JP5967778B2 - 導電性ポリマー−金属複合体の析出方法、導電性ポリマー−金属複合体、フレキシブル基板上への導電配線パターン形成方法、及びフレキシブル基板 - Google Patents
導電性ポリマー−金属複合体の析出方法、導電性ポリマー−金属複合体、フレキシブル基板上への導電配線パターン形成方法、及びフレキシブル基板 Download PDFInfo
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- JP5967778B2 JP5967778B2 JP2013526899A JP2013526899A JP5967778B2 JP 5967778 B2 JP5967778 B2 JP 5967778B2 JP 2013526899 A JP2013526899 A JP 2013526899A JP 2013526899 A JP2013526899 A JP 2013526899A JP 5967778 B2 JP5967778 B2 JP 5967778B2
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Classifications
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
- H05K3/106—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam by photographic methods
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
- H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
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- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
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Description
前記エネルギーを与えるために、光とともに熱又は音を使用してもよい。
また、前記モノマーは共役構造を有する直鎖系、芳香族系、複素環式化合物系またはヘテロ原子化合物系の有機ポリマーを与えるモノマーであってよい。
また、前記モノマーはピロール、3,4−エチレンジオキシチオフェン及びアニリンからなる群から選ばれてよい。
また、前記溶液の溶媒はアセトニトリル、エタノール、水からなる群から選択されてよい。
また、前記金属イオンは、金、白金、パラジウム、ルテニウム、イリジウム、銀、銅、ニッケル、鉄、クロム、亜鉛、カドミウム、テルル、スズ、鉛からなる群から選ばれた少なくとも一つの金属のイオンであってよい。
また、前記モノマーとしてピロールを使用するとともに、その前記溶液中の濃度を0.1mol/L以上とし、前記金属イオンとしてAg+を使用するとともに、その前記溶液中の濃度を前記ピロールの濃度の5倍以上20倍以下としてよい。
また、前記モノマーとしてピロールを使用するとともに、その前記溶液中の濃度を0.05mol/L以上とし、前記金属イオンとしてCu2+を使用するとともに、その前記溶液中の濃度を前記ピロールの濃度の等倍以上10倍以下としてよい。
本発明の他の側面によれば、前記何れかの方法によって析出した導電性ポリマー−金属複合体が与えられる。
本発明の更に他の側面によれば、有機導電性ポリマーと金属ナノ粒子を含む線状体を有し、前記金属ナノ粒子の少なくとも一部が前記線状体である有機導電性ポリマーの表面に露出している、導電性ポリマー−金属複合体が与えられる。
ここで、前記線状体の直径は1μm以下であってよい。
また、前記線状体の直径は0.1μm以上であってよい。
また、前記線状体のアスペクト比は2〜10であってよい。
また、前記金属ナノ粒子の直径は10〜200nmであってよい。
上で説明した反応機構によれば、図2に示すようにポリマー中の電子が励起され到達し得る高いエネルギー順位(たとえばLUMO)よりも金属のRedox電位が低いエネルギー位置にある場合、ポリマーと金属との複合材料が析出し得ることがわかる。
上述の反応機構の説明及び以下の実施例から、以下にあげるモノマー及び金属を本発明の原料に使用することができることがわかる。
・モノマー:共役構造を有する直鎖系、芳香族系、複素環式化合物系、ヘテロ原子化合物系の有機ポリマーを得ることができるモノマー。
・金属:金、白金、パラジウム、ルテニウム、イリジウム、銀、銅、ニッケル、鉄、クロム、亜鉛、カドミウム、テルル、スズ、鉛、およびそれらの合金。
導電性ポリマーを得るためのモノマーとしてピロール、3,4−エチレンジオキシチオフェン(EDOT)、アニリンを、金属イオンとしてCu2+、Ag+を、またアニオンとしてCu2+の場合には塩化物イオン(Cl−)を、Ag+に対しては硝酸イオン(NO3 −)を使用して、紫外線照射による導電性ポリマー−金属複合体の析出を行った。モノマーの種類と濃度、金属イオンの種類と濃度を変化させて30通りの実験を行った。もちろん、これらの実施例は単なる例示であって、特許請求の範囲に定義される本発明の技術的範囲を限定するものでないことに注意すべきである。これらの実験の際の実験条件、測定条件は以下の通りである。
温度:室温
溶媒:アセトニトリル、エタノール、水
基材:ガラス
紫外光の強度:50mW/cm2
波長:436nm・405nm・365nm(輝線)
析出時間:0.5〜240min
○抵抗値の測定方法
三菱化学製Loresta AP MCP−T400を用いた4探針法
(測定原理は良く知られているので省略するが、必要であれば非特許文献6を参照されたい)
このようにして行った実験の結果を表2に示す。
本発明と非特許文献4の比較実験を行った。実験条件、測定条件は以下の通りであった。
ピロール濃度:0.1mol/L
金属イオン濃度:0.1mol/L
アニオン:NO3 −、アニオン濃度:0.1mol/L
溶媒:アセトニトリル
基材:ガラス
反応時間:60min
なお、比較対照実験の結果、導電性ポリピロール単体(PTSアニオンドープ)の抵抗は0.2×102Ωであった。
注2:非特許文献2からのデータ
注3:特許文献1及び非特許文献3からのデータ
導電性ポリマー−金属複合体を析出させる際に与えるエネルギーとして光と熱の両者を使用した場合の反応系の挙動の例について以下に示す。
本発明の導電性ポリマー−金属複合体と基材との密着性を調べるために、以下の条件で、テープ剥離試験を行った。
膜厚の薄い試料を作るために、あらかじめ溶液中に分散した状態の複合体(おそらく従来よりも粒子サイズが小さい)を作製し、その溶液をテープ剥離試験対象の各種の基材上に滴下・乾燥させた。
より詳細な実験条件は以下の通りであった。
○用意した溶液
ピロール濃度:0.2mol/L
金属(Ag)イオン濃度:1.0mol/L
アニオン:NO3 −、アニオン濃度:1.0mol/L
溶媒:アセトニトリル(ピロールをアセトニトリル10mlに溶解)
○重合処理
上記溶液を以下の構造のセル(小さく薄い容器)に収容し、輝線波長436nm、405nm又は365nm、強度60mW/cm2の光で10分間、室温で重合を行った。
セル構造:厚さ1mmのSiシートを切り抜き、周りを厚さ1mmの光学ガ ラスで挟み込んだもの。
○試験対象基材への複合体の付着処理
重合処理後の複合体が分散した溶液を、マイクロピペットを用いて試験対象基材上に滴下した。滴下量は50μLに固定した。溶液滴下後の基材をドラフト中で自然乾燥させた。自然乾燥時の証明条件は、全暗黒ではなく、通常の室内作業時の照明条件(蛍光灯)下で行った。乾燥中の照明光の照射量は積算光量計で1mW以下であった。
○テープ剥離試験
テープ剥離試験は、めっきの密着性試験方法(JIS-H8504)の中の引きはがし試験方法の1つである。この試験は、めっき面に粘着性のあるテープをはり付け、これを急速にかつ強く引きはがすことによって、めっきの密着性を調べるものである。テープ剥離試験は一般には貴金属のめっき等、比較的薄いめっきに適しており、厚いめっきには適さない。しかし、密着性が良好な場合には、非破壊試験となることから完成品の確認検査として用いられるので、本発明の導電性ポリマー−金属複合体と基材との密着性を調べるために、このテープ剥離試験を用いた。
一部の基材については密着性が不十分(×)、あるいはかなり低い(△)という実験結果が出た(図11〜図13、図15〜図17、図19)が、これは本発明の複合体が必ずしも当該基材一般に適合しないことを意味するものではない。基材として表面未処理のガラス(つまり非常に平滑なガラス:図19)と表面ブラスト処理(表面にブラスト剤を噴射して粗面化)したガラス(図18)では密着性が大きく異なるというテープ剥離試験結果からわかるように、基材表面の物理的状態(表面粗さなど)が密着性に大きな影響を与える。従って、実施例のテープ剥離試験の結果が十分でなかった基材についても、同種の別の特定の基材を使用した場合には、基材の製造に実際に使用する原料や製造方法、あるいはその後の処理方法の違いから、良好な密着性が得られる可能性があると考えられる。
何れにせよ、重合処理が終わった後の複合体が分散している溶液を単に滴下して乾燥させるという単純でかつ広範な状況に簡単に適用可能な付着方法を使用するだけで、通常密着性が非常に低いテフロンでさえ高い密着性を得ることができる本発明の複合体の実用性は非常に高いと考えられる。
密着性試験で接着剤、各種塗布剤などの通常の材料との密着性が非常に低いことで知られているテフロンに対して、本発明の導電性ポリマー−金属複合体が高い密着性を示したことに着目して、密着状態にある両者の断面を作成し、これを顕微鏡で観察した写真を図20に示す。
なお、写真中で「埋込樹脂」と表示しているものは、サンプルをエポキシなどの「樹脂」に「埋込」み、研磨によって、観察する断面を露出させる際に用いるものである。また、小倍率と大倍率の写真を二組示しているが、この理由は以下の通りである。ここで観察した材料は新規な材料であるため、断面調整法が確立されておらず、視野全体に渡ってきれいな平滑面が出ていない(視野全体にわたって焦点があっていない)。そこで、2箇所の観察視野のそれぞれについて、断面作成や撮影についてできるだけ条件を揃えた上で小倍率と大倍率の写真を示し、これらが同様な断面状態になっているように見えることを示した。
断面写真中で、本発明の導電性ポリマー−金属複合体である導電材料とテフロン製の基材との界面を見ると、大倍率側の断面写真である右側の写真で見ても、基材の非常に細かな凹凸にまで導電材料が入り込んでいて、剥離することなく、ほとんど一体化していると言えるまでに密着していることが判る。また、2箇所の断面の何れでも全く同じ密着状況が観察されたことにより、他の任意の断面においても同様な状態になっていることの蓋然性が高い。
テフロンが通常の溶剤に溶解しないことは周知の事項であり、またこの導電材料を基材上に塗布・形成する際に使用した溶媒も当然テフロンを溶解するものではない。それにもかかわらず、両者の間に全く隙間が認められない程度まで両者が密着していることは注目すべきことである。
本発明の導電性ポリマー−金属複合体付き基材を折り曲げ試験をした結果を図21及び図22に示す。
本発明の導電性ポリマー−金属複合体を柔軟な材料の上に形成しても、本複合体がそのような基材の変形に対して剥離することなく十分追随し、かつ大きく変形した状態でも導電性を維持することを示すため、紙製の基材上に本発明の導電性ポリマー−金属複合体を形成して実際に基材を変形させる実験を行った。なお、ここで、基材上に形成した本発明の導電性ポリマー−金属複合体は「テープ剥離試験」に使用したポリマー及び金属と同じものを使用した。
1枚目の図21の写真はそのようにして作製した複合体付き基材である。この複合体が低い抵抗値を有することをテスターで測定した(測定された抵抗値:約340Ω)。
これを基材の左右片がほぼ90度程度の角度をなす程度まで大きく折り曲げてみたが、2枚目の図22の写真に示すように、剥離などは全く見られなかった。また、この状態における抵抗値を測定したところ、測定点や測定時のプローブの押圧力を無変形時と変形(折り曲げ)時で同一とすることが困難であったため、両者の測定値を直ちに比較することはできないが、それでも測定された抵抗値は2kΩと、十分に低い値を示し、折り曲げによっても導電性が失われないことが判った。
Claims (15)
- 導電性有機ポリマーの原料となるモノマーとアニオン、金属イオンとを含む溶液に、前記金属イオンを還元可能なエネルギーレベルに電子を励起するに必要なエネルギーを有する光を照射する導電性ポリマー−金属複合体析出方法。
- 前記エネルギーを与えるために、光とともに熱又は音を使用する、請求項1に記載の方法。
- 前記モノマーは共役構造を有する直鎖系、芳香族系、複素環式化合物系またはヘテロ原子化合物系の有機ポリマーを与えるモノマーである、請求項1に記載の方法。
- 前記モノマーはピロール、3,4−エチレンジオキシチオフェン及びアニリンからなる群から選ばれる、請求項3に記載の方法。
- 前記溶液の溶媒はアセトニトリル、エタノール、水からなる群から選択される、請求項1に記載の方法。
- 前記金属イオンは、金、白金、パラジウム、ルテニウム、イリジウム、銀、銅、ニッケル、鉄、クロム、亜鉛、カドミウム、テルル、スズ、鉛からなる群から選ばれた少なくとも一つの金属のイオンである、請求項1に記載の方法。
- 前記モノマーとしてピロールを使用するとともに、その前記溶液中の濃度を0.1mol/L以上とし、
前記金属イオンとしてAg+を使用するとともに、その前記溶液中の濃度を前記ピロールの濃度の5倍以上20倍以下とする、
請求項6に記載の方法。 - 前記モノマーとしてピロールを使用するとともに、その前記溶液中の濃度を0.05mol/L以上とし、
前記金属イオンとしてCu2+を使用するとともに、その前記溶液中の濃度を前記ピロールの濃度の等倍以上10倍以下とする、
請求項6に記載の方法。 - 請求項1から8の何れか1項に記載の方法によって、フレキシブル基板上へ導電性ポリマー−金属複合体を析出させることを特徴とする、フレキシブル基板上への導電配線パターン形成方法。
- 有機導電性ポリマーと金属ナノ粒子を含み、アスペクト比が2以上である線状体を有し、前記金属ナノ粒子の少なくとも一部が前記線状体である有機導電性ポリマーの表面に露出している、導電性ポリマー−金属複合体。
- 前記線状体の直径は1μm以下である、請求項10に記載の導電性ポリマー−金属複合体。
- 前記線状体の直径は0.1μm以上である、請求項11に記載の導電性ポリマー−金属複合体。
- 前記線状体のアスペクト比は10以下である、請求項10に記載の導電性ポリマー−金属複合体。
- 前記金属ナノ粒子の直径は10〜200nmである、請求項10〜13の何れか1項に記載の導電性ポリマー−金属複合体。
- 請求項10〜14の何れか1項に記載の導電性ポリマー−金属複合体を用いて導電配線パターンを形成したフレキシブル基板。
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
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JP2011168502 | 2011-08-01 | ||
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PCT/JP2012/069236 WO2013018732A1 (ja) | 2011-08-01 | 2012-07-27 | 導電性ポリマー-金属複合体の析出方法及び導電性ポリマー-金属複合体 |
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US9622346B2 (en) * | 2012-10-24 | 2017-04-11 | National Institute For Materials Science | Adhesive body comprising conductive polymer-metal complex and substrate and method for forming the same, conductive polymer-metal complex dispersion liquid, method for manufacturing the same and method for applying the same, and method for filling hole using conductive material |
US9841369B1 (en) * | 2016-02-03 | 2017-12-12 | Myron E. Taylor, Jr. | System of analyzing a coating test |
KR101783124B1 (ko) * | 2016-02-03 | 2017-09-28 | 인천대학교 산학협력단 | 금속-폴리아닐린 복합체의 합성방법 |
JP2019046728A (ja) * | 2017-09-06 | 2019-03-22 | 国立研究開発法人物質・材料研究機構 | 薄膜用導電性ポリマー・金属複合体材料 |
CN111171356B (zh) | 2018-10-24 | 2021-06-22 | 电子科技大学 | 一种制备复合型导电聚合物的方法 |
CN112164685B (zh) * | 2020-08-31 | 2023-03-31 | 浙江大学 | 一种有机包覆抗腐的键合银丝及其制备方法 |
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US5855755A (en) | 1995-06-19 | 1999-01-05 | Lynntech, Inc. | Method of manufacturing passive elements using conductive polypyrrole formulations |
US6334965B1 (en) | 1999-09-07 | 2002-01-01 | Lynntech, Inc. | Electronically conductive polymers |
JP2004087427A (ja) | 2002-08-29 | 2004-03-18 | Hitachi Chem Co Ltd | 導電性高分子−金属クラスタ複合体電極およびその製造方法 |
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JP5550843B2 (ja) | 2009-03-19 | 2014-07-16 | ラピスセミコンダクタ株式会社 | 半導体装置の製造方法 |
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