JP2004117709A - Positive photosensitive resin composition, method for manufacturing pattern, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition containing a heat resistant resin having photosensitivity, a method for manufacturing patterns using the same, and electronic components. <P>SOLUTION: The positive photosensitive resin composition contains (A) a polymeric compound having at least one phenolic hydroxyl group or carboxyl group in the molecule, (B) a compound generating an acid by irradiation with active rays, and (C) a compound having an organic group convertible to carboxylic acid by an acid catalyst effect, and has excellent sensitivity and resolution. <P>COPYRIGHT: (C)2004,JPO

Description

ここで、前記構造中のＹは、具体的にはジフェニル、ジフェニルエーテル、ジフェニルチオエーテル、ベンゾフェノン、ジフェニルメタン、ジフェニルプロパン、ジフェニルヘキサフルオロプロパン、ジフェニルスルホキシド、ジフェニルスルホン、ベンゼン、ナフタレン、ペリレンなどの骨格を有する芳香族炭化水素残基や、ブタン、シクロブタン、シクロヘキサン、アダマンタンなどの骨格を有する脂肪族炭化水素残基、あるいは次の構造を有するものが挙げられる。なお、ｐはポリマーを示す。
【００３１】
【化２】

（式中、Ｚ、Ｚ’はアルキル基あるいはアルキル置換又は無置換のヘテロ原子を示す。）またＲは酸の作用で分解し水素原子に変換し得る一価の有機基を示す。
【００３２】
この酸触媒作用で分解し水素原子に変換し得る一価の基Ｒとしては、例えば次の構造を有するアセタール若しくはケタールを構成するものが好ましいものとして挙げられる。
【００３３】
【化３】

（式中、Ｒ’、Ｒ”及びＲ’’’は各々独立に炭素数５以下のアルキル基であり、Ｘは炭素数３以上（好ましくは２０以下）の２価のアルキレン基（側鎖を有していてもよい）である。）
具体的には、テトラヒドロピラニル基、テトラヒドロフラニル基、アルキル置換テトラヒドロピラニル基、アルキル置換テトラヒドロフラニル基、アルコキシ置換テトラヒドロピラニル基、アルコキシ置換テトラヒドロフラニル基などが典型的な例として例示されるが、これらに限定されるものではない。
最も好ましい基はテトラヒドロピラニル基である。
【００３４】
また酸の作用で分解し水素原子に変換し得る一価の基として、一価のアルコキシアルキル基又はアルキルシリル基、アルコキシカルボニル基なども挙げられる。これらに特に制限はないが、好ましい炭素数としてはアルコキシアルキル基では２〜５、アルキルシリル基では１〜２０、アルコキシカルボニル基では２〜１５である。
【００３５】
具体的には、メトキシメチル基、エトキシメチル基、イソプロポキシメチル基、ｔ−ブトキシメチル基、エトキシエチル基、メチルシリル基、エチルシリル基、ｔ−ブチルジメチルシリル基、ｔ−ブトキシカルボニル基などが典型的な例として例示されるが、これらに限定されるものではない。
好ましい基はメトキシメチル基、１−エトキシメチル基、ｔ−ブチルジメチルシリル基、ｔ−ブトキシカルボニル基である。
【００３６】
また、前記−ＣＯＯＲで示される基中のＲに関しては一価のアルキル基を用いることもできる。これらに特に制限はないが、好ましい炭素数としては１〜１０である。
【００３７】
具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、アミル基などが典型的な例として例示されるが、これらに限定されるものではない。
最も好ましい基はｔ−ブチル基である。
【００３８】
（Ｃ）成分の量は、感度と硬化後の膜質の観点から（Ｃ）成分がオリゴマーあるいはポリマーの場合に（Ａ）成分１００重量部に対して１〜１００重量部とすることが好ましく、１０〜１００重量部とすることがより好ましい。それ以外の場合は（Ａ）成分１００重量部に対して１〜５０重量部とすることが好ましく、１〜２５重量部とすることがより好ましい。
【００３９】
本発明におけるポジ型感光性樹脂組成物には、必要により密着性付与のための有機ケイ素化合物、シランカップリング剤、レベリング剤等の密着性付与剤を添加してもよい。
これらの例としては、例えば、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、尿素プロピルトリエトキシシラン、トリス（アセチルアセトネート）アルミニウム、アセチルアセテートアルミニウムジイソプロピレートなどが挙げられる。
密着性付与剤を用いる場合は、（Ａ）成分１００重量部に対して、０．１〜２０重量部が好ましく、０．５〜１０重量部がより好ましい。
【００４０】
本発明においてはこれらの成分を溶剤に溶解し、ワニス状にして使用することができる。
溶剤としては、例えばＮ−メチル−２−ピロリドン、γ−ブチロラクトン、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、２−メトキシエタノール、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル−１，３−ブチレングリコールアセテート、１，３−ブチレングリコールアセテート、シクロヘキサノン、シクロペンタノン、テトラヒドロフランなどがあり、単独でも混合して用いても良い。
溶剤の量に特に制限はないが、一般に組成物中溶剤の割合が４０〜７５重量％となるように用いられる。
【００４１】
本発明のポジ型感光性樹脂組成物を使用し、パターンを製造する方法について、以下に説明する。
（１）まず該組成物を適当な支持体、例えば、シリコンウエハ、セラミック、アルミ基板などに塗布する。
ここで、塗布方法としてはスピンナーを用いた回転塗布法、スプレーコータを用いた噴霧塗布法、浸漬法、印刷法、ロールコーティング法などが挙げられるが、特に限定されるものではない。
（２）次に好ましくは６０〜１２０℃でプリベークして塗膜を乾燥する。
（３）その後、所望のパターン形状に活性光線を照射する。
（４）次に、好ましくは５０〜１５０℃で加熱を行う。ここで活性光線を照射した後に加熱を行うのは、この加熱により、照射部表層部に発生した酸を底部にまで拡散させることができ、好ましいからである。
（５）次に現像して照射部を溶解除去することによりパターンを得る。
【００４２】
ここで、現像に用いる現像液としては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、珪酸ナトリウム、メタ珪酸ナトリウム、アンモニアなどの無機アルカリ類、エチルアミン、ｎ−プロピルアミンなどの一級アミン類、ジエチルアミン、ジ−ｎ−プロピルアミンなどの二級アミン類、トリエチルアミン、メチルジエチルアミンなどの三級アミン類、ジメチルエタノールアミン、トリエタノールアミンなどのアルコールアミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシドなどの、四級アンモニウム塩などのアルカリ水溶液などを挙げることができる。また、これに水溶性有機溶媒や界面活性剤を適当量添加した水溶液を好適に使用することができる。
【００４３】
現像方法としては例えば、スプレー法、パドル法、浸漬法、超音波法などの公知の方式が可能である。次に現像によって形成したパターンをリンスすることができる。リンス液としては蒸留水を使用することができる。
次に加熱処理を行い、耐熱性に富む最終パターンを得ることができる。加熱温度は一般に１５０〜４５０℃とされる。
【００４４】
本発明の感光性樹脂組成物は、半導体装置や多層配線板などの電子部品に使用することができ、具体的には、半導体装置の表面保護膜層や層間絶縁膜層、多層配線板の層間絶縁膜層などの形成に使用することができる。本発明の半導体装置は、前記組成物を用いて形成される表面保護膜層や層間絶縁膜層を有すること以外は特に制限されず、様々な構造をとることができる。
【００４５】
本発明の半導体装置製造工程の一例を図面を参照して以下に説明する。
図１は多層配線構造の半導体装置の製造工程図である。
図１において、回路素子を有するＳｉ基板などの半導体基板１は、回路素子の所定部分を除いてシリコン酸化膜などの保護膜層２などで被覆され、露出した回路素子上に第１導体層３が形成されている。その後、前記半導体基板１上にスピンコート法などで層間絶縁膜層４が形成される（工程（ａ））。
【００４６】
次に塩化ゴム系、フェノールノボラック系等の感光性樹脂層５が前記層間絶縁膜層４上にスピンコート法で形成され、公知の写真食刻技術によって所定部分の層間絶縁膜層４が露出する様に窓６Ａが設けられている（工程（ｂ））。
前記窓６Ａの層間絶縁膜層４は、酸素、四フッ化炭素などのガスを用いるドライエッチング手段によって選択的にエッチングされ、窓６Ｂがあけられている。ついで窓６Ｂから露出した第１導体層３を腐食することなく、感光樹脂層５のみを腐食するようなエッチング溶液を用いて感光樹脂層５が完全に除去される（工程（ｃ））。
【００４７】
さらに公知の写真食刻技術を用いて、第二導体層７を形成させ、第１導体層３との電気的接続が完全に行われる（工程（ｄ））。
３層以上の多層配線構造を形成する場合には、前記の工程を繰り返して行い各層を形成することができる。
【００４８】
次に表面保護膜層８が形成される。
この図１の例では、この表面保護膜層８に対し、前記感光性樹脂組成物をスピンコート法にて塗布、乾燥し、所定部分に窓６Ｃを形成するパターンを描いたマスク上から光を照射した後アルカリ水溶液にて現像してパターンを形成し、加熱して樹脂膜層とする。この樹脂膜層は、導体層を外部からの応力、α線などから保護するものであり、得られる半導体装置は信頼性に優れる。
なお、前記例において、層間絶縁膜層を本発明の感光性樹脂組成物を用いて形成することも可能である。
【００４９】
【実施例】
以下、実施例により本発明を具体的に説明する。
【００５０】
本実施例では、（Ａ）成分（下記「化４」に示す）を１００重量部に対し、（Ｂ）成分（酸発生剤（下記「化５」に示す））、（Ｃ）成分（下記「化６」に示す）、および必要に応じて増感剤（下記「化７」に示す）を「表１」に示した所定量にて配合し、γ−ブチロラクトンに溶解させ、得られた溶液を用いて塗膜を形成し、感光特性評価を行った。
【００５１】
［実施例１］
本実施例では、表１に示すように、（Ａ）成分（ポリアミドフェノール（Ａ１））１００重量部に対し、（Ｂ）成分（酸発生剤（ＤＩＡＳ））、（Ｃ）成分（Ｃ１）を「表１」に示した所定量にて配合しγ−ブチロラクトンに溶解させた。
【００５２】
前記溶液をシリコンウエハ上にスピンコートして、乾燥膜厚２〜３μｍの塗膜を形成し、そののち干渉フィルターを介して、超高圧水銀灯を用いてｉ線（３６５ｎｍ）露光を行った。
露光後、１２０℃で３分間加熱し、テトラメチルアンモニウムヒドロキシドの２．３８％水溶液にて露光部のシリコンウエハが露出するまで現像した後、水でリンスしパターン形成に必要な最小露光量と解像度を求めた。
その結果を「表２」に記す。
【００５３】
［実施例２］
実施例１において、表１に示すように、（Ｃ）成分を（Ｃ２）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００５４】
［実施例３］
実施例１において、表１に示すように、（Ｃ）成分を（Ｃ３）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００５５】
［実施例４］
実施例１において、表１に示すように、（Ｃ）成分を（Ｃ４）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００５６】
［実施例５］
実施例１において、表１に示すように、（Ｃ）成分をポリマータイプの（Ｃ５）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００５７】
［実施例６］
実施例１において、表１に示すように、酸発生剤成分をＤＰＩに変更すると共に増感剤（９ＭｅＡｎ）を添加した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００５８】
［実施例７］
実施例６において、表１に示すように、酸発生剤成分をＭＰＩに変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００５９】
［実施例８］
実施例６において、表１に示すように、（Ａ）成分を（Ａ２）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００６０】
［実施例９］
実施例６において、表１に示すように、（Ａ）成分を（Ａ３）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００６１】
［実施例１０］
実施例６において、表１に示すように、（Ａ）成分を（Ａ４）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００６２】
［実施例１１］
実施例６において、表１に示すように、（Ａ）成分を（Ａ５）に変更した以外は実施例１と同様に操作し、同様な評価を行った。
その結果を「表２」に記す。
【００６３】
【表１】

【００６４】
【化４】

【００６５】
【化５】

【００６６】
【化６】

【００６７】
【化７】

【００６８】
【表２】

【００６９】
［比較例１］
実施例１において（Ｃ）成分を用いずに、ポリアミドフェノールの水酸基を酸活性基であるｔ−ブトキシカルボニル基にて保護した（Ａ６）を用い、以下同様に感光特性評価を行った。
その結果、解像度が３０μｍ、露光量が４００ｍＪ／ｃｍ^２であり、膨潤による解像度の低下、剥離が見られたうえ感度も低かった。
【００７０】
［比較例２］
実施例１においてＣ成分として保護基を導入していないフタル酸を用いて以下同様に感光特性評価を行った。
その結果、パターンは全く得られなかった。
【００７１】
［比較例３］
実施例１においてＣ成分として酸触媒作用にてフェノールを生ずる（Ｃ６）を用いて以下同様に感光特性評価を行った。
その結果、露光部の溶解速度が遅く、未露光部との間に良好な溶解速度差を得ることができず、露光量１０００　ｍＪ／ｃｍ^２にて解像度５０　μｍであった。
【００７２】
［比較例４］
実施例１においてＢ成分としてオニウム塩ではないＮＢＡＳを用いて以下同様に感光特性評価を行った。
その結果、未露光部の溶解阻止効果が不十分で、パターン形成に十分なコントラストが得られなかった。
【００７３】
【化８】

【００７４】
【化９】

【００７５】
【化１０】

【００７６】
本実施例のものは、すべて露光量が少なくて済むと共に、解像度がいずれも良好であった。これに対し、比較例のものはいずれも解像度の低下がみられたり、パターンが得られなかったり、露光量が高く良好なものではなかった。
【００７７】
【発明の効果】
本発明では、（Ａ）分子中に少なくとも一つのフェノール性水酸基あるいはカルボキシル基を有する高分子化合物、（Ｂ）活性光線照射により酸を発生する化合物、（Ｃ）酸触媒作用でカルボン酸に変換し得る有機基を有する化合物を含有したポジ型感光性樹脂組成物としたので、感度、解像度に優れるうえ、感光性を付与する耐熱性樹脂がいかなる構造であっても充分に対応でき、かつ、従来からのフォトレジストが有する問題を解決し、しかも接着性、耐熱性に富むという、効果を奏する。
【００７８】
また本発明のパターンの製造法によれば、前記組成物の使用により、機械特性、感度、解像度および耐熱性に優れ、良好な形状のパターンが得られる。
【００７９】
また、本発明の電子部品は、良好な形状と特性のパターンを有することにより、信頼性の高いものである。
【図面の簡単な説明】
【図１】多層配線構造の半導体装置の製造工程図である。
【符号の説明】
１…半導体基板
２…保護膜層
３…第１導体層
４…層間絶縁膜層
５…感光樹脂層
６Ａ、６Ｂ、６Ｃ…窓
７…第２導体層
８…表面保護膜層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a positive photosensitive resin composition containing a heat-resistant resin having photosensitivity, a method for producing a pattern using the same, and an electronic component.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film layer and an interlayer insulating film layer of a semiconductor element. However, in recent years, as semiconductor elements have become more highly integrated and larger, there has been a demand for thinner and smaller sealing resin packages, and methods such as LOC (lead-on-chip) and surface mounting by solder reflow have been adopted. Therefore, a resin having more excellent mechanical properties, heat resistance and the like than before has been required.
[0003]
On the other hand, photosensitive polyimide in which photosensitive properties are imparted to the resin itself has been used. However, the use of such a polyimide has a feature that a pattern forming process can be simplified and a complicated manufacturing process can be shortened.
Conventionally, heat-resistant photoresists using a photosensitive polyimide or a precursor thereof, and uses thereof are well known.
For example, in a negative photosensitive resin composition, for example, (1) a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, see Patent Documents 1, 2, 3, and 4); 2) a soluble polyimide having a photopolymerizable olefin (for example, see Patent Documents 7, 8, 9, and 10); and 3) an alkyl group at the ortho position of an aromatic ring having a benzophenone skeleton and a nitrogen atom bonded thereto. Self-sensitizing polyimides (for example, see Patent Documents 11 and 12) have been proposed.
[0004]
In the negative photosensitive resin composition, since an organic solvent such as N-methylpyrrolidone is required for development, a positive photosensitive resin that can be developed with an alkaline aqueous solution has recently been proposed. .
On the other hand, in a positive photosensitive resin composition, for example, (1) a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (for example, see Non-Patent Document 1), (2) a soluble hydroxylimide Alternatively, a method of mixing a naphthoquinonediazide compound with a polyoxazole precursor (for example, see Patent Documents 13 and 14), and a method of introducing naphthoquinonediazide into a soluble polyimide via an ester bond (for example, see Non-Patent Document 2). And (4) a mixture of naphthoquinonediazide and a polyimide precursor (for example, see Patent Document 15).
[0005]
However, the above-mentioned negative photosensitive resin composition has problems in terms of its function, such as resolution, and also, depending on the application, causes a decrease in the yield during production.
Further, in the above-mentioned ones, since the structure of the polymer used is limited, the physical properties of the finally obtained coating are limited, which is not suitable for multipurpose use.
On the other hand, the positive photosensitive resin composition also has the same problem as described above, because of the problem associated with the absorption wavelength of the photosensitive agent, the sensitivity and resolution are low, and the structure is limited.
[0006]
In addition, a compound obtained by mixing a diazonaphthoquinone compound with a polybenzoxazole precursor (see, for example, Patent Document 16), a compound in which a phenol moiety is introduced into a polyamic acid via an ester bond (see, for example, Patent Document 17), and the like. Although those in which a phenolic hydroxyl group is introduced instead of an acid have been proposed, these have a problem in that the developability is insufficient and the film loss of an unexposed portion and peeling of the resin from the base material occur. .
For the purpose of improving such developability and adhesion, a mixture of a polyamic acid having a siloxane moiety in a polymer skeleton (for example, see Patent Documents 18 and 19) has been proposed. There is a problem that storage stability deteriorates due to use.
In addition, for the purpose of improving storage stability and adhesion, those in which an amine terminal group is sealed with a polymerizable group (for example, see Patent Documents 20, 21, and 22) have been proposed. Since a diazoquinone compound containing a large number of aromatic rings is used as a generator, mechanical properties after thermosetting are remarkably reduced, and there is a problem that sensitivity is low, so that it is hard to say that the material is of a practical level.
[0007]
Various chemical amplification systems have been proposed for the purpose of improving the problems of the diazoquinone compounds. For example, (1) chemically amplified polyimide (for example, see Patent Document 23), (2) chemically amplified polyimide or polybenzoxazole precursor (for example, see Patent Documents 24, 25, 26, 27, and 28) Among these, those with high sensitivity show a decrease in film properties caused by low molecular weight, and those with excellent film properties show a decrease in sensitivity due to insufficient solubility caused by high molecular weight. It is hard to say.
Therefore, in reality, none of them are sufficient at a practical level.
[0008]
[Patent Document 1]
JP-A-49-11541
[Patent Document 2]
JP-A-50-40922
[Patent Document 3]
JP-A-54-145794
[Patent Document 4]
JP-A-56-38038
[Patent Document 5]
JP-A-59-108031
[Patent Document 6]
JP-A-59-220730
[Patent Document 7]
JP-A-59-232122
[Patent Document 8]
JP-A-60-6729
[Patent Document 9]
JP-A-60-72925
[Patent Document 10]
JP-A-61-57620
[Patent Document 11]
JP-A-59-219330
[Patent Document 12]
Japanese Patent Application Laid-Open No. 23-1533
[Patent Document 13]
JP-B-64-60630
[Patent Document 14]
U.S. Pat. No. 4,395,482
[Patent Document 15]
JP-A-52-13315
[Patent Document 16]
JP-A-1-46862
[Patent Document 17]
JP-A-10-307393
[Patent Document 18]
JP-A-4-31861
[Patent Document 19]
JP-A-4-46345
[Patent Document 20]
JP-A-5-197153
[Patent Document 21]
JP-A-9-183846
[Patent Document 22]
JP 2001-183835 A
[Patent Document 23]
JP-A-3-763
[Patent Document 24]
JP-A-7-219228
[Patent Document 25]
JP-A-10-186664
[Patent Document 26]
JP-A-11-202489
[Patent Document 27]
JP-A-2000-56559
[Patent Document 28]
JP 2001-194791 A
[Non-patent document 1]
J. Macromol. Sci. Chem. , A24, 10, 1407, 1987
[Non-patent document 2]
Macromolecules, 23, 1990
[0009]
[Problems to be solved by the invention]
The present invention uses a solubility-converting agent in which an alkali-soluble group is protected by a protecting group that can be removed under acid conditions, so that the sensitivity and the resolution are excellent, and the heat-resistant resin that imparts photosensitivity has any structure. A conventional photoresist can be prepared by blending a compound capable of sufficiently responding to the heat-resistant resin and capable of inducing the elimination reaction of the protective group in the solubility-converting agent by irradiation with actinic rays. It is an object of the present invention to provide a positive photosensitive resin composition which solves the above-mentioned problems and has excellent adhesiveness and heat resistance.
[0010]
The present invention also provides a method for producing a pattern which can be developed with an aqueous alkali solution, is excellent in sensitivity, resolution and heat resistance, and provides a pattern having a good shape by using the composition.
Further, the present invention provides a highly reliable electronic component by having a pattern having a good shape and characteristics.
[0011]
[Means for Solving the Problems]
A first invention for solving the above-mentioned problems is (A) a polymer compound having at least one phenolic hydroxyl group or carboxyl group in a molecule, (B) a compound which generates an acid upon irradiation with actinic rays, and (C) an acid catalyst. A positive photosensitive resin composition comprising a compound having an organic group which can be converted into a carboxylic acid by an action.
[0012]
In a second aspect based on the first aspect, the component (A) is selected from the group consisting of polyimide, polyoxazole, polythiazole, polyamideimide, polyamide, polyamic acid, polyhydroxyamide, polymercaptoamide, and polyphenylene oxide. The positive photosensitive resin composition is a polymer compound selected.
[0013]
In a third aspect, in the first or the second aspect, 0.01 to 50 parts by weight of the compound capable of generating an acid by irradiation with actinic rays of the above (B) is added to 100 parts by weight of the polymer compound of the above (A). And a positive photosensitive resin composition comprising
[0014]
A fourth invention is the positive photosensitive resin composition according to any one of the first to third inventions, wherein the compound (B) that generates an acid upon irradiation with actinic rays is an onium salt. It is in.
[0015]
According to a fifth aspect, in any one of the first to fourth aspects, the compound (C) which can be converted into a carboxylic acid by the action of an acid catalyst contains -COOR (where R is an action of an acid) in a molecule. And a monovalent organic group which can be decomposed and converted to a hydrogen atom.)
[0016]
According to a sixth aspect, in any one of the first to fifth aspects, an organic group capable of being converted into a carboxylic acid by the acid catalyst of the above (C) is added to 100 parts by weight of the polymer compound of the above (A). 1 to 100 parts by weight of a compound having a positive photosensitive resin composition.
[0017]
A seventh invention uses the positive photosensitive resin composition according to any one of the first to sixth inventions, and coats and dries on a supporting substrate, exposes, and uses an alkaline aqueous solution. A method for producing a pattern, comprising a step of developing and a step of heat treatment.
[0018]
An eighth invention is the method for producing a pattern according to the seventh invention, further comprising a drying step after the exposure step.
[0019]
A ninth aspect of the present invention resides in an electronic component having a pattern obtained by the manufacturing method according to the seventh or eighth aspect as a surface protective film layer or an interlayer insulating film layer.
[0020]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the contents of the present invention will be described in detail by embodiments.
[0021]
The positive photosensitive resin composition of the present invention comprises: (A) a polymer compound having at least one phenolic hydroxyl group or carboxyl group in a molecule; (B) a compound which generates an acid upon irradiation with actinic rays; A) a compound having an organic group that can be converted into a carboxylic acid by an acid catalyst.
[0022]
That is, in the present invention, since the positive photosensitive resin composition having each of the compound components (A), (B) and (C) is used, the composition is excellent in sensitivity and resolution and heat resistance for imparting photosensitivity. The present invention can sufficiently cope with any structure of the conductive resin, can solve the problems of the conventional photoresist, and can provide a resin having excellent adhesiveness and heat resistance.
[0023]
In the present invention, the component (A) needs to have at least one phenolic hydroxyl group or carboxyl group in the molecule. Due to their presence, appropriate solubility in a developing solution and adhesion to a substrate are provided.
[0024]
Here, the structure of the component (A) is not particularly limited, but may be selected from, for example, polyimide, polyoxazole, polythiazole, polyamideimide, polyamide, polyamic acid, polyhydroxyamide, polymercaptoamide, and polyphenylene oxide. A molecular compound is preferable, for example, in terms of processability and heat resistance. Further, they can be used as a copolymer or a mixture of two or more of these.
[0025]
Although the molecular weight of the polymer compound of the component (A) is not particularly limited, it is generally preferable that the average molecular weight is 4,000 to 200,000. The molecular weight can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
[0026]
In the composition of the present invention, a compound capable of generating an acid upon irradiation with actinic rays (hereinafter referred to as “acid generator”) is used as the component (B) together with the polymer compound used as the component (A).
Here, the amount of the component (B) is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the component (A) in order to improve the sensitivity and resolution at the time of exposure. 0.01 to 20 parts by weight, more preferably 0.5 to 15 parts by weight.
[0027]
The acid generator (B) used in the present invention is a compound having an organic group which can be converted into a carboxylic acid by an acid catalyst, which is a component (C), while exhibiting acidity by irradiation with actinic rays such as ultraviolet rays (specifically, (A solubility converter).
Examples of the compound of the component (B) include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, and nitro compounds. Benzyl ester, aromatic N-oxyimidosulfonate, aromatic sulfamide, naphthoquinonediazide-4-sulfonic acid ester and the like are used. Such compounds can be used in combination of two or more, if necessary, or in combination with other sensitizers.
Of these, onium salts such as diaryliodonium salts and triarylsulfonium salts can be expected to have a dissolution inhibiting effect, and have high contrast when combined with a compound having an organic group which can be converted to a carboxylic acid by an acid catalyst as the component (C). It is particularly preferable because the conversion can be achieved.
Here, in addition to the above-mentioned ultraviolet rays, for example, X-rays, electron beams, visible rays, and the like can be used as the actinic rays. In particular, those having a wavelength of 200 nm to 500 nm are preferable. Further, monochromatic light such as g-line and i-line can also be used.
[0028]
Here, the component (C) used in the present invention needs to have an organic group that can be converted into a carboxylic acid by an acid catalyst. Accordingly, a dissolution inhibiting effect is expected in an unexposed portion, and a dissolution promoting effect is expected in an exposed portion, so that an appropriate contrast can be exhibited.
The component (C) used in the present invention is not particularly limited in its structure, but has a structure of -COOR (where R represents a monovalent organic group which can be decomposed by an action of an acid and converted into a hydrogen atom). The compound having the group represented by the formula (1) is preferable from the viewpoint of conversion efficiency.
[0029]
In the present invention, preferable examples of the component (C) are shown below, but are not limited to the following.
[0030]
Embedded image

Here, Y in the above structure is specifically an aromatic compound having a skeleton such as diphenyl, diphenyl ether, diphenylthioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenylsulfoxide, diphenylsulfone, benzene, naphthalene, and perylene. And aliphatic hydrocarbon residues having a skeleton such as butane, cyclobutane, cyclohexane, and adamantane, and those having the following structures. Here, p represents a polymer.
[0031]
Embedded image

(In the formula, Z and Z ′ each represent an alkyl group or an alkyl-substituted or unsubstituted heteroatom.) R represents a monovalent organic group that can be decomposed by the action of an acid and converted into a hydrogen atom.
[0032]
Preferred examples of the monovalent group R which can be decomposed by an acid catalyst and converted into a hydrogen atom include those constituting an acetal or ketal having the following structure.
[0033]
Embedded image

(Wherein R ′, R ″ and R ′ ″ are each independently an alkyl group having 5 or less carbon atoms, and X is a divalent alkylene group having 3 or more carbon atoms (preferably 20 or less) May be included).)
Specific examples include a tetrahydropyranyl group, a tetrahydrofuranyl group, an alkyl-substituted tetrahydropyranyl group, an alkyl-substituted tetrahydrofuranyl group, an alkoxy-substituted tetrahydropyranyl group, and an alkoxy-substituted tetrahydrofuranyl group. However, the present invention is not limited to these.
The most preferred group is a tetrahydropyranyl group.
[0034]
Examples of the monovalent group that can be decomposed by the action of an acid and converted into a hydrogen atom include a monovalent alkoxyalkyl group, an alkylsilyl group, and an alkoxycarbonyl group. Although there is no particular limitation, the preferred number of carbon atoms is 2 to 5 for an alkoxyalkyl group, 1 to 20 for an alkylsilyl group, and 2 to 15 for an alkoxycarbonyl group.
[0035]
Specifically, a methoxymethyl group, an ethoxymethyl group, an isopropoxymethyl group, a t-butoxymethyl group, an ethoxyethyl group, a methylsilyl group, an ethylsilyl group, a t-butyldimethylsilyl group, a t-butoxycarbonyl group and the like are typical. However, the present invention is not limited thereto.
Preferred groups are a methoxymethyl group, a 1-ethoxymethyl group, a t-butyldimethylsilyl group, and a t-butoxycarbonyl group.
[0036]
Further, as for R in the group represented by -COOR, a monovalent alkyl group can be used. Although there is no particular limitation on these, the preferred number of carbon atoms is 1 to 10.
[0037]
Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, amyl group and the like are exemplified as typical examples, but are not limited thereto. Absent.
The most preferred group is a t-butyl group.
[0038]
When the component (C) is an oligomer or a polymer, the amount of the component (C) is preferably 1 to 100 parts by weight based on 100 parts by weight of the component (A) from the viewpoint of sensitivity and film quality after curing. More preferably, the amount is set to 100 parts by weight. In other cases, the amount is preferably 1 to 50 parts by weight, more preferably 1 to 25 parts by weight, per 100 parts by weight of the component (A).
[0039]
The positive photosensitive resin composition of the present invention may optionally contain an adhesion imparting agent such as an organosilicon compound for imparting adhesion, a silane coupling agent, or a leveling agent.
Examples of these include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyl Examples thereof include triethoxysilane, aluminum tris (acetylacetonate), and aluminum acetylacetate diisopropylate.
When the adhesion imparting agent is used, it is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the component (A).
[0040]
In the present invention, these components can be dissolved in a solvent and used in the form of a varnish.
Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran, and the like. May be used.
The amount of the solvent is not particularly limited, but is generally used such that the proportion of the solvent in the composition is 40 to 75% by weight.
[0041]
The method for producing a pattern using the positive photosensitive resin composition of the present invention will be described below.
(1) First, the composition is applied to a suitable support, for example, a silicon wafer, ceramic, or aluminum substrate.
Here, examples of the coating method include a spin coating method using a spinner, a spray coating method using a spray coater, an immersion method, a printing method, and a roll coating method, but are not particularly limited.
(2) Next, the coating film is dried by pre-baking preferably at 60 to 120 ° C.
(3) Thereafter, the desired pattern shape is irradiated with actinic rays.
(4) Next, heating is preferably performed at 50 to 150 ° C. Here, the reason why heating is performed after irradiation with actinic rays is that this heating is preferable because the acid generated in the surface layer portion of the irradiated portion can be diffused to the bottom.
(5) Next, a pattern is obtained by developing and dissolving and removing the irradiated portion.
[0042]
Here, examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as ammonia, primary amines such as ethylamine and n-propylamine, and diethylamine. , Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. And alkaline aqueous solutions such as quaternary ammonium salts. Further, an aqueous solution to which an appropriate amount of a water-soluble organic solvent or a surfactant is added can be suitably used.
[0043]
As the developing method, for example, known methods such as a spray method, a paddle method, an immersion method, and an ultrasonic method can be used. Next, the pattern formed by development can be rinsed. Distilled water can be used as the rinsing liquid.
Next, heat treatment is performed to obtain a final pattern having high heat resistance. The heating temperature is generally from 150 to 450 ° C.
[0044]
The photosensitive resin composition of the present invention can be used for electronic components such as a semiconductor device and a multilayer wiring board. Specifically, a surface protective film layer and an interlayer insulating film layer of a semiconductor device and an interlayer of a multilayer wiring board can be used. It can be used for forming an insulating film layer and the like. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film layer and an interlayer insulating film layer formed using the composition, and can have various structures.
[0045]
One example of the semiconductor device manufacturing process of the present invention will be described below with reference to the drawings.
FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.
In FIG. 1, a semiconductor substrate 1 such as a Si substrate having circuit elements is covered with a protective film layer 2 such as a silicon oxide film except for a predetermined portion of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Is formed. Thereafter, an interlayer insulating film layer 4 is formed on the semiconductor substrate 1 by a spin coating method or the like (step (a)).
[0046]
Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film layer 4 by a spin coating method, and a predetermined portion of the interlayer insulating film layer 4 is exposed by a known photolithography technique. Window 6A is provided as described above (step (b)).
The interlayer insulating film layer 4 of the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that does not corrode the first conductor layer 3 exposed from the window 6B, but corrodes only the photosensitive resin layer 5 (step (c)).
[0047]
Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (step (d)).
When a multilayer wiring structure having three or more layers is formed, the above steps are repeated to form each layer.
[0048]
Next, a surface protective film layer 8 is formed.
In the example of FIG. 1, the photosensitive resin composition is applied to the surface protective film layer 8 by a spin coating method and dried, and light is irradiated from a mask on which a pattern for forming a window 6C in a predetermined portion is drawn. After irradiation, the pattern is formed by developing with an aqueous alkali solution, and heated to form a resin film layer. This resin film layer protects the conductor layer from external stress, α-rays, and the like, and the obtained semiconductor device has excellent reliability.
In the above example, the interlayer insulating film layer can be formed using the photosensitive resin composition of the present invention.
[0049]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
[0050]
In this example, the component (B) (acid generator (shown in the following "Chemical Formula 5") and the component (C) (the following "Chemical Formula 5") were added to 100 parts by weight of the component (A) (shown in the following "Chemical Formula 4"). (Chemical formula 6)) and, if necessary, a sensitizer (Chemical formula 7 below) were blended in the predetermined amounts shown in "Table 1", and dissolved in γ-butyrolactone. A coating film was formed using the solution, and the photosensitive characteristics were evaluated.
[0051]
[Example 1]
In this example, as shown in Table 1, component (B) (acid generator (DIAS)) and component (C) (C1) were added to 100 parts by weight of component (A) (polyamide phenol (A1)). It was blended in a predetermined amount shown in Table 1 and dissolved in γ-butyrolactone.
[0052]
The solution was spin-coated on a silicon wafer to form a coating film having a dry film thickness of 2 to 3 μm, and then exposed to i-line (365 nm) using an ultra-high pressure mercury lamp through an interference filter.
After the exposure, the substrate is heated at 120 ° C. for 3 minutes, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide until the silicon wafer at the exposed portion is exposed, and then rinsed with water to obtain a minimum exposure amount necessary for pattern formation. The resolution was determined.
The results are shown in Table 2.
[0053]
[Example 2]
In Example 1, as shown in Table 1, the same operation was performed as in Example 1 except that the component (C) was changed to (C2), and the same evaluation was performed.
The results are shown in Table 2.
[0054]
[Example 3]
In Example 1, as shown in Table 1, the same operation was performed as in Example 1 except that the component (C) was changed to (C3), and the same evaluation was performed.
The results are shown in Table 2.
[0055]
[Example 4]
In Example 1, as shown in Table 1, the same operation was performed as in Example 1 except that the component (C) was changed to (C4), and the same evaluation was performed.
The results are shown in Table 2.
[0056]
[Example 5]
In Example 1, as shown in Table 1, the same operation was performed as in Example 1 except that the component (C) was changed to the polymer type (C5), and the same evaluation was performed.
The results are shown in Table 2.
[0057]
[Example 6]
In Example 1, as shown in Table 1, the same operation was performed as in Example 1 except that the acid generator component was changed to DPI and a sensitizer (9MeAn) was added, and the same evaluation was performed.
The results are shown in Table 2.
[0058]
[Example 7]
In Example 6, as shown in Table 1, the same operation was performed as in Example 1 except that the acid generator component was changed to MPI, and the same evaluation was performed.
The results are shown in Table 2.
[0059]
Example 8
In Example 6, as shown in Table 1, the same operation was performed as in Example 1 except that the component (A) was changed to (A2), and the same evaluation was performed.
The results are shown in Table 2.
[0060]
[Example 9]
In Example 6, as shown in Table 1, the same operation was performed as in Example 1 except that the component (A) was changed to (A3), and the same evaluation was performed.
The results are shown in Table 2.
[0061]
[Example 10]
In Example 6, as shown in Table 1, the same operation was performed as in Example 1 except that the component (A) was changed to (A4), and the same evaluation was performed.
The results are shown in Table 2.
[0062]
[Example 11]
In Example 6, as shown in Table 1, the same operation was performed as in Example 1 except that the component (A) was changed to (A5), and the same evaluation was performed.
The results are shown in Table 2.
[0063]
[Table 1]

[0064]
Embedded image

[0065]
Embedded image

[0066]
Embedded image

[0067]
Embedded image

[0068]
[Table 2]

[0069]
[Comparative Example 1]
In Example 1, (A6) in which the hydroxyl group of polyamide phenol was protected by a t-butoxycarbonyl group, which is an acid active group, without using the component (C), the photosensitive characteristics were evaluated in the same manner.
As a result, the resolution was 30 μm and the exposure amount was 400 mJ / cm. ² In addition, a decrease in resolution and peeling due to swelling were observed, and the sensitivity was low.
[0070]
[Comparative Example 2]
The evaluation of the photosensitive properties was carried out in the same manner as in Example 1 except that phthalic acid having no protecting group introduced therein was used as the C component.
As a result, no pattern was obtained.
[0071]
[Comparative Example 3]
The photosensitive characteristics were evaluated in the same manner as in Example 1 except that (C6), which produces phenol by acid catalysis as the C component, was used.
As a result, the dissolution rate of the exposed part was low, and a good dissolution rate difference between the exposed part and the unexposed part could not be obtained. ² And the resolution was 50 μm.
[0072]
[Comparative Example 4]
In Example 1, NBAS which is not an onium salt was used as the B component, and the photosensitive characteristics were evaluated in the same manner as described below.
As a result, the dissolution inhibiting effect of the unexposed portions was insufficient, and sufficient contrast for pattern formation could not be obtained.
[0073]
Embedded image

[0074]
Embedded image

[0075]
Embedded image

[0076]
In the case of this embodiment, the exposure amount was small and the resolution was good. On the other hand, in each of the comparative examples, the resolution was reduced, no pattern was obtained, and the exposure amount was high, which was not good.
[0077]
【The invention's effect】
In the present invention, (A) a polymer compound having at least one phenolic hydroxyl group or carboxyl group in a molecule, (B) a compound which generates an acid upon irradiation with actinic rays, and (C) a compound which is converted into a carboxylic acid by an acid catalyst. The positive photosensitive resin composition containing a compound having an organic group to be obtained is excellent in sensitivity and resolution, and can sufficiently cope with any structure of a heat-resistant resin for imparting photosensitivity, and is conventionally used. This has the effect of solving the problems of photoresists from the United States, as well as having excellent adhesiveness and heat resistance.
[0078]
Further, according to the method for producing a pattern of the present invention, a pattern having a good shape with excellent mechanical properties, sensitivity, resolution and heat resistance can be obtained by using the composition.
[0079]
Further, the electronic component of the present invention has high reliability by having a pattern having a good shape and characteristics.
[Brief description of the drawings]
FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.
[Explanation of symbols]
1 .... Semiconductor substrate
2 ... Protective film layer
3. First conductor layer
4: Interlayer insulating film layer
5. Photosensitive resin layer
6A, 6B, 6C… Window
7 Second conductor layer
8: Surface protective film layer

Claims (9)

(A) a polymer compound having at least one phenolic hydroxyl group or carboxyl group in the molecule, (B) a compound that generates an acid upon irradiation with actinic rays, and (C) an organic group that can be converted into a carboxylic acid by an acid catalyst. A positive photosensitive resin composition comprising a compound having the same. 2. The composition according to claim 1, wherein the component (A) is a polymer selected from the group consisting of polyimide, polyoxazole, polythiazole, polyamideimide, polyamide, polyamic acid, polyhydroxyamide, polymercaptoamide, and polyphenylene oxide. A positive photosensitive resin composition, characterized in that: 3. The method according to claim 1, wherein the polymer (B) contains 0.01 to 50 parts by weight of a compound capable of generating an acid upon irradiation with actinic rays, based on 100 parts by weight of the polymer compound (A). 4. Positive photosensitive resin composition. In any one of claims 1 to 3,
The positive photosensitive resin composition according to (B), wherein the compound that generates an acid upon irradiation with actinic rays is an onium salt. The compound according to any one of claims 1 to 4, wherein the compound (C) which can be converted into a carboxylic acid by the action of an acid catalyst contains -COOR (where R is decomposed into a hydrogen atom by the action of an acid) in the molecule. (Indicating a monovalent organic group to be obtained). The compound according to any one of claims 1 to 5, wherein 100 parts by weight of the polymer compound (A) has 1 to 100 parts by weight of a compound having an organic group that can be converted into a carboxylic acid by the acid catalysis of (C). A positive photosensitive resin composition comprising: A step of applying and drying the positive photosensitive resin composition according to any one of claims 1 to 6 on a support substrate, and
Exposing;
Developing with an aqueous alkaline solution,
And b. Performing a heat treatment. 8. The method according to claim 7, further comprising a heating step after the exposing step. An electronic component comprising a pattern obtained by the method according to claim 7 or 8 as a surface protective film layer or an interlayer insulating film layer.

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