨張性のネガ型感光性ポリイミド ········································································ 106[６]高感度なネガ型感光性ポリイミド ················································································ 108

４.１.３

ポジ型感光性ポリイミド の開発 ·················································································· 109[１]

ポジ型感光性ポリイミドの構造とその特性 ································································· 109[２]低熱膨張性のポジ型感光性ポリイミド ········································································ 111[３]低誘電率なポジ型感光性ポリイミド ············································································ 114[４]高感度なポジ型感光性ポリイミド ················································································ 116[５]

柔軟性に富んだポジ型感光性ポリイミド ····································································· 118

４.２

半導体用表面保護コーティング材料(ポリベンゾオキサゾール系) ·············· 119

４.２.１

ポジ型感光性ポリベンゾオキサゾールの開発 ····························································· 119[１]

ポジ型感光性ポリイミドの問題点 ················································································ 120[２]

ポジ型感光性ポリベンゾオキサゾールの開発 ····························································· 120[３]

ポジ型感光性ポリベンゾオキサゾールの実用化 ························································· 125

４.２.２

ポジ型感光性ポリベンゾオキサゾールの改良研究 ····················································· 125[１]

高感度なポジ型感光性ポリベンゾオキサゾール ························································· 125[２]

感度、解像度が優れるポジ型感光性ポリベンゾオキサゾール ·································· 129[３]

i 線透過性に優れるポジ型感光性ポリベンゾオキサゾール ······································· 134[４]

現像残さ(スカム)が無いポジ型感光性ポリベンゾオキサゾール ······························ 137[５]

接着性の優れたポジ型感光性ポリベンゾオキサゾール ············································· 139[６]低温硬化性に優れるポジ型感光性ポリベンゾオキサゾール ······································ 141

４.２.３

ポジ型感光性ポリベンゾオキサゾールの製品 ····························································· 145

４.２.４

ネガ型感光性ポリベンゾオキサゾールの開発 ····························································· 146

４.３

半導体用層間絶縁膜材料 ······························································································· 148

４.３.１

平坦化用層間絶縁膜の開発 ···························································································· 148[１]

ネガ型感光性ポリイミド ································································································ 148[２]

ポジ型感光性ポリイミド ································································································ 149

４.３.２

低誘電率層間絶縁膜の開発 ···························································································· 149[１]

ポリイミド ······················································································································· 150[２]ポリベンゾシクロブテン ································································································ 152[３]

ポリシラザン ··················································································································· 156[４]

ポリフェニレンエーテル ································································································ 157[５]

ナフタリン ······················································································································· 158[６]

ノルボルネン ··················································································································· 159[７]

シリコーン ······················································································································· 160[８]

ポリアリールエーテルケトン ························································································ 161

４.４

半導体用再配線材料 ········································································································ 162

４.４.１

ネガ型感光性エポキシ樹脂の開発 ················································································ 163

４.４.２

ポジ型感光性ポリベンゾオキサゾールの開発 ····························································· 164

４.４.３

ネガ型感光性ポリイミドの開発 ···················································································· 164４.５半導体用実装基板材料 ···································································································· 165

４.５.１

LSI 高密度実装用高分子材料の開発 ············································································· 165

４.５.２

LSI 実装用厚メッキ銅多層配線材料の開発 ································································· 166

第５章 電子基板回路形成用フォトレジストの最新動向 ················································ 168
５.１ 電子基板回路形成用フォトレジストの開発最前線の概要 ································· 168
５.１.１

フォトレジストの開発動向 ···························································································· 168[１]

直描用レジスト ··············································································································· 169[２]

放熱用レジスト ··············································································································· 169

５.１.２

主要レジストメーカーの動向 ························································································ 170

５.２

液状フォトレジスト ········································································································ 172

５.２.１

液状フォトレジストの特徴 ···························································································· 172

５.２.２

ネガ型液状フォトレジストの開発 ················································································ 173

５.２.３

ポジ型液状フォトレジストの開発 ················································································ 174

５.２.４

液状フォトレジストの改良研究 ···················································································· 176[１]

微細配線用液状フォトレジストの開発 ········································································ 176[２]

高密着性微細加工用フォトレジストの開発 ································································· 176[３]高耐熱性フォトレジストの開発 ···················································································· 176[４]高感度な重合開始剤の開発 ···························································································· 176[５]

反応現像型フォトレジストの開発 ················································································ 177[６]

微細加工が可能なポジ型感光性樹脂組成物の開発 ····················································· 178[７]

ファインライン形成用の感光性樹脂組成物の開発 ····················································· 179[８]

耐溶剤性、耐水性、印刷適性に優れた感光性樹脂組成物の開発 ······························ 180

５.３

ドライフィルムフォトレジスト ·················································································· 181

５.３.１

ドライフィルムフォトレジストの特徴 ········································································ 181

５.３.２

ドライフィルムフォトレジストの組成とその反応機構 ············································· 182

５.３.３

ポジ型ドライフィルムフォトレジストの開発 ····························································· 184

５.３.４

ドライフィルムフォトレジストの改良研究 ································································ 186[１]

高解像度レジストの開発 ································································································ 186[２]

柔軟性レジストの開発 ···································································································· 187[３]

テント信頼性レジストの開発 ························································································ 187[４]ギザ性改良エレメントの開発 ························································································ 187[５]耐メッキ性レジストパターンの開発 ············································································ 188[６]

P-BGA 用高解像度レジストの開発 ··············································································· 188[７]

CSP、FC 用ファインピッチレジストの開発 ······························································ 189[８]

WL-CSP 用ドライフィルムレジストの開発 ································································ 189[９]

室温保存可能なオキセタン系ソルダーレジストの開発 ············································· 190[10]高追従性ドライフィルムソルダーマスクの開発 ························································· 191[11]

高感度、高密着性、高柔軟性感光性樹脂組成物の開発 ············································· 191

５.４

電着フォトレジスト ········································································································ 192

５.４.１

電着フォトレジストの特徴 ···························································································· 192

５.４.２

ネガ型電着フォトレジストの開発 ················································································ 194

５.４.３

ポジ型電着フォトレジストの開発 ················································································ 194[１]

乾燥不要な高感度ポジ型電着レジストの開発 ····························································· 195[２]

高温加熱不要なアニオン型電着レジストの開発 ························································· 196

５.５

直描用フォトレジスト ···································································································· 197

５.５.１

レーザーダイレクトイメージングシステムの特徴 ····················································· 197

５.５.２

LDI 用レジストの開発 ···································································································· 198[１]

ポジ型 LDI 用レジストの開発 ························································································ 198[２]

可視光 LDI 用レジストの開発 ························································································ 199[３]

LDI 用ポジ型転写レジストの開発 ················································································· 200

５.５.３

マイクロミラーアレイ直描対応感光性フィルムの開発 ············································· 201

５.５.４

各社の直描用フォトレジスト ························································································ 202

第６章 電子基板用感光性材料の最新動向 ············································································ 207
６.１ 電子基板用層間絶縁膜 ···································································································· 207
６.１.１

多層電子基板の特徴 ······································································································· 207

６.１.２

多層電子基板用感光性樹脂の製品 ················································································ 210

６.１.３

多層電子基板用感光性樹脂の改良研究 ········································································ 212[１]ポリイミド系感光性樹脂の開発 ···················································································· 212[２]ポリベンゾオキサゾール系感光性樹脂の開発 ····························································· 214[３]

シクロオレフィンポリマー系感光性樹脂の開発 ························································· 215[４]ポリフェニレンエーテル系感光性樹脂の開発 ····························································· 216[５]エポキシ樹脂系感光性樹脂の開発 ················································································ 217[６]芳香族ホルムアルデヒド樹脂系感光性樹脂の開発 ····················································· 218

６.２

電子基板用カバーレイ ···································································································· 219

６.２.１

電子基板用カバーレイ材料の必要特性 ········································································ 219

６.２.２

電子基板用カバーレイ材料の改良研究 ········································································ 219[１]

微細パターンを位置精度良く形成できる感光性カバーレイフィルムの開発 ·········· 219[２]低吸湿性に優れるポリイミド系感光性カバーレイフィルムの開発 ·························· 222[３]

熱可塑性のポリイミド系ネガ型感光性カバーレイフィルムの開発 ·························· 222[４]

可溶性ポリイミドからなる高耐熱性カバーレイフィルムの開発 ······························ 224[５]電気特性に優れ、低反り性のエポキシ変性
ポリイミド系カバーレイフィルムの開発 ···································································· 225[６]

ノンハロゲン難燃性感光性カバーレイフィルムの開発 ············································· 226[７]

現像性、可とう性に優れる絶縁フィルムからなるフレキシブル配線板の開発 ······· 227

６.３電子基板用ソルダーレジスト ······················································································ 228

６.３.１

電子基板用ソルダーレジストの種類 ············································································ 228

６.３.２

電子基板用ドライフィルムソルダーレジストの改良研究 ········································· 230[１]

テープ CSP 対応ドライフィルムソルダーレジストの開発 ······································· 230[２]

高解像度エポキシ系ドライフィルムフォトレジストの開発 ······································ 231[３]高強度、高耐熱、高接着性を有する
ポリイミド系ドライフィルムレジストの開発 ····························································· 232[４]

剥離性の良い感光性樹脂組成物、およびドライフィルムフォトレジストの開発 ····························································· 232[５]帯電防止層を有するドライフィルムレジストの開発 ················································· 234

６.３.３電子基板用液状ソルダーレジストの改良研究 ····························································· 234[１]

ポリイミド系ソルダーレジストインキの開発 ····························································· 234[２]エポキシアクリレート樹脂系ソルダーレジストインキの開発 ·································· 237[３]エポキシ樹脂系ソルダーレジストインキの開発 ························································· 242[４]

アクリル樹脂系ソルダーレジストインキの開発 ························································· 245

６.４高密度実装用感光性樹脂 ······························································································· 248

６.４.１

インターポーザー用感光性樹脂の開発 ········································································ 248[１]

高密度実装用インターポーザー ···················································································· 248[２]

超高速伝送・超高密度実装を実現する LSI チップ接続インターポーザー ·············· 250[３]光電気複合実装 3 次元モジュール用高密度配線インターポーザー ·························· 250

６.４.２

バンプ用感光性樹脂の開発 ···························································································· 251

６.５

高速伝送用光導波路 ········································································································ 253

６.５.１

光・電気複合回路基板の技術動向 ················································································ 253

６.５.２

ポリマー光導波路の開発 ······························································································· 255[１]

代表的なポリマー光導波路 ···························································································· 255[２]

紫外線硬化アクリル樹脂の開発 ···················································································· 256[３]

感光性ゾルゲル材料の開発 ···························································································· 256

６.５.３

光導波路の作製 ··············································································································· 258[１]

光導波路の各種作製方法 ································································································ 258[２]

加熱エンボス法による POF と接続可能な大口径高分子光導波路の作製 ················ 258[３]

自己形成光導波路の作製 ································································································ 260

６.５.４

光導波路の実装製品の開発 ···························································································· 261

第７章 フラットパネルディスプレイ用感光性材料の最新動向 ·································· 265
７.１ 液晶ディスプレイ ············································································································· 265
７.１.１

カラーフィルタ(含ブラックマトリックス) ······························································· 266[１]

カラーフィルタの構造 ···································································································· 266[２]

カラーフィルタの製造方法 ···························································································· 267[３]

ネガ型カラーフィルタ用レジストの開発 ····································································· 273[４]

ポジ型カラーフィルタ用レジストの開発 ····································································· 275[５]

スピンレス用ポジ型カラーフィルタ用レジストの開発 ············································· 275[６]

高コントラストカラーフィルタ用レジストの開発 ····················································· 276[７]

ハーフトーンカラーフィルタ用レジストの開発 ························································· 278[８]線幅均一性カラーフィルタ用レジストの開発 ····························································· 278[９]高密着性カラーフィルタ用レジストの開発 ································································· 278[10]

高透明性カラーフィルタ用オレフィン系レジストの開発 ········································· 279[11]耐熱性、安定性、相溶性の優れる光ラジカル発生剤の開発 ······································ 280[12]高感度なブラックマトリックスの開発 ········································································ 281[13]

低温硬化ポリイミド系ブラックマトリックスの開発 ················································· 282[14]

次世代カラーフィルタ用レジストに求められる特性 ················································· 283

７.１.２

スペーサー(セルギャップ)用材料の開発 ···································································· 284

７.１.３永久膜(オーバーコート)の開発 ···················································································· 285[１]

透明性、耐熱性、平坦性、塗布性、現像性がよい感光性樹脂組成物の開発 ·········· 286[２]

薄膜パターン形成用感光性樹脂組成物の開発 ····························································· 287[３]

耐クラック性に富むポリシロキサン系ネガ型感光性樹脂組成物の開発 ·················· 289

７.１.４

液晶配向膜の開発 ··········································································································· 290[１]

カルコン基側鎖を有するスチレン骨格樹脂の開発 ····················································· 291[２]

カルコン基側鎖を有するポリイミド骨格樹脂の開発 ················································· 293[３]

ラビングレス液晶配向膜用樹脂の開発 ········································································ 293

７.１.５

市場の動向 ······················································································································· 295

７.１.６

各社の状況 ······················································································································· 295

７.２

プラズマディスプレイ ···································································································· 298

７.２.１

プラズマディスプレイの特徴 ························································································ 298７.２.２

バス電極形成用材料の開発 ···························································································· 300

７.２.３

透明電極形成用材料の開発 ···························································································· 302

７.２.４

リブ(隔壁)形成用材料の開発 ························································································ 302７.２.５

蛍光体形成用材料の開発 ······························································································· 305

７.２.６

誘電体形成用材料の開発 ······························································································· 305

７.２.７

市場の動向 ······················································································································· 306

７.２.８

各社の状況 ······················································································································· 306

７.３

EL ディスプレイ ··············································································································· 308７.３.１

低分子発光材料と高分子発光材料 ················································································ 309

７.３.２

駆動方式の種類とその特長 ···························································································· 310

７.３.３

フォトレジストの開発 ··································································································· 312

７.３.４

長寿命化材料の開発 ······································································································· 315

７.３.５

市場の動向 ······················································································································· 317

７.３.６

各社の状況 ······················································································································· 318

７.４
７.５

表面電界ディスプレイ ···································································································· 319
フレキシブルディスプレイ ··························································································· 321

７.５.１

有機トランジスタの開発 ······························································································· 322

７.５.２

フィルム型液晶(LC)ディスプレイの開発 ··································································· 325

７.５.３

フレキシブル EL ディスプレイの開発 ········································································· 326

第８章

結語 ··································································································································· 328

略 語 表 ················································································································································· 335
参考文献 ················································································································································· 338