JPH03198059A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPH03198059A JPH03198059A JP1339496A JP33949689A JPH03198059A JP H03198059 A JPH03198059 A JP H03198059A JP 1339496 A JP1339496 A JP 1339496A JP 33949689 A JP33949689 A JP 33949689A JP H03198059 A JPH03198059 A JP H03198059A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- acid
- base resin
- dissolution
- photosensitive resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 abstract description 21
- 229920005989 resin Polymers 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000000452 restraining effect Effects 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- -1 Halogen ions Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001459 lithography Methods 0.000 description 4
- 238000000206 photolithography Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical class [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical class C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 239000002812 cholic acid derivative Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical class O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical class [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、感光性樹脂組成物に関する６本発明の感光性
樹脂組成物は、例えば、フォトリソグラフィー技術にお
いて微細加工を行うためのフォトレジストとして利用す
ることができる。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photosensitive resin composition. The photosensitive resin composition of the present invention can be used, for example, as a photoresist for microfabrication in photolithography technology. can be used.
但しＲは酸により脱離可能な置換基を表し、は４〜１１
の整数を表す。However, R represents a substituent that can be removed by acid, and is 4 to 11
represents an integer.
本発明の感光性樹脂組成物は、特定の構造の化合物を含
有させることにより、溶解不良や結晶析出などの不都合
の生じない、塗布性の優れた感光性組成物としたもので
ある。The photosensitive resin composition of the present invention contains a compound with a specific structure, so that it is a photosensitive composition that does not suffer from inconveniences such as poor dissolution or crystal precipitation and has excellent coating properties.
し■３
〔発明の背景及び解決すべき問題点〕
従来より感光性樹脂組成物は、数々の分野に利用されて
いる。−船釣には、感光性樹脂組成物は何らかの支持体
か、あるいは被加工物上に塗布されて、使用される。従
って、塗布性が良好であることが要請される。3 [Background of the invention and problems to be solved] Photosensitive resin compositions have been used in a number of fields. - For boat fishing, the photosensitive resin composition is used by being coated on some kind of support or a workpiece. Therefore, good coating properties are required.
しかし従来の感光性樹脂組成物は、場合により、上記塗
布性が十分に得られないことがある。However, in some cases, conventional photosensitive resin compositions may not have sufficient coating properties.
以下、電子材料、特に半導体装置のフォトリソグラフィ
ー技術に用いるフォトレジストとして感光性樹脂組成物
を用いる場合を例にとって、上記の問題を説明する。The above-mentioned problems will be explained below by taking as an example a case where a photosensitive resin composition is used as a photoresist for use in photolithography technology for electronic materials, particularly semiconductor devices.
即ち、例えば半導体集積回路の最小加工寸法は年々微細
化しており、研究開発レベルでは、例えば、０．５μｍ
以下のレベルになるに至っている。That is, for example, the minimum processing dimensions of semiconductor integrated circuits are becoming finer year by year, and at the research and development level, for example, 0.5 μm.
It has reached the following level.
これに伴って、フォトリソグラフィー工程においても、
微細寸法を高精度で制御しなければならなくなっている
。このような状況下で、従来の高、圧水銀打から発せら
れるｇ線やｉ線等の紫外光線を用いたリソグラフィー技
術から、更に短波長化したＫｒＦエキシマレーザ−リソ
グラフィー技術が注目されている。それは波長を短くす
るとそれだけ解像限界がのび、従って微細なパターンを
容易に形成できるからである。Along with this, in the photolithography process,
It is now necessary to control fine dimensions with high precision. Under these circumstances, KrF excimer laser lithography technology, which has a shorter wavelength, is attracting attention from the conventional lithography technology using ultraviolet light such as g-line and i-line emitted from high-pressure mercury flashing. This is because the shorter the wavelength, the greater the resolution limit, which makes it easier to form fine patterns.
しかし、ＫｒＦエキシマレーザ−リソグラフィー技術に
おいては、用いるレーザー光の波長に対して、大部分の
レジストが不透明であるという問題がある。つまりその
波長（２５０ｎｍ）は、レジストとして使用される大部
分の材料（主として有機物）が吸収を有する領域にある
。このためＫｒＦエキシマレーザ−リソグラフィー技術
については、使用できる適切なレジストがなく、材料的
な面で困難となっている。ネガ型レジストは一般に比較
的吸収があってもよいとされているが、精密なパターン
形成のためには吸収がないのが望ましいのは当然であり
、更に吸収のないことが厳しく要請されるポジ型レジス
トについては、上記ＫｒＦレーザー光を用いたフォトリ
ソグラフィー技術に適用できる好適な材料がないのが現
状である。However, KrF excimer laser lithography technology has a problem in that most resists are opaque to the wavelength of the laser light used. That is, the wavelength (250 nm) is in the region where most materials (mainly organic materials) used as resists have absorption. For this reason, the KrF excimer laser lithography technique is difficult in terms of materials because there is no suitable resist that can be used. Negative resists are generally considered to have relatively good absorption, but it is natural that no absorption is desirable for precise pattern formation, and even more so for positive resists, which strictly require no absorption. Regarding the mold resist, there is currently no suitable material that can be applied to the photolithography technique using the above KrF laser beam.
このような状況の中でＫｒＦエキシマレーザ−用のポジ
型レジストに関しては、特に最近、化学増幅型レジスト
が注目されている。化学増幅型レジストは、ＫｒＦエキ
シマレーザ−光に対して従来型のレジスト、例えばナフ
トキノンジアジド／ノボラック樹脂系のレジストが強い
吸収を有するのに対して、該レーザー光の波長に対し透
明にできるからである。Under these circumstances, chemically amplified resists have been attracting particular attention recently as positive resists for KrF excimer lasers. This is because chemically amplified resists can be made transparent to the wavelength of KrF excimer laser light, whereas conventional resists, such as naphthoquinonediazide/novolac resin resists, have strong absorption of KrF excimer laser light. be.
また、化学増幅型レジストは、高解像度、及び良好なレ
ジスト形状をもたらし得るという点でも、注目されてい
る。Additionally, chemically amplified resists are attracting attention because they can provide high resolution and good resist shapes.
化学増幅型レジストは、一般に、光により酸を発生ずる
いわゆる光酸発生剤を用い、ネガ型レジストにあっては
一般に発生した酸が架橋反応を起こさせてその部分の溶
剤（現像剤）に対する溶解性を低下させるように作用し
、ポジ型レジストにあっては一般に発生した酸が樹脂の
保護基を外して溶解性を高めるように作用するものであ
る。Chemically amplified resists generally use a so-called photoacid generator that generates acid when exposed to light, and in negative resists, the generated acid generally causes a crosslinking reaction and dissolves that area in a solvent (developer). In the case of positive resists, the generated acid generally acts to remove the protective groups of the resin and increase its solubility.
よってネガ型の化学増幅型レジストは通常、ベース樹脂
と、光酸発生剤と、酸により架橋が進行する架橋剤の三
成分系から成る（三成分の内二成分を兼ねる化合物を用
いることもできる）。Therefore, negative chemically amplified resists usually consist of a three-component system consisting of a base resin, a photoacid generator, and a crosslinking agent whose crosslinking progresses with acid (compounds that serve as two of the three components can also be used). ).
またポジ型の化学増幅型レジストは通常、ベース樹脂と
、光酸発生剤との二成分を必須のものとして成り、但し
ベース樹脂には保護基が導入されているか、′または別
途保護作用をする化合物、通常溶解性を抑制する溶解抑
止剤を含有するものである。In addition, positive chemically amplified resists usually consist of two essential components: a base resin and a photoacid generator; however, the base resin has a protective group introduced into it, or has a protective effect separately. The compound usually contains a solubility inhibitor to inhibit solubility.
上記ポジ型の化学増幅型レジストで、溶解抑止剤を含有
するものは、光により発生した酸がその溶解抑止効果・
を失効させ、光が照射された部分が溶剤（現像剤）によ
り溶解し得るようにしたものである。Among the positive type chemically amplified resists mentioned above, those containing a dissolution inhibitor have a dissolution inhibiting effect due to the acid generated by light.
It is made so that the portion exposed to light can be dissolved by a solvent (developer).
ベース樹脂と、溶解抑止剤と、光酸発生剤との三成分系
から成るレジストについては、その溶解抑止剤として、
フタルアルデヒド誘導体や、ビスフェノールＡ保護体、
またコリン酸誘導体などが注目されている。For resists consisting of a three-component system consisting of a base resin, a dissolution inhibitor, and a photoacid generator, as the dissolution inhibitor,
Phthalaldehyde derivatives, protected bisphenol A,
Also, cholic acid derivatives are attracting attention.
この中で特に好適な形状を与えるものとして、下式のよ
うなビスフェノールＡ誘導体を挙げることができる。Among these, bisphenol A derivatives as shown in the following formula can be mentioned as those that give a particularly suitable shape.
組成物としての機能を必ずしも十分に発揮させ得るもの
ではなかった。It was not always possible to fully demonstrate the function of the composition.
上記化合物は、ビスフェノールＡについて、溶解抑制の
保護基としてｔ ＢＯＣ基を導入したものである。The above compound is bisphenol A into which a tBOC group is introduced as a protective group for inhibiting dissolution.
ところがビスフェノールＡ誘導体は、これを用いて感光
性組成物を調製するとき、あまり多聞に用いると、溶解
不良を起こしたり、相分＾１て、結晶が析出する等の問
題点がある。これは分子の対称性が良すぎるためではな
いかと考えられるが、いずれにしても、ビスフェノール
Ａ誘導体はその使用量に限界があり、多量に用いると−
Ｆ記溶解不良等により塗布性が悪くなって、実際上使用
できないことがある。よって所望の溶解抑制効果を達成
しようとしても、それに要する量が含有できない場合が
あり、フォトレジスト等に用いる感光性〔発明の目的〕
本発明は上記問題点を解決して、溶解不良などの不都合
が生じない溶解抑止剤を含有する感光性組成物を堤供す
ることを目的とする。However, when bisphenol A derivatives are used to prepare photosensitive compositions, if they are used too much, they may cause problems such as poor dissolution, phase separation, and precipitation of crystals. It is thought that this is because the symmetry of the molecule is too good, but in any case, there is a limit to the amount of bisphenol A derivatives that can be used, and if they are used in large amounts, -
F: Due to poor dissolution, etc., the coating properties may deteriorate and the product may become unusable. Therefore, even if an attempt is made to achieve a desired dissolution suppressing effect, it may not be possible to contain the required amount. It is an object of the present invention to provide a photosensitive composition containing a dissolution inhibitor that does not cause such dissolution.
〔問題点を解決するための手段及び作用〕本発明の感光
性樹脂組成物は、上記目的を達成するため、下記一般式
〔Ｉ〕で表される化合物（以下の記載で適宜「本発明に
係る化合物」ということもある）の少なとも１種を含有
する構成としたものである。[Means and effects for solving the problems] In order to achieve the above object, the photosensitive resin composition of the present invention contains a compound represented by the following general formula [I] (as appropriate in the following description). It has a structure containing at least one type of compound (sometimes referred to as "such compound").
一般式［１］
但しＲは酸により脱離可能な置換基を表し、ｎは４〜１
１の整数を表す。General formula [1] where R represents a substituent that can be eliminated by an acid, and n is 4 to 1
Represents an integer of 1.
置換基Ｒは、酸により脱離可能なものなら何であっても
かまわないことはいうまでもない。好まＣ８゜
（以下ｔ ＢＯＣと略記することもある）ミが、これら
に限定されるわけではない。It goes without saying that the substituent R may be anything as long as it can be removed by an acid. The preferred C8° (hereinafter sometimes abbreviated as tBOC) is not limited to these.
上記化合物は、−ａ式（１）のＲが水素であるビスフェ
ノール誘導体を原料として用い、これをエーテル化する
ことにより、あるいはエステル化することによって置換
基Ｒを導入することにより、合成できる。例えばｎ＝５
の場合、化合物の中央の炭素を含めて飽和６員環が構成
されるが、この場合でＲが水素である化合物は、三菱瓦
斯化学■の市販品で容易かつ比較的安価に入手可能であ
り、原料供給等に問題ない。The above compound can be synthesized by using a bisphenol derivative in which R in formula (1) -a is hydrogen as a raw material and introducing a substituent R by etherifying it or esterifying it. For example n=5
In this case, a saturated 6-membered ring is formed including the central carbon of the compound, but the compound in which R is hydrogen is easily and relatively inexpensively available as a commercial product from Mitsubishi Gas Chemical. There are no problems with the supply of raw materials, etc.
一般式〔１〕で表される化合物は、ベース樹脂に対しそ
の溶解性を低下させる溶解抑止剤として作用することが
できる。またこの化合物はその置換ｇＲが酸により脱離
するので、これにより溶解抑止効果がなくなり得るもの
である。よって光（特定の波長の放射エネルギであって
よい）により酸を発生する光酸発生剤と組み合わせるこ
とによって、光が照射された部分のみベース樹脂が溶解
可能になるポジ型レジストにすることができる。The compound represented by the general formula [1] can act as a dissolution inhibitor that reduces the solubility of the base resin. Furthermore, since the substituted gR of this compound is eliminated by acid, the dissolution inhibiting effect may be lost. Therefore, by combining it with a photoacid generator that generates acid using light (which may be radiant energy of a specific wavelength), it is possible to create a positive resist in which the base resin can be dissolved only in the areas irradiated with light. .
かつ一般式〔Ｉ〕で表される化合物は、その性質上、溶
解性が良く、多量に用いる場合も結晶析出などが起こら
ない。従って、塗布性の良好な感光性組成物とすること
ができる。Moreover, the compound represented by the general formula [I] has good solubility due to its nature, and does not cause crystal precipitation even when used in a large amount. Therefore, a photosensitive composition with good coating properties can be obtained.
本発明の感光性樹脂組成物は、上記したように一般式Ｃ
Ｉ）で表される化合物と、ベース樹脂と、光酸発生剤と
を含する組成物（ポジ型のいわゆる化学増幅型レジスト
）の態様で好ましく利用できる。The photosensitive resin composition of the present invention has the general formula C as described above.
It can be preferably used in the form of a composition (positive type so-called chemically amplified resist) containing the compound represented by I), a base resin, and a photoacid generator.
この場合、ベース樹脂としては、一般式〔Ｉ〕で表され
る化合物が溶解抑止剤として機能できる樹脂であればい
ずれも使用できるが、ポリビニルフェノール、ポリヒド
ロキシスチレン（例えばポリ−ｐ−ヒドロキシスチレン
）、ポリビニルジメチルフェノール、またこれらの共重
合体などのビニル系樹脂を好ましく用いることができる
。In this case, as the base resin, any resin can be used as long as the compound represented by the general formula [I] can function as a dissolution inhibitor, such as polyvinylphenol, polyhydroxystyrene (for example, poly-p-hydroxystyrene). Vinyl resins such as , polyvinyldimethylphenol, and copolymers thereof can be preferably used.
また、光酸発生剤としては、露光エネルギにより酸を発
生する化合物であれば、いずれも使用できる。例えば、
以下例示の光酸発生剤を好ましく用いることができる。Further, as the photoacid generator, any compound can be used as long as it generates an acid by exposure energy. for example,
The photoacid generators exemplified below can be preferably used.
■ ハロゲンイオン（例えば肛４ｅ＋ＰＦ６０ＡｓＦ、
θ、 ＣＦ３ＳＯ３０等）をアニオンとするオニウム塩
（例えばアンモニウム塩、ジアゾニウム塩、ヨードニウ
ム塩、スルホニウム塩、フォスフオニウム塩、セレノニ
ウム塩、アルソニウム塩等）。■ Halogen ions (e.g. anal 4e + PF60AsF,
Onium salts (for example, ammonium salts, diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenonium salts, arsonium salts, etc.) having an anion of θ, CF3SO30, etc.
例えば下記式（Ａ）で示されるジアゾニウム塩、式（Ｂ
）で示されるヨードニウム塩、式（Ｃ）で示されるスル
ホニウム塩を好ましく用いることができる。但しＸθは
上記ハロゲンイオンである。For example, a diazonium salt represented by the following formula (A), a diazonium salt represented by the formula (B)
) and sulfonium salts represented by formula (C) can be preferably used. However, Xθ is the above-mentioned halogen ion.
■有機ポリハロゲン化物 例えば下記化合物を挙げることができる。■Organic polyhalides For example, the following compounds can be mentioned.
−ＣＣ１、など
■スルホン酸発生化合物
Ｏ２
■光酸発生ポリマー
ＥＬ：エチル基
Ｐｈ：フェニル基
Ｔｏｓ：）ルエンスルホン酸基
ＸＯ，ハロゲン原子等
ｒ０
ｒ０
Ｘ ！ｅ： ＨＳＯ４ｅ
ＳＣＮθ
ｒ０
Ｍｅ：メチル基
〔実施例〕
以下本発明の一実施例について、比較例とともに説明す
る。但し当然のことではあるが、本発明は以下述べる実
施例により限定されるものではない。-CC1, etc. ■Sulfonic acid generating compound O2 ■Photoacid generating polymer EL: Ethyl group Ph: Phenyl group Tos:) Luenesulfonic acid group XO, halogen atom, etc. r0 r0 X! e: HSO4e SCNθ r0 Me: Methyl group [Example] An example of the present invention will be described below along with a comparative example. However, it goes without saying that the present invention is not limited to the examples described below.
（実施例）
本実施例では下記感光性組成物を用いて、下記のように
パターン形成実験を行った。(Example) In this example, a pattern formation experiment was conducted as described below using the photosensitive composition shown below.
感光性組成物：ポリビニルフェノール（高純度品、重量
平均分子１３，６００、丸首石油化学製）１０ｇと、本
発明に係る化合物として、一般式〔Ｉ〕においてｎ＝５
、Ｒ＝ｔＢＯＣである化合物３ｇと、光酸発生剤として
ポリフェニルスルホニウムへキサフロロアンチモネート
０．４ｇとを、３０ＩｄのＥＣＡ （エチルセロソルブ
）に溶解して、感光性組成物とした。Photosensitive composition: 10 g of polyvinylphenol (high purity product, weight average molecular 13,600, manufactured by Marukubi Petrochemical) and the compound according to the present invention, n = 5 in general formula [I]
, R=tBOC, and 0.4 g of polyphenylsulfonium hexafluoroantimonate as a photoacid generator were dissolved in 30Id ECA (ethyl cellosolve) to prepare a photosensitive composition.
なお、用いた本発明に係る化合物は、一般式〔Ｉ〕にお
いてｎ＝５、Ｒ＝Ｈである市販のビスフェノール化合物
をエーテル化（エステル化でもよい）により、ｔＢＯＣ
基を導入して、得たものである。The compound according to the present invention used was obtained by etherifying (or esterifying) a commercially available bisphenol compound in which n=5 and R=H in the general formula [I].
It was obtained by introducing a group.
上記感光性組成物をメンブレンフィルターで濾過したも
のを、２００°Ｃで脱水ベータ後室温でＨＭ。The above photosensitive composition was filtered through a membrane filter, dehydrated at 200°C, and then subjected to HM at room temperature.
ＤＳ（ヘキサメチルジシラザン）蒸気処理を１分間行っ
た５インチ径のシリコンウェハ上に回転塗布して、９０
℃で９０秒間ベータし、１．０μｍ膜厚に形成した。こ
れをＫｒＦエキシマレーザ−ステッパ（ＮＡ：０．３７
、σ： ０．５）で、ラインアンドスペースパターン形
成用マスクを用い、露光量１０ｍＪ／ｃｄで露光した。90% by spin coating on a 5-inch diameter silicon wafer that had been subjected to DS (hexamethyldisilazane) vapor treatment for 1 minute.
The film was incubated at °C for 90 seconds to form a film with a thickness of 1.0 μm. This was applied using a KrF excimer laser stepper (NA: 0.37).
, σ: 0.5), using a line-and-space pattern forming mask at an exposure dose of 10 mJ/cd.
その後、１２０℃で１分間ベータし、テトラメチルアン
モニウムハイドロオキサイド（ＴＭＡＨ）水溶液（１，
５６％）を現像液とし、１分３０秒デイツプ現像を行い
、水洗した。得られたパターンを観察したところ、０．
３５μｍ幅のラインアンドスペースパターンが形成でき
ていた。Thereafter, it was incubated at 120°C for 1 minute, and a tetramethylammonium hydroxide (TMAH) aqueous solution (1,
56%) was used as a developer, deep development was performed for 1 minute and 30 seconds, and the film was washed with water. When the obtained pattern was observed, it was found that 0.
A line and space pattern with a width of 35 μm was formed.
上記感光性組成物において溶解抑止剤として用いた本発
明に係る化合物の量を２倍にふやして実施したところ（
即ち樹脂に対して３０％使用から６０％使用に増量した
ところ）、結晶の析出はみられず、良好な塗布性を保っ
ていた。When the amount of the compound according to the present invention used as a dissolution inhibitor in the above photosensitive composition was doubled (
That is, when the amount used was increased from 30% to 60% based on the resin), no crystal precipitation was observed and good coating properties were maintained.
（比較例）
ビスフェノールＡの、ｔＢＯＣ誘導体を溶解抑止剤とし
て用いて、そのほかは上記と同様に実験したところ、溶
解抑止剤を樹脂に対して３５％添加したところで、成膜
したときに結晶析出がみられた。(Comparative example) When we conducted an experiment in the same manner as above except for using a tBOC derivative of bisphenol A as a dissolution inhibitor, we found that when 35% of the dissolution inhibitor was added to the resin, crystal precipitation occurred when the film was formed. It was seen.
上述したとおり、本発明の感光性樹脂組成物は、本発明
に係る化合物を溶解抑止剤として十分に含有させた場合
にも溶解不良や結晶析出などの不都合が生じず、良好な
塗布性を保ち、有効に使用できるものである。As mentioned above, the photosensitive resin composition of the present invention does not suffer from inconveniences such as poor dissolution or crystal precipitation even when it contains a sufficient amount of the compound according to the present invention as a dissolution inhibitor, and maintains good coating properties. , can be used effectively.
Claims (1)
種を含有することを特徴とする感光性樹脂組成物。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 但しＲは酸により脱離可能な置換基を表し、ｎは４〜１
１の整数を表す。 ２、置換基Ｒが▲数式、化学式、表等があります▼ ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼の いずれかであることを特徴とする請求項１に記載の感光
性樹脂組成物。[Claims] 1. At least one compound represented by the following general formula [I]
A photosensitive resin composition characterized by containing seeds. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R represents a substituent that can be removed by acid, and n is 4 to 1.
Represents an integer of 1. 2. Substituent R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
2. The photosensitive resin composition according to claim 1, which has a table or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339496A JPH03198059A (en) | 1989-12-27 | 1989-12-27 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339496A JPH03198059A (en) | 1989-12-27 | 1989-12-27 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03198059A true JPH03198059A (en) | 1991-08-29 |
Family
ID=18328021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1339496A Pending JPH03198059A (en) | 1989-12-27 | 1989-12-27 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03198059A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223858A (en) * | 1990-01-30 | 1991-10-02 | Matsushita Electric Ind Co Ltd | Formation of pattern |
| JPH055985A (en) * | 1990-11-26 | 1993-01-14 | Minnesota Mining & Mfg Co <3M> | Optical image formable composition containing alkoxy alkyl ester dissolution inhibitor |
| JPH07312331A (en) * | 1992-11-03 | 1995-11-28 | Internatl Business Mach Corp <Ibm> | Photoresist image formation process and integrated circuit |
| EP0747768A2 (en) | 1995-06-05 | 1996-12-11 | Fuji Photo Film Co., Ltd. | Chemically amplified positive resist composition |
-
1989
- 1989-12-27 JP JP1339496A patent/JPH03198059A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223858A (en) * | 1990-01-30 | 1991-10-02 | Matsushita Electric Ind Co Ltd | Formation of pattern |
| JPH055985A (en) * | 1990-11-26 | 1993-01-14 | Minnesota Mining & Mfg Co <3M> | Optical image formable composition containing alkoxy alkyl ester dissolution inhibitor |
| JPH07312331A (en) * | 1992-11-03 | 1995-11-28 | Internatl Business Mach Corp <Ibm> | Photoresist image formation process and integrated circuit |
| EP0747768A2 (en) | 1995-06-05 | 1996-12-11 | Fuji Photo Film Co., Ltd. | Chemically amplified positive resist composition |
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