JPS62215944A - Heat resistant photosensitive resin composition and formation of insulating layer - Google Patents
Heat resistant photosensitive resin composition and formation of insulating layerInfo
- Publication number
- JPS62215944A JPS62215944A JP5975486A JP5975486A JPS62215944A JP S62215944 A JPS62215944 A JP S62215944A JP 5975486 A JP5975486 A JP 5975486A JP 5975486 A JP5975486 A JP 5975486A JP S62215944 A JPS62215944 A JP S62215944A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- compound
- resin composition
- heat
- 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 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title abstract 2
- -1 aromatic azido compound Chemical class 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 13
- 229920006015 heat resistant resin Polymers 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 230000007261 regionalization Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OMEDIQVDAHJDBD-UHFFFAOYSA-N 1-trichlorosilylprop-2-en-1-one Chemical compound Cl[Si](Cl)(Cl)C(=O)C=C OMEDIQVDAHJDBD-UHFFFAOYSA-N 0.000 description 1
- JATWHCYXJVKSHV-UHFFFAOYSA-N 2-methyl-1-trichlorosilylprop-2-en-1-one Chemical compound C(=O)(C(=C)C)[Si](Cl)(Cl)Cl JATWHCYXJVKSHV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 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
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- HSVFKFNNMLUVEY-UHFFFAOYSA-N sulfuryl diazide Chemical class [N-]=[N+]=NS(=O)(=O)N=[N+]=[N-] HSVFKFNNMLUVEY-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
Abstract
Description
【発明の詳細な説明】
〔概要〕
本発明は、耐熱性の高いシリル化ポリオルガノシルセス
キオキサンをペースレジンとして感光性を付与すること
により、従来の絶縁層形成方法の欠点をカバーできる新
材料を提供する。[Detailed Description of the Invention] [Summary] The present invention is a new method that can overcome the drawbacks of conventional insulating layer forming methods by imparting photosensitivity to highly heat-resistant silylated polyorganosilsesquioxane as a paste resin. Provide materials.
又、本発明は半導体装置の絶縁層の製造法に関する。The present invention also relates to a method for manufacturing an insulating layer of a semiconductor device.
本発明において絶縁層とけ、多層配線における層間絶縁
膜及び層間絶縁膜が表面層であるパッシベーション膜を
意味する。In the present invention, it refers to an insulating layer, an interlayer insulating film in a multilayer wiring, and a passivation film in which the interlayer insulating film is a surface layer.
本発明は、半導体装置の多層配線構造体の絶縁層の製造
方法に関する。半導体装置の絶縁膜の形成には、そのパ
ターン形成には、感光性材料を用いたはん雑なレジスト
プロセスを用いている。このプロセスを改良するために
、感光性の耐熱樹脂の開発が行なわれている。しかし、
耐熱樹脂をパターン形成材料として使用するには、感光
剤を混合しなければならないため、高温で感光剤の分解
がおこり、均一な膜の形成が困難となる０このため、高
温で処理した後も均一な膜組成が得られるような感光性
耐熱樹脂の開発が必要とされている０〔従来の技術〕
従来、半導体装置の絶縁層の形成に際しては、そのパタ
ーン形成グの為に感光性レジストを各層上に塗布し、露
光、現儂し、そして各層をエツチングするという方法が
とられている０これらのレジストを用いたプロセスは非
常にはん雑であり、また多くの副資材を必要とする０
このはん雑さを解消でるため、近年、感光性の絶縁材料
を用いるプロセスが開発されているが、絶縁材料にはそ
のプロセス上非常に高い耐熱性が必要であるため、適音
レジストに用いられる様な感光性有機材料は用いる仁と
ができない０最近この問題を解決するため感光性ポリイ
ミドを用いたプロセスが開発されたが、この耐熱性は決
して従来のポリイミドを上まわるものではなく、感光性
ポリイミドの場合には、感光性化合物を全て熱分解しよ
うとすると主鎖のポリイミド骨格も熱分解されてしまう
ため半導体の製造プロセスに大きな制限をともなうもの
でありた。The present invention relates to a method for manufacturing an insulating layer of a multilayer wiring structure of a semiconductor device. In forming an insulating film for a semiconductor device, a complicated resist process using a photosensitive material is used for pattern formation. In order to improve this process, photosensitive heat-resistant resins are being developed. but,
To use heat-resistant resin as a pattern-forming material, it is necessary to mix it with a photosensitizer, which causes decomposition of the photosensitizer at high temperatures, making it difficult to form a uniform film.For this reason, even after processing at high temperatures, There is a need to develop a photosensitive heat-resistant resin that can obtain a uniform film composition.0 [Prior art] Conventionally, when forming an insulating layer for a semiconductor device, a photosensitive resist is used for pattern formation. The process using these resists is very complicated and requires many auxiliary materials. 0 In order to eliminate this complexity, processes using photosensitive insulating materials have been developed in recent years, but since the insulating materials require extremely high heat resistance for the process, it is difficult to use suitable photoresists. Recently, a process using photosensitive polyimide has been developed to solve this problem, but its heat resistance is by no means superior to that of conventional polyimide. In the case of photosensitive polyimide, if an attempt was made to thermally decompose all of the photosensitive compound, the main chain polyimide skeleton would also be thermally decomposed, resulting in significant limitations on the semiconductor manufacturing process.
従来の絶縁膜形成プロセスを、簡略化する目的で絶縁膜
として感光性耐熱樹脂の使用が試みられているが、耐熱
樹脂に感光性を与えるためには、感光剤を用いなければ
ならない。しかしながら、感光剤を用いると、パターン
形成後の熱処理により、感光剤の分解がおこるため膜に
抜は穴が生じていた。Attempts have been made to use a photosensitive heat-resistant resin as an insulating film in order to simplify the conventional process for forming an insulating film, but in order to impart photosensitivity to the heat-resistant resin, a photosensitizer must be used. However, when a photosensitive agent is used, the photosensitive agent decomposes during heat treatment after pattern formation, resulting in holes in the film.
本発明は、（１）一般式
で示されるポリシルセスキオキサンに、芳香族アジド化
合物、および芳香族スルホニル化合物を混合してなる感
光性耐熱樹脂組成物及び、（２）一般式
％式％
Ｒ＋、Ｒｖ＆１メチル基、アクリロイル基あるいはメタ
クリロイル基
で示されるポリシルセスキオキサンに、芳香族アジド化
合物、および芳香族スルホニル化合物を混により達成さ
れる。The present invention provides (1) a photosensitive heat-resistant resin composition prepared by mixing a polysilsesquioxane represented by the general formula with an aromatic azide compound and an aromatic sulfonyl compound; This is achieved by mixing an aromatic azide compound and an aromatic sulfonyl compound with a polysilsesquioxane represented by R+, Rv & 1 methyl group, acryloyl group or methacryloyl group.
本発明は、耐熱性（５００℃以上）、耐クラック性（３
μｍＡｌ上〕、レベリング性に優れたシリル化ポリオル
ガノシルセスキオキサンと芳香族アジド化合物および芳
香族スルホニルアジド化合物との混合物を配線層の形成
された基材の上に塗布し露光、現像後年活性ガス雰囲気
下３５０℃、ｌｈの加熱を行うことを特徴とする。The present invention has heat resistance (500℃ or higher) and crack resistance (3
μmAl], a mixture of silylated polyorganosilsesquioxane with excellent leveling properties, an aromatic azide compound, and an aromatic sulfonyl azide compound was applied onto the substrate on which the wiring layer was formed, and after exposure and development. It is characterized by heating at 350° C. and 1h in an active gas atmosphere.
本発明において、絶縁層の製造に用いられる感光性耐熱
樹脂組成物はペースレジンのシリル化ポリオルガノシル
セスキオキサンと、感光性化合物である芳香族アジド化
合物あるいは芳香族スルホニルアジド化合物を適当な溶
剤の存在下で混合することにより容易に得られるｏｔた
上記の感光性耐熱樹脂組成物は、ペースレジンが、耐熱
性、耐クラック性、レベリング性に優れたシリル化ポリ
オルガノシルセスキオキサンであるため、その耐熱性に
おいては、ポリイミドの場合、高くても４００〜４５０
℃であるのに対し５００℃である０また、耐クラツク性
においては、末端ヒドロオシラダーシロキサンの場合、
高くてもＳｉ基板上０．３ｔｔｍ程度、 Ａｌ上０．２
ｔｔｒｎ ａ変ｆ ；Ａ ル（Ｄ ｔ／（Ｊ’ｊ Ｌ
、、Ｓｔ基板上１．５μｍ以上、 Ａｌ上１．０μｍ以
上である。In the present invention, the photosensitive heat-resistant resin composition used for manufacturing the insulating layer is a paste resin silylated polyorganosilsesquioxane and a photosensitive compound such as an aromatic azide compound or an aromatic sulfonyl azide compound in a suitable solvent. In the above photosensitive heat-resistant resin composition, which can be easily obtained by mixing in the presence of Therefore, in the case of polyimide, its heat resistance is at most 400 to 450
In addition, in terms of crack resistance, in the case of terminal hydroosilada siloxane,
At most 0.3 ttm on Si substrate, 0.2 ttm on Al
ttrn a change f ;A le(D t/(J'j L
,, 1.5 μm or more on the St substrate, and 1.0 μm or more on the Al substrate.
さらにシリル化ポリオルガノシルセスキオキサンの熱分
解温度は５００℃以上であるため、露光。Furthermore, since the thermal decomposition temperature of silylated polyorganosilsesquioxane is 500°C or higher, exposure to light is necessary.
現偉後に加熱して熱分解温度が４００℃以下である感光
性化合物を熱分解し、シリル化ポリオルガノシルセスキ
オキサンのみの膜を形成できる。このとき、シリル化ポ
リオルガノシルセスキオキサンは、溶融するので、感光
剤の抜は穴を埋め、微密な膜を形成出来る。After heating, a photosensitive compound having a thermal decomposition temperature of 400° C. or less can be thermally decomposed to form a film made only of silylated polyorganosilsesquioxane. At this time, since the silylated polyorganosilsesquioxane melts, it can fill the holes left by the removal of the photosensitizer and form a fine film.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
本発明の感光性耐熱樹脂のペースレジンであるシリル化
ポリオルガノシルセスキオキサンは一般式Ｒ８１ＣＪｓ
（ここでは、Ｒはメチル基、ビニル基。The silylated polyorganosilsesquioxane, which is the paste resin of the photosensitive heat-resistant resin of the present invention, has the general formula R81CJs.
(Here, R is a methyl group or a vinyl group.
あるいはアリル基であるうで示されるトリクロロシラン
を加水分解し、第４級アンモニウム塩全触媒として加圧
重縮合し、（ＣＨｓ）ｘｓｉｃＪで末端の活性水素を置
換することにより得られる。上述の如く得られた下記一
般式で示されるクリル化ポリシルセスキオキサン
Ｒ＋
Ｒ章
に於て、ｎは１０〜１０００の整数が好ましく、Ｒ１＋
Ｒｔはメチル基、アクリロイル基、あるいはメタクリロ
イル基から選ばれた基であるのが好ましい。Alternatively, it can be obtained by hydrolyzing trichlorosilane, which is an allyl group, and performing pressure polycondensation using a quaternary ammonium salt as a total catalyst, and replacing the terminal active hydrogen with (CHs)xsicJ. Acrylated polysilsesquioxane R+ represented by the following general formula obtained as described above In the R section, n is preferably an integer of 10 to 1000;
Rt is preferably a group selected from a methyl group, an acryloyl group, or a methacryloyl group.
Ｒ，、Ｒ１がメチル基、アクリロイル基、Ｔｏるいはメ
タクリロイル基であるのが好ましいのは下記理由による
０
側鎖にメチル基金もつラダーシリコン樹脂は、耐熱性が
高い。従って、シリル化ポリメチルシルセスキオキサン
をペースとして、感光基であるアクリロイル基あるいは
メタクロイル基金、メチル基のかわりに数〜数１０チ入
れかえたものを使用するＯ
ｎが１０〜１０００の整数であるのが好ましいのは下記
理由による。ｎが１０より少では皮膜性が乏しく、ｎが
１０００より大ではパターンを形成したときの解像性が
低下するためである。It is preferable that R, , R1 be a methyl group, an acryloyl group, a To group, or a methacryloyl group for the following reason: Ladder silicone resin having a methyl group in its side chain has high heat resistance. Therefore, using silylated polymethylsilsesquioxane as a base, the photosensitive group, acryloyl group or methacryloyl group, or a methyl group replaced with several to several tens of groups, is used. The reason why this is preferable is as follows. This is because when n is less than 10, film properties are poor, and when n is more than 1000, resolution when forming a pattern is reduced.
感光性化合物としては、光照射により活性種ナイトレン
を生成し、二量化、二重結合への付加。As a photosensitive compound, it generates the active species nitrene upon irradiation with light, dimerizes it, and adds it to double bonds.
水素引き抜き反応を起こす芳香族アジド化合物。An aromatic azide compound that causes a hydrogen abstraction reaction.
および芳香族スルホニル化合物を用いる。and aromatic sulfonyl compounds.
従って、感光性耐熱樹脂組放物は、上記反応を経由して
露光部と未露光部に現像液に対する溶解性の差をもたら
し、パターンの形成が可能になる。Therefore, the photosensitive heat-resistant resin composition brings about a difference in solubility in a developing solution between the exposed and unexposed areas through the above reaction, making it possible to form a pattern.
本発明に用いられる芳香族アジド化合物としては例えば Ｎ。Examples of aromatic azide compounds used in the present invention include N.
ビＣ庶ｐ函Ｎ山）。BIC庶pBoxN山).
０Ｈ
等のビスアジド化合物などがあるＯまた、芳香族スルホ
ニルアジド化合物としては、例えば””” Ｉｃｏｏａ
ｉ、ｃｏ南Ｎ（ａｔ、）。There are also bisazide compounds such as 0H.Also, aromatic sulfonyl azide compounds include, for example,
i,co south N(at,).
””” ＜ Ｃ００Ｑ（、Ｇ（、ｃ）ｌ、Ｎ（Ｃ，Ｈ３
）１等のモノスルホニルアジド化合物
等のビススルホニルアジド化合物などがある。これらの
感光性化合物は単独でまたは二種以上を併用して用いる
ことができる。"""< C00Q(,G(,c)l,N(C,H3
) bissulfonyl azide compounds such as monosulfonyl azide compounds such as 1) and the like. These photosensitive compounds can be used alone or in combination of two or more.
本発明の半導体装置の絶縁層形成に用いられる上記の感
光性シリコーン樹脂組放物は、通常シリル化ポリメチル
シルセスキオキサンと感光性化合物とを適当な有機溶媒
に溶解した状態で使用されるが、この場合両化合物のい
ずれも溶解することが好ましく、例えばベンゼン、トル
エン、キシレン等の芳香族炭化水素、アセトン、メチル
エチルケトン等のケトン系溶媒などが用いられる。これ
らは単独で用いてもよいし混合して用いることも可能で
ある。The photosensitive silicone resin composition used for forming the insulating layer of the semiconductor device of the present invention is usually used in a state in which silylated polymethylsilsesquioxane and a photosensitive compound are dissolved in a suitable organic solvent. However, in this case, it is preferable that both compounds are dissolved, and for example, aromatic hydrocarbons such as benzene, toluene, and xylene, and ketone solvents such as acetone and methyl ethyl ketone are used. These may be used alone or in combination.
また上記の感光性シリコーン樹脂組放物には種々の増感
剤を併用することが可能である。増感剤は感光性化合物
の感光波長域をひろげたり、感光性化合物へ光エネルギ
ーを効率良く与えるなどして感光感度の向上をはかるも
のであり、本発明においては、例えばベンゾイン又はベ
ンゾインエーテル類、ベンジルとその誘導体、アリール
ジアゾニウム塩、アントラキノンとその誘導体、アセト
フェノン又はその誘導体、ジフェニルジスルフィド等の
イオウ化合物、ベンゾフェノン又はその誘導体などが使
用可能であり、これらは一種または二種以上の混合物と
して用いられる。Furthermore, various sensitizers can be used in combination with the photosensitive silicone resin compound. Sensitizers aim to improve photosensitivity by expanding the sensitive wavelength range of photosensitive compounds and efficiently imparting light energy to photosensitive compounds. In the present invention, for example, benzoin or benzoin ethers, Benzyl and its derivatives, aryl diazonium salts, anthraquinone and its derivatives, acetophenone or its derivatives, sulfur compounds such as diphenyl disulfide, benzophenone or its derivatives, etc. can be used, and these can be used alone or as a mixture of two or more.
次（本発明の半導体装置の絶縁層の製造法について具体
的に述べる。Next, a method for manufacturing an insulating layer of a semiconductor device according to the present invention will be specifically described.
まず、配線層が形成されたシリコンウェーハ。First, a silicon wafer with a wiring layer formed on it.
ガリウムーヒ素ウェーハ、ガラス、セラミック等の基材
上に、上記の感光性シリコーン樹脂組成物をスピンナ等
を用いて塗布する。次に溶媒？：８０℃〜１５０℃、好
櫨しくけ１００℃〜１２０℃の温度で１０分〜６０分、
好ましくＦ′１２０分〜３０分乾燥して除去した後、マ
スクを介して露光を行なう。The photosensitive silicone resin composition described above is applied onto a substrate such as a gallium-arsenide wafer, glass, or ceramic using a spinner or the like. Next is the solvent? : 10 minutes to 60 minutes at a temperature of 80 degrees Celsius to 150 degrees Celsius, 100 degrees Celsius to 120 degrees Celsius,
Preferably, after drying and removing F' for 20 to 30 minutes, exposure is performed through a mask.
この際露光の条件は用いる感光性化合物によって異なる
が特に制限はない。At this time, the exposure conditions vary depending on the photosensitive compound used, but are not particularly limited.
その後、前述の溶媒等を用いて現偉しパターンを形成す
る。現像条件は、膜厚、パターン形状。Thereafter, a pattern is formed using the above-mentioned solvent or the like. Development conditions include film thickness and pattern shape.
寸法などにより異なるが、特に制限はない。Although it varies depending on dimensions etc., there is no particular restriction.
次に、パターン化された該組成物膜を、必要によシ適当
な温度で熱処理して、絶縁層とさせる。Next, the patterned composition film is heat treated at an appropriate temperature as necessary to form an insulating layer.
この加熱は、溶媒を完全に除去するためにあるいは、微
密な膜を得るために必要である。好ましい加熱温度は、
２５０〜４００℃である。This heating is necessary to completely remove the solvent or to obtain a finely packed film. The preferred heating temperature is
The temperature is 250-400°C.
上記シリル化ポリシルセスキオキサン、芳香族アジド化
合物、及び芳香族スルホニル化合物からなる感光性耐熱
樹脂組成物の好ましい組成比は下記の通りである。The preferred composition ratio of the photosensitive heat-resistant resin composition comprising the silylated polysilsesquioxane, aromatic azide compound, and aromatic sulfonyl compound is as follows.
シリル化ポリシルセスキオキサンヲ１００重量部とした
とき、芳香族アジド化合物あるいは芳香族スルホニル化
合物；芳香族アジド化合物あるいは芳香族ビスアジド化
合物５〜２０重量部である。When the silylated polysilsesquioxane is 100 parts by weight, the aromatic azide compound or aromatic sulfonyl compound; the aromatic azide compound or the aromatic bisazide compound is 5 to 20 parts by weight.
５１ｉｔ以下では感度が低くなシ、２０重量部よシ大で
は熱処理後の成膜性が悪くなるからである。This is because if it is less than 51 it, the sensitivity will be low, and if it is more than 20 parts by weight, the film forming properties after heat treatment will be poor.
〔実施例１〕
メチルトリクロルシラン（ＣＨｓ ５ｋＣ１，）とアク
リロイルトリクロルシラン（ＣＨｓＣＨＣＯ８ｔＣ１ｓ
）のに１溶液を一２０℃以下の温度で加水分解し、ト
リエチルアミン塩酸塩触媒下９０±３℃で５時間加圧重
縮合して得られたポリメチル（アクリロイル）シルセス
キオキサンをピリジンの存在下トリメチルクロルシラン
（（ＣＨｓ ）ｓ ５ＩＣｌ）でシリル化してシリル化
ポリメチル（アクリロイル）シルセスキオキサンを得た
。得られた樹脂の重量平均分子量Ｍｗは３．８Ｘ１０’
であった。こうして得られたシリル化ポリメチル（アク
リロイル）シルセスキオキサン１０Ｆに３，３′−ジア
ジドフェニルスルフォン１ｆを添加し、ベンゼン１００
ｆに溶解して感光性耐熱樹脂組成物を得た。[Example 1] Methyltrichlorosilane (CHs 5kC1,) and acryloyltrichlorosilane (CHsCHCO8tC1s
) in the presence of pyridine, the resulting polymethyl(acryloyl)silsesquioxane was hydrolyzed at a temperature below -20°C and polycondensed under pressure at 90±3°C for 5 hours under a triethylamine hydrochloride catalyst. The mixture was silylated with trimethylchlorosilane ((CHs)s 5ICl) to obtain silylated polymethyl(acryloyl)silsesquioxane. The weight average molecular weight Mw of the obtained resin is 3.8X10'
Met. To the thus obtained silylated polymethyl(acryloyl)silsesquioxane 10F, 3,3'-diazidophenyl sulfone 1f was added, and benzene 100% was added.
f to obtain a photosensitive heat-resistant resin composition.
次に、第一層のＡＡ’配線の形成されたシリコン基板上
に上記樹脂をスビ／コート法により塗布し、１２０℃、
３０分の溶剤乾燥を行い０．６μｍ厚の膜を形成した。Next, the above resin was coated on the silicon substrate on which the first layer of AA' wiring was formed by a coating/coating method, and heated at 120°C.
Solvent drying was performed for 30 minutes to form a film with a thickness of 0.6 μm.
次に石英マスク（大日本印刷製ＤＮＰファインラインテ
ストパターン）を介してＸｓ−Ｈｇランプにより３０ｆ
ｉＷ／ｄで光照射した後、メチルイソブチルケトンで１
分間現像し、イングロビルアルコールで３０秒リンスを
行い、良好なパターンを得た。Next, a 30 f
After irradiation with light at iW/d, 1
After developing for a minute and rinsing with Inglobil alcohol for 30 seconds, a good pattern was obtained.
コノパターンニングされた膜をＮｔ雰囲気下。The cono-patterned film was placed in an Nt atmosphere.
３５０℃、ｌｈの熱処理を行いパターン化された絶縁膜
を得た。この膜は、さらに５００ ”Ｃ、ｌｈの熱処理
を施しても全くクラックは見られなかった。A patterned insulating film was obtained by performing heat treatment at 350° C. for lh. No cracks were observed in this film even after further heat treatment at 500''C and lh.
〔実施例２〕
メチルトリクロルシランとメタクリロイルトリクロルシ
ラン（ＣＨｓＣ（ＣＨｓ ）Ｈ８ＩＣ１ｓ）の１：１混
合溶液金用い実施例１と同様にしてシリル化ポリメチル
（メタクロイル）シルセスキオキサン重量平均分子量Ｍ
ｗ ＝ ３．５ Ｘ １０’ ）を得た。[Example 2] A 1:1 mixed solution of methyltrichlorosilane and methacryloyltrichlorosilane (CHsC(CHs)H8IC1s) was prepared in the same manner as in Example 1 using gold, and silylated polymethyl(methacryloyl)silsesquioxane weight average molecular weight M
w = 3.5 x 10') was obtained.
得られた樹脂１０ｊ’とＰ−アジド安息香酸−２−（ジ
アミノメチル）エチル４ｆｔ：メチルインブチルケトン
１００１に溶解し、感光性耐熱樹脂組成物を得た。これ
を実施例１と同様に露光、現像し、パターンニングされ
た絶縁膜（膜厚１．０μｍ）を得た。この膜は、さらに
Ｎ！雰囲気下５００’Ｃ、ｌｈの加熱を行ってもクラッ
クの発生は見られなかった。The obtained resin 10j' was dissolved in 4ft of P-azidobenzoate-2-(diaminomethyl)ethyl: methyl in butyl ketone 1001 to obtain a photosensitive heat-resistant resin composition. This was exposed and developed in the same manner as in Example 1 to obtain a patterned insulating film (thickness: 1.0 μm). This film is even more N! No cracks were observed even after heating at 500'C and lh in an atmosphere.
特公昭４０−１５９８９号公報の参考例１及び実施例Ｉ
Ｋ従って得られるポリフェニルシルセスキオキサン中間
体を水酸化カリウム触媒を用い高分子量化し、重量平均
分子量（Ｍｗ） １．ＯＸ １０“のポリフェニルシル
セスキオキサンヲ得り。Reference Example 1 and Example I of Japanese Patent Publication No. 40-15989
Therefore, the resulting polyphenylsilsesquioxane intermediate was made to have a high molecular weight using a potassium hydroxide catalyst, and the weight average molecular weight (Mw) was increased to 1. Obtained polyphenylsilsesquioxane of OX 10.
このポリフェニルシルセスキオ中すン１０ｆｌＶＣ実施
例１と同様の感光剤をベンゼン１５０ｊ’中に溶解し、
得られた膜は、パターン形成出来なかった。In this polyphenylsilsesquio medium, 10 fl VC The same photosensitizer as in Example 1 was dissolved in benzene 150 j',
The resulting film could not be patterned.
本発明によれば、それ自体感光性をもち、かつ十分な耐
熱性、耐クラツク性を有する膜を形成可能なため、はん
雑なレジストプロセスを用いることなく、多ｒ−配線形
成が容易に行なえる。According to the present invention, since it is possible to form a film that is photosensitive and has sufficient heat resistance and crack resistance, it is possible to easily form multiple r-wirings without using a complicated resist process. I can do it.
Claims (2)
合物、および芳香族スルホニル化合物を混合してなるこ
とを特徴とする感光性耐熱樹脂組成物。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [n is an integer from 10 to 1000 R_1, R_2 is a methyl group, acryloyl group, or methacryloyl group] An aromatic azide compound , and an aromatic sulfonyl compound.
合物、および芳香族スルホニル化合物を混合してなる感
光性耐熱樹脂組成物を配線層の形成された基材の上に塗
布し、露光、現像した後、不活性ガス雰囲気下３５０℃
、１ｈの熱処理を施すことを特徴とする絶縁層形成方法
。(2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [n is an integer from 10 to 1000 R_1, R_2 is a methyl group, acryloyl group, or methacryloyl group] An aromatic azide compound , and an aromatic sulfonyl compound is applied onto the base material on which the wiring layer is formed, exposed and developed, and then heated at 350°C in an inert gas atmosphere.
, a method for forming an insulating layer, characterized by performing heat treatment for 1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5975486A JPS62215944A (en) | 1986-03-18 | 1986-03-18 | Heat resistant photosensitive resin composition and formation of insulating layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5975486A JPS62215944A (en) | 1986-03-18 | 1986-03-18 | Heat resistant photosensitive resin composition and formation of insulating layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62215944A true JPS62215944A (en) | 1987-09-22 |
Family
ID=13122356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5975486A Pending JPS62215944A (en) | 1986-03-18 | 1986-03-18 | Heat resistant photosensitive resin composition and formation of insulating layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62215944A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0299955A (en) * | 1988-10-06 | 1990-04-11 | Fujitsu Ltd | Production of photosensitive heat resistant resin composition and insulating layer |
| JPH03237460A (en) * | 1990-02-15 | 1991-10-23 | Oki Electric Ind Co Ltd | Resist material |
| JPH10319597A (en) * | 1997-05-23 | 1998-12-04 | Mitsubishi Electric Corp | Photosensitive silicone ladder polymer composition and method for transferring pattern to this composition and semiconductor device using this composition |
| US6284858B1 (en) | 1997-03-14 | 2001-09-04 | Nippon Steel Chemical Co., Ltd. | Silicone compounds and process for producing the same |
| US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
| US8992806B2 (en) | 2003-11-18 | 2015-03-31 | Honeywell International Inc. | Antireflective coatings for via fill and photolithography applications and methods of preparation thereof |
| CN115943187A (en) * | 2020-06-23 | 2023-04-07 | Nck株式会社 | Composition for film encapsulation |
-
1986
- 1986-03-18 JP JP5975486A patent/JPS62215944A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0299955A (en) * | 1988-10-06 | 1990-04-11 | Fujitsu Ltd | Production of photosensitive heat resistant resin composition and insulating layer |
| JPH03237460A (en) * | 1990-02-15 | 1991-10-23 | Oki Electric Ind Co Ltd | Resist material |
| US6284858B1 (en) | 1997-03-14 | 2001-09-04 | Nippon Steel Chemical Co., Ltd. | Silicone compounds and process for producing the same |
| JPH10319597A (en) * | 1997-05-23 | 1998-12-04 | Mitsubishi Electric Corp | Photosensitive silicone ladder polymer composition and method for transferring pattern to this composition and semiconductor device using this composition |
| US8992806B2 (en) | 2003-11-18 | 2015-03-31 | Honeywell International Inc. | Antireflective coatings for via fill and photolithography applications and methods of preparation thereof |
| US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
| CN115943187A (en) * | 2020-06-23 | 2023-04-07 | Nck株式会社 | Composition for film encapsulation |
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