JP4250937B2 - Positive photosensitive resin composition, pattern manufacturing method, and electronic component - Google Patents

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。
【００６２】
［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。
【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/ｃｍ²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／ｃｍ²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]
BACKGROUND OF THE INVENTION
The present invention relates to a positive photosensitive resin composition containing a heat-resistant resin having photosensitivity, a pattern production method using the same, and an electronic component.
[0002]
[Prior art]
Conventionally, a polyimide resin having both 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 devices have been highly integrated and increased in size, there has been a demand for thinner and smaller sealing resin packages, and LOC (lead-on-chip) and surface mounting methods such as solder reflow have been adopted. Therefore, a resin excellent in mechanical characteristics, heat resistance and the like has been required more than ever.
[0003]
On the other hand, photosensitive polyimide having a photosensitive property imparted to the resin itself has been used. However, when this is used, the pattern creation process can be simplified, and complicated manufacturing processes can be shortened.
Conventionally, a heat-resistant photoresist using a photosensitive polyimide or a precursor thereof and its application 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 (see, for example, Patent Documents 1, 2, 3, and 4), 2) Soluble polyimide having a photopolymerizable olefin (see, for example, 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 bonded with a nitrogen atom. Self-sensitized polyimides (see, for example, Patent Documents 11 and 12) have been proposed.
[0004]
Since the negative photosensitive resin composition requires an organic solvent such as N-methylpyrrolidone during 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 naphthoquinone diazide compound with a polyoxazole precursor (for example, see Patent Documents 13 and 14), and (3) a method of introducing naphthoquinone diazide into a soluble polyimide via an ester bond (for example, see Non-Patent Document 2). And (4) those in which naphthoquinone diazide is mixed with a polyimide precursor (for example, see Patent Document 15).
[0005]
However, the above-mentioned negative photosensitive resin composition has a problem in resolution due to its function, and in some applications, it causes a decrease in yield during production.
Moreover, since the structure of the polymer to be used is limited in the above, the physical properties of the finally obtained film are limited, which is not suitable for multipurpose use.
On the other hand, the positive type photosensitive resin composition also has the same problems as described above due to the problems associated with the absorption wavelength of the photosensitive agent, the sensitivity and resolution are low, and the structure is limited.
[0006]
In addition, a polybenzoxazole precursor mixed with a diazonaphthoquinone compound (for example, see Patent Document 16), a polyamic acid in which a phenol moiety is introduced via an ester bond (for example, see Patent Document 17), and the like Although the thing which introduce | transduced the phenolic hydroxyl group instead of the acid is proposed, these things have the problem that developability is inadequate and the film reduction of the unexposed part and peeling from the base material of resin occur. .
For the purpose of improving developability and adhesion, a mixture of polyamic acids having a siloxane moiety in the polymer skeleton has been proposed (see, for example, Patent Documents 18 and 19). Since it is used, there is a problem that storage stability deteriorates.
In addition, for the purpose of improving storage stability and adhesion, those in which amine end groups are sealed with a polymerizable group have been proposed (for example, see Patent Documents 20, 21, and 22). Since a diazoquinone compound containing a large number of aromatic rings is used as the generator, there are problems that the mechanical properties after thermosetting are significantly reduced and the sensitivity is low, and it is difficult to say that the material is at a practical level.
[0007]
In order to improve the problems of the diazoquinone compound, those using various chemical amplification systems have been proposed. 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), etc. However, these high-sensitivity materials have reduced membrane properties caused by low molecular weights, while those with excellent membrane properties have reduced sensitivity due to insufficient solubility caused by high molecular weights, both of which are materials at a practical level. It is hard to say.
Therefore, in reality, none of them is sufficient for practical use.
[0008]
[Patent Document 1]
Japanese Patent Laid-Open No. 49-11541
[Patent Document 2]
Japanese Patent Laid-Open No. 50-40922
[Patent Document 3]
JP 54-145794 A
[Patent Document 4]
JP 56-38038 A
[Patent Document 5]
JP 59-108031 A
[Patent Document 6]
JP 59-220730 A
[Patent Document 7]
JP 59-232122 A
[Patent Document 8]
Japanese Unexamined Patent Publication No. 60-6729
[Patent Document 9]
JP-A-60-72925
[Patent Document 10]
JP-A-61-57620
[Patent Document 11]
JP 59-219330 A
[Patent Document 12]
Japanese Unexamined Patent Publication No. 23-1533
[Patent Document 13]
Japanese Examined Patent Publication No. 64-60630
[Patent Document 14]
US Pat. No. 4,395,482
[Patent Document 15]
JP 52-13315 A
[Patent Document 16]
JP-A-1-46862
[Patent Document 17]
JP-A-10-307393
[Patent Document 18]
JP-A-4-31861
[Patent Document 19]
Japanese Patent Laid-Open No. 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]
Japanese Patent Laid-Open No. 3-763
[Patent Document 24]
JP 7-219228 A
[Patent Document 25]
Japanese Patent Laid-Open No. 10-186664
[Patent Document 26]
Japanese Patent Laid-Open No. 11-202489
[Patent Document 27]
JP 2000-56559 A
[Patent Document 28]
JP 2001-194791 A
[Non-Patent Document 1]
J. et al. 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 converter that protects an alkali-soluble group with a protecting group that can be removed under acid conditions, so that the heat-resistant resin imparting photosensitivity with any structure is excellent in sensitivity and resolution. Conventional photoresists can be prepared by blending these heat-resistant resins with a compound capable of inducing the elimination reaction of the protective group in the solubility converter by irradiation with actinic rays. The present invention provides a positive photosensitive resin composition that solves the above-mentioned problems and has excellent adhesion and heat resistance.
[0010]
The present invention also provides a method for producing a pattern that can be developed with an alkaline aqueous solution by using the above composition and that has a good sensitivity, resolution, and heat resistance, and that has a good shape.
In addition, 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]
The first invention for solving the above-mentioned problems is (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 active light, and (C) an acid catalyst. Containing a compound having an organic group that can be converted into a carboxylic acid by action. In addition, the component (A) is a polymer compound selected from any one of polyimide, polyoxazole, polythiazole, polyamideimide, polyamide, polyamic acid, polyhydroxyamide, polymercaptoamide, and polyphenylene oxide (however, ( A) except that a polymer precursor selected from a polyoxazole precursor or a polyimide precursor having an organic group having a functional group capable of being polymerized by heat at the molecular end is used as a component), and (B) The compound that generates an acid upon irradiation with actinic rays is an onium salt. The positive photosensitive resin composition is characterized in that.
[0013]
First 2 The invention of the 1's In the present invention, the positive photosensitive material is characterized by containing 0.01 to 50 parts by weight of the compound (B) that generates an acid upon irradiation with actinic rays with respect to 100 parts by weight of the polymer compound (A). In the resin composition.
[0015]
First 3 The invention of the first Or 2 In the invention, the compound (C) that can be converted to a carboxylic acid by the action of an acid catalyst is -COOR in the molecule (where R represents a monovalent organic group that can be decomposed by the action of an acid and converted to a hydrogen atom). .) In a positive photosensitive resin composition characterized by being a compound having a group represented by
[0016]
First 4 The invention of the first to the 3 In any one of the inventions, 1 to 100 parts by weight of the compound having an organic group that can be converted into a carboxylic acid by the acid catalysis of (C) with respect to 100 parts by weight of the polymer compound (A). The positive photosensitive resin composition is characterized in that.
[0017]
First 5 The invention of the first to the 4 Using the positive photosensitive resin composition according to any one of the inventions, a step of applying and drying on a support substrate, a step of exposing, a step of developing using an alkaline aqueous solution, and a step of heat treatment, In the manufacturing method of the pattern characterized by including.
[0018]
First 6 The invention of the 5 According to the present invention, there is provided a pattern manufacturing method comprising a drying step after the exposure step.
[0019]
First 7 The invention of the 5 or 6 An electronic component comprising a pattern obtained by the production method described in the invention as a surface protective film layer or an interlayer insulating film layer.
[0020]
DETAILED DESCRIPTION OF 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 the molecule, (B) a compound that generates an acid upon irradiation with actinic rays, and (C And a compound having an organic group that can be converted into a carboxylic acid by acid catalysis.
[0022]
That is, in the present invention, since it is a positive photosensitive resin composition having the compound components (A), (B), and (C), it is excellent in sensitivity and resolution, and has heat resistance imparting photosensitivity. It is possible to satisfactorily cope with any structure of the adhesive resin, solve the problems of conventional photoresists, and provide a resin having high 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 the presence of these substances, moderate solubility in a developing solution and adhesion to a substrate are given.
[0024]
Here, the structure of the component (A) is not particularly limited. For example, the structure selected from polyimide, polyoxazole, polythiazole, polyamideimide, polyamide, polyamic acid, polyhydroxyamide, polymercaptoamide, polyphenylene oxide, and the like. A molecular compound is preferable in terms of processability and heat resistance, for example. Moreover, it can also be used as these 2 or more types of copolymers and mixtures.
[0025]
Although there is no restriction | limiting in particular in the molecular weight of the high molecular compound of the said (A) component, Generally it is preferable that it is 4,000-200,000 by an average molecular weight. The molecular weight can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
[0026]
In the composition of this invention, the compound (henceforth an "acid generator") which generate | occur | produces an acid by actinic ray irradiation is used as (B) component with the high molecular compound used as (A) component.
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 sensitivity and resolution during exposure. More preferably, the content is 0.01 to 20 parts by weight, and even 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 that exhibits acidity upon irradiation with actinic rays such as ultraviolet rays and can be converted into a carboxylic acid by acid catalysis as the component (C) (specifically In particular, it has the conversion action of a soluble conversion agent.
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, nitro Benzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, naphthoquinonediazide-4-sulfonic acid ester and the like are used. Two or more kinds of such compounds can be used in combination as needed, or can be used in combination with other sensitizers.
Among them, onium salts such as diaryliodonium salts and triarylsulfonium salts can be expected to have a dissolution inhibiting effect, and (C) a high contrast by combining with a compound having an organic group that can be converted into a carboxylic acid by acid catalysis. It is particularly preferable because it can be made into a large size.
Here, in addition to the above-described ultraviolet rays, for example, X-rays, electron beams, visible rays and the like can be used as the actinic rays. In particular, a wavelength of 200 nm to 500 nm is preferable. Also, monochromatic light such as g-line or i-line can 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 acid catalysis. As a result, a dissolution inhibiting effect is expected in the unexposed area, and a dissolution promoting effect is expected in the exposed area, and an appropriate contrast can be expressed.
The component (C) used in the present invention is not particularly limited as a structure, but in the molecule is -COOR (where R represents a monovalent organic group that can be decomposed by the action of an acid and converted into a hydrogen atom). ) Is preferable from the viewpoint of conversion efficiency.
[0029]
In the present invention, preferred examples of the component (C) are shown below, but are not limited to the following.
[0030]
[Chemical 1]

Here, Y in the structure is specifically an aromatic 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, or those having the following structure. P represents a polymer.
[0031]
[Chemical formula 2]

(In the formula, Z and Z ′ represent an alkyl group or an alkyl-substituted or unsubstituted heteroatom.) R represents a monovalent organic group that can be decomposed and converted into a hydrogen atom by the action of an acid.
[0032]
Preferred examples of the monovalent group R that can be decomposed by acid catalysis and converted into a hydrogen atom include those constituting an acetal or ketal having the following structure.
[0033]
[Chemical 3]

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 (preferably 20 or less) carbon atoms (with a side chain) You may have).)
Specific examples include tetrahydropyranyl group, tetrahydrofuranyl group, alkyl-substituted tetrahydropyranyl group, alkyl-substituted tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group and the like as typical examples. However, it 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. These are not particularly limited, but preferred carbon numbers are 2 to 5 for alkoxyalkyl groups, 1 to 20 for alkylsilyl groups, and 2 to 15 for alkoxycarbonyl groups.
[0035]
Specifically, methoxymethyl group, ethoxymethyl group, isopropoxymethyl group, t-butoxymethyl group, ethoxyethyl group, methylsilyl group, ethylsilyl group, t-butyldimethylsilyl group, t-butoxycarbonyl group and the like are typical. Although illustrated as an example, it is not limited to these.
Preferred groups are a methoxymethyl group, a 1-ethoxymethyl group, a t-butyldimethylsilyl group, and a t-butoxycarbonyl group.
[0036]
A monovalent alkyl group may be used for R in the group represented by -COOR. Although there is no restriction | limiting in particular in these, As a preferable carbon number, it is 1-10.
[0037]
Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an 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]
The amount of the component (C) is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the component (A) when the component (C) is an oligomer or polymer from the viewpoint of sensitivity and film quality after curing. It is more preferable to set it to -100 weight part. In other cases, the amount is preferably 1 to 50 parts by weight, more preferably 1 to 25 parts by weight with respect to 100 parts by weight of component (A).
[0039]
If necessary, an adhesiveness-imparting agent such as an organosilicon compound, a silane coupling agent, and a leveling agent may be added to the positive photosensitive resin composition in the present invention.
Examples of these include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyl. Examples include triethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate.
When using an adhesiveness imparting agent, 0.1 to 20 parts by weight is preferable and 0.5 to 10 parts by weight is more preferable with respect to 100 parts by weight of 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, 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, etc. It may be used.
Although there is no restriction | limiting in particular in the quantity of a solvent, Generally, it uses so that the ratio of the solvent in a composition may be 40 to 75 weight%.
[0041]
A 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 such as a silicon wafer, ceramic, aluminum substrate and the like.
Here, examples of the coating method include a spin coating method using a spinner, a spray coating method using a spray coater, a dipping method, a printing method, and a roll coating method, but are not particularly limited.
(2) Next, the coating film is dried preferably by prebaking at 60 to 120 ° C.
(3) Then, actinic rays are irradiated to a desired pattern shape.
(4) Next, heating is preferably performed at 50 to 150 ° C. The reason why heating is performed after irradiation with actinic rays is that it is preferable because this heating can diffuse the acid generated in the surface layer of the irradiated portion to the bottom.
(5) Next, development is performed to dissolve and remove the irradiated portion to obtain a pattern.
[0042]
Here, examples of the developer used for the development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and 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, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. And an aqueous alkali solution such as a quaternary ammonium salt. Moreover, the aqueous solution which added appropriate amount of water-soluble organic solvent and surfactant to this can be used conveniently.
[0043]
As a developing method, for example, known methods such as a spray method, a paddle method, an immersion method, and an ultrasonic method are possible. Next, the pattern formed by development can be rinsed. Distilled water can be used as the rinse liquid.
Next, heat treatment can be performed to obtain a final pattern with high heat resistance. The heating temperature is generally 150 to 450 ° C.
[0044]
The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, the surface protective film layer, interlayer insulating film layer of semiconductor devices, and interlayers of multilayer wiring boards are used. It can be used for forming an insulating film layer or 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]
An 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 coat method or the like (step (a)).
[0046]
Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac 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. Similarly, a window 6A is provided (step (b)).
The interlayer insulating film layer 4 of the window 6A is selectively etched by dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).
[0047]
Furthermore, 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, each layer can be formed by repeating the above steps.
[0048]
Next, the 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 coat method and dried, and light is applied from above a mask on which a pattern for forming a window 6C is formed at a predetermined portion. After irradiation, development is performed with an alkaline aqueous solution to form a pattern, which is then 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 resulting semiconductor device is excellent in 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 described specifically by way of examples.
[0050]
In this example, 100 parts by weight of component (A) (shown in “Chemical Formula 4” below), (B) component (acid generator (shown in “Chemical Formula 5” below)), component (C) (shown below) And a sensitizer (shown in the following “Chemical Formula 7”) in a predetermined amount shown in “Table 1” and, if necessary, 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, (B) component (acid generator (DIAS)) and (C) component (C1) are added to 100 parts by weight of component (A) (polyamidephenol (A1)). They were blended in the prescribed amounts 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 exposure, heat at 120 ° C. for 3 minutes, develop with a 2.38% aqueous solution of tetramethylammonium hydroxide until the exposed silicon wafer is exposed, then rinse with water to obtain the minimum exposure required 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 evaluation was performed as in Example 1 except that the component (C) was changed to (C2).
The results are shown in “Table 2”.
[0054]
[Example 3]
In Example 1, as shown in Table 1, the same evaluation was performed as in Example 1 except that the component (C) was changed to (C3).
The results are shown in “Table 2”.
[0055]
[Example 4]
In Example 1, as shown in Table 1, the same evaluation was performed as in Example 1 except that the component (C) was changed to (C4).
The results are shown in “Table 2”.
[0056]
[Example 5]
In Example 1, as shown in Table 1, the same evaluation was performed as in Example 1 except that the component (C) was changed to the polymer type (C5).
The results are shown in “Table 2”.
[0057]
[Example 6]
In Example 1, as shown in Table 1, the same evaluation was performed as in Example 1 except that the acid generator component was changed to DPI and a sensitizer (9MeAn) was added.
The results are shown in “Table 2”.
[0058]
[Example 7]
In Example 6, as shown in Table 1, the same evaluation was performed as in Example 1 except that the acid generator component was changed to MPI.
The results are shown in “Table 2”.
[0059]
[Example 8]
In Example 6, as shown in Table 1, the same evaluation was performed as in Example 1 except that the component (A) was changed to (A2).
The results are shown in “Table 2”.
[0060]
[Example 9]
In Example 6, as shown in Table 1, the same evaluation was performed as in Example 1 except that the component (A) was changed to (A3).
The results are shown in “Table 2”.
[0062]
[Example 10 ]
In Example 6, as shown in Table 1, the component (A) was changed to (A 4 The same evaluation was performed as in Example 1 except that the above was changed.
The results are shown in “Table 2”.
[0063]
[Table 1]

[0064]
[Formula 4]

[0065]
[Chemical formula 5]

[0066]
[Chemical 6]

[0067]
[Chemical 7]

[0068]
[Table 2]

[0069]
[Comparative Example 1]
Using Example (A6) in which the hydroxyl group of polyamidephenol was protected with a t-butoxycarbonyl group which is an acid active group without using the component (C) in Example 1, the photosensitive characteristics were evaluated in the same manner.
As a result, the resolution is 30 μm and the exposure amount is 400 mJ / cm. ² The resolution was reduced due to swelling, peeling was observed, and the sensitivity was low.
[0070]
[Comparative Example 2]
Using Example 1 phthalic acid having no protective group introduced therein as C component, the photosensitive characteristics were evaluated in the same manner.
As a result, no pattern was obtained.
[0071]
[Comparative Example 3]
Using Example 1 (C6), which generates phenol by acid catalysis as the C component, the photosensitive characteristics were evaluated in the same manner.
As a result, the dissolution rate of the exposed part is slow, and a good dissolution rate difference cannot be obtained between the exposed part and the exposure dose of 1000 mJ / cm. ² The resolution was 50 μm.
[0072]
[Comparative Example 4]
In Example 1, NBAS that is not an onium salt was used as the B component, and the photosensitive characteristics were evaluated in the same manner.
As a result, the effect of preventing dissolution of unexposed portions was insufficient, and a sufficient contrast for pattern formation could not be obtained.
[0073]
[Chemical 8]

[0074]
[Chemical 9]

[0075]
[Chemical Formula 10]

[0076]
In all of the examples, the exposure amount was small and the resolution was good. On the other hand, none of the comparative examples showed a decrease in resolution, a pattern was not obtained, or the exposure amount was high and 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 the molecule, (B) a compound that generates an acid upon irradiation with actinic rays, (C) it is converted into a carboxylic acid by acid catalysis. Since it is a positive photosensitive resin composition containing a compound having an organic group to be obtained, it is excellent in sensitivity and resolution, and can sufficiently cope with any structure of a heat-resistant resin imparting photosensitivity, and conventionally The problems of the photoresists from No. 1 are solved, and the adhesive and heat resistance are high.
[0078]
Further, according to the method for producing a pattern of the present invention, by using the composition, a pattern having a good shape and excellent mechanical properties, sensitivity, resolution and heat resistance can be obtained.
[0079]
In addition, the electronic component of the present invention is highly reliable by having a pattern with 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 ... 1st conductor layer
4 ... Interlayer insulating film layer
5 ... Photosensitive resin layer
6A, 6B, 6C ... windows
7 ... Second conductor layer
8 ... Surface protective film layer

Claims (7)

(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 to a carboxylic acid by acid catalysis. contains a compound having in a Rutotomoni,
The component (A) is a polymer compound selected from any one of polyimide, polyoxazole, polythiazole, polyamideimide, polyamide, polyamic acid, polyhydroxyamide, polymercaptoamide, and polyphenylene oxide (however, the component (A) And a polymer precursor selected from a polyoxazole precursor or a polyimide precursor having an organic group having a functional group capable of being polymerized by heat at the molecular terminal.
The positive photosensitive resin composition, wherein the compound (B) that generates an acid upon irradiation with actinic rays is an onium salt . Oite to claim 1, and characterized in that of the polymer compound 100 parts by weight of the (A), containing the compound 0.01 to 50 parts by weight which generates an acid by irradiation of active radiation (B) A positive photosensitive resin composition. 3. The compound according to claim 1 or 2 , wherein the compound (C) that can be converted into a carboxylic acid by the action of an acid catalyst is a -COOR in the molecule (where R is decomposed by the action of an acid and can be converted into a hydrogen atom). A positive photosensitive resin composition, which is a compound having a group represented by the formula: In any one of Claims 1 thru | or 3 , 1-100 weight of compounds which have an organic group which can be converted into carboxylic acid by the acid catalyst action of said (C) with respect to 100 weight part of said high molecular compounds of said (A). A positive photosensitive resin composition comprising a part. Using the positive photosensitive resin composition according to any one of claims 1 to 4 , and applying and drying on a support substrate;
A step of exposing;
Developing with an aqueous alkaline solution;
And a step of heat-treating the pattern. 6. The pattern manufacturing method according to claim 5 , further comprising a heating step after the exposure step. An electronic component comprising a pattern obtained by the production method according to claim 5 or 6 as a surface protective film layer or an interlayer insulating film layer.

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