JPS62268132A - Organic insulating film for semiconductor - Google Patents
Organic insulating film for semiconductorInfo
- Publication number
- JPS62268132A JPS62268132A JP11168586A JP11168586A JPS62268132A JP S62268132 A JPS62268132 A JP S62268132A JP 11168586 A JP11168586 A JP 11168586A JP 11168586 A JP11168586 A JP 11168586A JP S62268132 A JPS62268132 A JP S62268132A
- Authority
- JP
- Japan
- Prior art keywords
- bismaleimide
- aryl
- film
- resin
- group
- 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
- 239000004065 semiconductor Substances 0.000 title claims description 11
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 20
- 229920003986 novolac Polymers 0.000 claims abstract description 16
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000000057 synthetic resin Substances 0.000 claims 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 abstract description 4
- 229930003836 cresol Natural products 0.000 abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 3
- 239000000126 substance Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 6
- -1 maleimide compound Chemical class 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- FJKKJQRXSPFNPM-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(N2C(C=CC2=O)=O)C=C1N1C(=O)C=CC1=O FJKKJQRXSPFNPM-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical compound CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Local Oxidation Of Silicon (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は特定の熱硬化性樹脂からなる半導体用有機絶縁
膜に関する。さらに詳しくは回転又は没、Ｘ法等により
塗布した後、加熱硬化する方法によって、絶縁膜を形成
する特定の熱硬化性樹脂からなる半導体用有機絶縁膜に
関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an organic insulating film for semiconductors made of a specific thermosetting resin. More specifically, the present invention relates to an organic insulating film for semiconductors made of a specific thermosetting resin that forms an insulating film by a method of coating by rotating, sinking, X method, etc. and then heating and curing.
〈従来の技術〉
半導体用有機絶縁膜は、アルミニウム配線間、アルミニ
ウムとポリシリコン配線間の眉間絶縁膜用途に使用され
るほかに、ｐｎ接合部保護膜、素子表面保護膜、ＩＣの
保護基板および封止材等の用途にも幅広く使用されてい
る。<Prior art> Organic insulating films for semiconductors are used as insulating films between aluminum wirings and between aluminum and polysilicon wirings, as well as pn junction protection films, element surface protection films, IC protection substrates, and It is also widely used as a sealing material.
熱硬化性樹脂を用いる有機絶縁膜の形成方法には、涜布
膜法、注型法、トランスファー成形法などがあり、層間
絶縁膜、保護膜用途には塗布膜法が、封止材用途には注
型法、トランスファー成形法が採用されている。Methods for forming organic insulating films using thermosetting resins include the cloth film method, casting method, and transfer molding method. The casting method and transfer molding method are used.
近年これらの各用途において半導体用絶縁膜の使用条件
は厳しくなる傾向にあり、特に材料の耐熱性は重要な特
性になっている。さらに、半導体の高集積度化が進むに
つれ、配線バタン間の溝が狭くなり、且つ素子表面の凹
凸が大きくなる方向にあり、従来のＣＶＤ法で堆積する
無機膜法では、表面構造依存性が大きすぎるために絶縁
性の保証が困難であり、平担性の優れた熱硬化性樹脂の
開発が要望されていた。In recent years, the conditions for use of insulating films for semiconductors have tended to become stricter in each of these applications, and in particular, the heat resistance of the material has become an important characteristic. Furthermore, as semiconductors become more highly integrated, the grooves between wiring battens are becoming narrower, and the unevenness of the device surface is becoming larger.The conventional inorganic film method deposited by CVD has a tendency to become less dependent on the surface structure. Since it is too large, it is difficult to guarantee insulation, and there has been a demand for the development of a thermosetting resin with excellent flatness.
従来、このような目的には熱硬化性のポリイミドｔＭ脂
が使用されていたが、平担性、耐クラツク性は優れてい
るものの加工性の面から高温で長時間の加熱が必要であ
った。Conventionally, thermosetting polyimide tM resin has been used for such purposes, but although it has excellent flatness and crack resistance, it requires heating at high temperatures for long periods of time due to processability. .
また、耐熱性に改良を加えたエポキシ樹脂は気密性、封
止性、加工性に優れているものの、高温時の機械特性、
電気特性および長期間使用時の耐熱劣化性など高度の耐
熱性能は不十分であった。In addition, although epoxy resins with improved heat resistance have excellent airtightness, sealing properties, and processability, they also have poor mechanical properties at high temperatures.
High heat resistance performance such as electrical properties and heat deterioration resistance during long-term use was insufficient.
これらに代る熱硬化性樹脂として、例九ばポリイミドお
よびアルケニルフェノールおよヒ／またはアルケニルフ
ェノールエーテルを含ム熱硬化性混合物（特開昭５２−
９９４号公報）、マレイミド系化合物、ポリアリル化フ
ェノール系化合物およびエポキシ樹脂を含む耐熱性樹脂
組成物（特開昭５８−１８４０９９号公報）等が提案さ
れているが、これらにおいて使用されているポリアリル
化フェノール系化合物には、フェノール性水酸基を有す
るか、或いは加熱硬化時にクライゼン転移によりフェノ
ール性水酸基が生成する構造を有しているため、高温時
の電気特性、耐熱劣化性等の問題を有していた。Examples of alternative thermosetting resins include thermosetting mixtures containing polyimide and alkenylphenol and/or alkenylphenol ether (Japanese Patent Application Laid-Open No.
994), a heat-resistant resin composition containing a maleimide compound, a polyallylated phenol compound, and an epoxy resin (Japanese Unexamined Patent Publication No. 184099/1989), etc., but the polyallylated Phenolic compounds either have phenolic hydroxyl groups or have a structure in which phenolic hydroxyl groups are generated by Claisen rearrangement during heat curing, so they have problems such as electrical properties at high temperatures and heat deterioration resistance. Ta.
〈発明が解決しようとする問題点〉
かかる現状において、本発明が解決すべき問題点は、耐
熱性に優れ、かつ微細バタン間の溝を充分に埋めること
ができ、平担化かつ加工性に優れた特定の熱硬化性樹脂
からなる塗布模型半導体用有機絶縁膜を提供することに
ある。<Problems to be Solved by the Invention> Under the current situation, the problems to be solved by the present invention are to have excellent heat resistance, to be able to sufficiently fill the grooves between the fine battens, and to be flattened and workable. An object of the present invention is to provide an organic insulating film for coated model semiconductors made of an excellent specific thermosetting resin.
く問題点を解決するための手段〉
本発明者らは、前述問題点に鋭意取り組み、ある特定の
樹脂とマレイミド系化合物を含む熱硬化性樹脂とからな
る塗布膜が・耐熱性に優れ、かつ微細バタン間の穴埋性
、平担性、かつ加工性に優れていることを見い出し本発
明を完成させるに至った。Means for Solving the Problems> The present inventors have worked diligently to solve the above problems and have found that a coating film made of a specific resin and a thermosetting resin containing a maleimide compound has excellent heat resistance and It was discovered that the material has excellent hole-filling properties between fine battens, flattening properties, and workability, leading to the completion of the present invention.
即チ本発明は、アリルエーテル化された置換フェノール
類ノボラック樹脂おヨヒＮ、Ｎ’−ビスマレイミド化合
物を、後者の二１待合に対する前者の二重結合の比が０
．２を越える３以下となる割合で
含有した熱硬化性樹脂からなる半導体用有１絶縁膜に係
るものである。In other words, the present invention provides an allyl etherified substituted phenolic novolac resin N,N'-bismaleimide compound in which the ratio of the double bonds of the former to the 21 bonds of the latter is 0.
．． This invention relates to an insulating film for semiconductors made of a thermosetting resin containing a thermosetting resin in a proportion of more than 2 and less than or equal to 3.
以下、本発明を具体的に説明する。The present invention will be explained in detail below.
本発明に於て、アリルエーテル化された置換フェノール
ノボラック樹脂は、アルキル基、アルケニル基、アリー
ル基、アラルキルｔ２いはハロゲン原子で置換されたフ
ェノール類、具体的には、クレゾール、エチルフェノー
ル、イソプロピルフェノール、ブチルフェノール、オク
チルフェノール、ノニルフェノール、ビニルフェノール
、イソプロペニルフェノール、フェニルフェノール、ベ
ンジルフェノール、クロルフェノール、ブロムフェノー
ル、キシレノール、メチルブチルフェノール（夫々異性
体を含む）等の置換フェノールの一種又は二種以上とホ
ルムアルデヒド、フルフラール、アクロレイン等のアル
デヒド類とを公知の方法で縮重合反応させて得られる通
常２〜１５の平均核体数を有するノボラック樹脂と塩化
アリル、臭化アリル、ヨウ化アリル等のハロゲン化アリ
ルとをアルカリの仔在下に反応させて得られもこれらの
ノボラック樹脂は実質的にフェノール性水酸基および核
置換アリル基を有さないアリルエーテル化された置換フ
ェノールノボラック樹脂が好ましく、特にクレゾールノ
ボラック樹脂のアリルエーテル化物が好適に使用される
。In the present invention, the allyl etherified substituted phenol novolac resin is a phenol substituted with an alkyl group, an alkenyl group, an aryl group, an aralkyl t2 or a halogen atom, specifically, cresol, ethylphenol, isopropyl One or more substituted phenols such as phenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, xylenol, methylbutylphenol (including isomers) and formaldehyde. , furfural, acrolein, and other aldehydes by a known method, and a novolac resin having an average number of nuclei of 2 to 15, and an allyl halide such as allyl chloride, allyl bromide, allyl iodide, etc. These novolac resins are preferably allyl etherified substituted phenol novolak resins which do not substantially have phenolic hydroxyl groups and nuclear substituted allyl groups, and particularly cresol novolak resins. Allyl etherified products are preferably used.
本発明に於て使用されるＮ 、 Ｎ’−ビスマレイミド
化合物としては、Ｎ、Ｎ’−ジフェニルメタンビスマレ
イミド、Ｎ、Ｎ−フエニレンビスマレイミＦ、Ｎ、Ｎ−
＊フェニルエーテルビスマレイミド、Ｎ、Ｎ−ジフェニ
ルスルホンピスマレイ疋ド、Ｎ、Ｎ’−シクロヘキシル
メタンビスマレイミド、Ｎ 、 Ｎ’−キシレンビスマ
レイミド、Ｎ、Ｎ’−トリレンビスマレイミド、Ｎ 、
Ｎ’−キシレンビスマレイミド、Ｎ 、 Ｎ’−ジフ
ェニルシクロヘキサンビスマレイミド（夫々異性体を含
ム）、Ｎ、Ｎ’−エチレンビスマレイミド、等があるが
、持にＮ、Ｎ’−ジフェニルメタンビスマレイミドが好
ましい。更にこれらＮ、 Ｎ’−ビスマレイミド化合物
とジアミン類を付加させてｉＧられる末端がＮ、Ｎ’−
ビスマレイミド骨核を有するプレポリマー等が使用でき
る。N,N'-bismaleimide compounds used in the present invention include N,N'-diphenylmethane bismaleimide, N,N-phenylenebismaleimide F, N,N-
*Phenyl ether bismaleimide, N, N-diphenylsulfone bismaleimide, N, N'-cyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-tolylene bismaleimide, N,
N'-xylene bismaleimide, N,N'-diphenylcyclohexane bismaleimide (each including isomers), N,N'-ethylene bismaleimide, etc., among which N,N'-diphenylmethane bismaleimide preferable. Furthermore, by adding these N,N'-bismaleimide compounds and diamines, the iG terminal becomes N,N'-
A prepolymer having a bismaleimide core can be used.
又、Ｎ、Ｎ″−ビスマレイミド化合物はゲル化が起こら
ない程度に予めアリル基と反応させてプレポリマーを生
成させておくことが好ましい。Further, it is preferable that the N,N''-bismaleimide compound is reacted with an allyl group in advance to form a prepolymer to an extent that gelation does not occur.
本発明になる熱硬化性樹脂において、アリルエーテル化
された置換フェノール特ノボラック樹脂とＮ、Ｎ’−ビ
スマレイミド化合物の割合は、後者の二重結合に対する
前者の二重結合の比が０．２を越え３以下、好ましくは
０．５を越九２以下となるように選ぶのが良い、０．２
以下又は８を越えると耐熱性が低下するため好ましくな
い。In the thermosetting resin of the present invention, the ratio of the allyl etherified substituted phenol special novolak resin and the N,N'-bismaleimide compound is such that the ratio of the former double bond to the latter double bond is 0.2. It is better to select a value that exceeds 3 and is preferably 0.5 and 92 or less, 0.2
If it is less than or exceeds 8, it is not preferable because the heat resistance decreases.
塗布膜形成方法は、上記アリルエーテル化された置換フ
ェノール類ノボラック樹脂とＮ 、Ｎ″−ビスマレイミ
ド化合物のプレポリマーをジオキサン、テトラヒドロフ
ラン等の環状エーテル系溶剤、又はジメチルホルムアミ
ド、ジメチルスルホキシド、アセトニトリル、Ｎ−メチ
ルピロリドン、ジメチルアセトアミド、ヘキサメチルホ
スホリルアミド、スルホラン、テトラメチル尿素等の非
プロトン性極性溶剤より選ばれる１皿の溶剤又は２Ｎ以
上の混合溶剤に必要な膜厚が得られるように溶剤量を調
節して溶解して一般に使用される回転法又は浸漬法等に
より塗布する。次で低温加熱Ｉこよりｉ剤を充分除去し
た後、２５０°Ｃ以上４５０ ”Ｃ以下、好ましくは８
００°Ｃ以上４００℃以下の温度で、１０分以上好まし
くは８０分以上加熱して硬化せしめることにより、従来
のめでリイミドと同等又はそれ以上の耐熱性に浸れ、か
つ平担性及び短時間加熱で硬化する加工性に優れた絶縁
膜が形成できる。The method for forming a coating film is to mix a prepolymer of the allyl etherified substituted phenolic novolac resin and N,N''-bismaleimide compound with a cyclic ether solvent such as dioxane or tetrahydrofuran, or with dimethylformamide, dimethylsulfoxide, acetonitrile, N - Adjust the amount of solvent to obtain the necessary film thickness for one plate of solvent or a mixed solvent of 2N or more selected from aprotic polar solvents such as methylpyrrolidone, dimethylacetamide, hexamethylphosphorylamide, sulfolane, and tetramethylurea. The solution is adjusted and melted and applied by a generally used rotation method or dipping method. Next, after sufficiently removing the agent I by heating at a low temperature, the temperature is 250°C or more and 450"C or less, preferably 8°C.
By heating and curing at a temperature of 00°C or more and 400°C or less for 10 minutes or more, preferably 80 minutes or more, it has heat resistance equal to or higher than conventional medelimide, and has flatness and short heating time. It is possible to form an insulating film with excellent workability that is cured by
また目的に応じて、本発明の特定の熱硬化性樹脂に他の
公知の熱硬化性樹脂、例えば他のアリル系樹脂、エポキ
シ樹脂、不飽和ポリエステル樹脂、フェノール樹脂、シ
リコーンｔｌＪＢＬトリアジン樹脂等を添加してもよい
。Depending on the purpose, other known thermosetting resins such as other allyl resins, epoxy resins, unsaturated polyester resins, phenolic resins, silicone tlJBL triazine resins, etc. may be added to the specific thermosetting resin of the present invention. You may.
かくして、本発明の特定の熱硬化性−詣から得られる塗
布膜は、耐熱性に優れ、平担性、かつ加工性に優れた半
導体用有ｔａ絶縁膜として有用である。Thus, the coating film obtained from the specific thermosetting method of the present invention is useful as a ta-containing insulating film for semiconductors that has excellent heat resistance, flatness, and processability.
〈実施例〉
以下本発明を実施例により具体的に説明するが、本発明
は何等これらに限定されるものではない、
物性値の測定は次の如く行った。<Example> The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these in any way. Physical property values were measured as follows.
（１）膜厚の測定
ランクテーラ−・ホブソン社のタリステップで膜厚を測
定した。(1) Measurement of Film Thickness Film thickness was measured using Talystep manufactured by Rank Taylor Hobson.
（２） 回転塗布法
ミカサ社のミカサスビンナーＩＨ−８６０型で、特定の
熱硬化樹脂と有機溶剤とからなる塗布液を数−シリコン
ウェハ上に滴下して５００〜８５００ｒｐｍで１５秒間
回転塗布して、塗布膜を形成した。(2) Spin coating method Using a Mikasa Binner IH-860 model manufactured by Mikasa Co., Ltd., a coating solution consisting of a specific thermosetting resin and an organic solvent was dropped onto a silicon wafer and spin coated at 500 to 8,500 rpm for 15 seconds. A coating film was formed.
（３） クラック確認法
光学ｆｉ微鏡を使用し、倍率８０倍にてクラック発生の
有焦を確認した。(3) Crack Confirmation Method Using an optical FI microscope, the occurrence of cracks was confirmed at 80x magnification.
実施例１
アリルエーテル化された置換フェノール類ノボラック樹
脂として、特開昭５９−２２７９１８号公報記載の方法
、即ちジメチルホルムアミド４００ｇに０−クレゾール
ノボラック型樹ｕｆｔ ｔ ｓ ｙ、水酸化ナトリウム
フレーク４８１を加へ、窒素雰囲気中、攪拌下に４０’
Ｃ迄昇温しで樹脂を完全に溶解した後、塩化アリル９２
ｇを８時間かけて滴下する。尚下後も１時間同温度に保
ち、ついで５０”Ｃ迄昇温し、８時間同温間に保持した
後、不溶の塩分を戸別し、濃縮、水洗により得た。アリ
ルエーテル化クレゾールノボラック（以下ＡＬＣＮと称
する）を、Ｎ、Ｎ’−ビスマレイミド化合物として、Ｎ
、Ｎ’ −４、４’−フェニルメタンビスマレイミド
（以下ＢＭＩと称する）を用い、ＢＭＩに対するＡＬＣ
Ｎの二重結合の比が１対１になるように混合して１６０
″Ｃ１８０分でプレ重合した樹脂組成物を夫々８０重量
％、４０重量％含むジオキサン溶液を、パタンのないシ
リコンウェハとに回転塗布して塗布膜を形成し、クリー
ンオーブン中で１００’Ｃ１１０分加熱後、拡散炉に入
れ８００°Ｃ１１０分間ベーキングした。この時の膜厚
は夫々ａｏ 、ｏｏｏ 人、１００．０００人であっ
た。Example 1 Allyl etherified substituted phenolic novolac resin was prepared using the method described in JP-A-59-227918, in which 400 g of dimethylformamide was added with 0-cresol novolak type tree uft sy and sodium hydroxide flakes 481. 40' under stirring in a nitrogen atmosphere.
After completely dissolving the resin by raising the temperature to C, allyl chloride 92
g was added dropwise over 8 hours. After lowering, the temperature was kept at the same temperature for 1 hour, then raised to 50"C, and kept at the same temperature for 8 hours. Insoluble salts were removed from each house, concentrated, and washed with water to obtain allyl etherified cresol novolac ( (hereinafter referred to as ALCN) as an N,N'-bismaleimide compound, N
, N'-4,4'-phenylmethane bismaleimide (hereinafter referred to as BMI) was used to perform ALC on BMI.
Mix so that the ratio of N double bonds is 1:1.
A dioxane solution containing 80% by weight and 40% by weight of a resin composition prepolymerized at 180 minutes at C was spin-coated onto a silicon wafer without a pattern to form a coating film, and heated in a clean oven at 100'C for 110 minutes. Thereafter, they were placed in a diffusion furnace and baked at 800° C. for 110 minutes.The film thicknesses at this time were ao, ooo, and 100,000, respectively.
クラックの発生は認められなかった。No cracks were observed.
更に４００ ’Ｃに再加熱し、８０分熱処理して、膜厚
を測定した所夫々２４，０００ 人、８１．０００人に
なったがクラックは発生していなかった。After further heating to 400'C and heat treatment for 80 minutes, the film thicknesses were measured to be 24,000 and 81,000, respectively, but no cracks were observed.
更に４５０″Ｃ１１０分熱処理をして膜厚を測定した所
夫々１７．ｏｏｏ人、６８，０００人になり膜の一部が
変色した。膜厚１７，０００人のものではクラックはな
かったが、一方、６８．０００人の膜厚では全面にクラ
ックが発生した。When the film was further heat treated at 450"C for 110 minutes and the film thickness was measured, it became 17.00 mm and 68,000 mm, respectively, and a part of the film was discolored. There were no cracks in the film with a thickness of 17,000 mm, but On the other hand, cracks occurred on the entire surface when the film thickness was 68,000.
次にＡＬＣＮ／ＢＭＩ の二重結合の比を１／１にし
て混合してプレ重合した樹脂組成物を８０％含むジオキ
サン溶液を、パタンのないシリコンウェハ上に、１，０
００ｒｐｍ で回転塗布して、同様に１００ ”Ｃ５１
０分次いで４００’Ｃ１１０分熱処理をして、２０．０
００人の膜厚を得た。更に同様の回転受布、加熱処理を
２回繰返して、合計６０，０００人の膜厚を得たが、い
ずれもクラックは認められなかった。Next, a dioxane solution containing 80% of a resin composition prepolymerized by mixing ALCN/BMI with a double bond ratio of 1/1 was placed on an unpatterned silicon wafer at 1,0%
Spin coat at 00 rpm and apply 100"C51 in the same way.
0 minutes, then heat treated at 400'C for 110 minutes, resulting in a temperature of 20.0
The film thickness of 00 people was obtained. Furthermore, the same rotating application and heat treatment were repeated twice to obtain a total film thickness of 60,000, but no cracks were observed in either case.
実施例２
ＡＬＣＮ／ＢＭＩ の二重結合比を１／１にして混合
してプレ重合した樹脂組成物を６０％含むジメチルホル
ムアミド溶液を、ジメチルホルムアミドで２．６倍に希
釈し、１μｍ段差のアルミニウム配線パタンのある４イ
ンチウェハ上に８５０ Ｏｒｐｍ で回転塗布した。Example 2 A dimethylformamide solution containing 60% of a resin composition prepolymerized by mixing ALCN/BMI with a double bond ratio of 1/1 was diluted 2.6 times with dimethylformamide, and an aluminum layer with a 1 μm step was diluted with dimethylformamide. It was spin-coated at 850 rpm onto a 4-inch wafer with a wiring pattern.
実施例１と同様の方法で１６０″Ｃ１１０分、更に４０
０ ’Ｏで８０分熱処理した。ウェハを壬
破断し、溝の穴埋性並びに平担性を退避型電子顕微鏡（
倍率１０，０００倍）で観察した結果、いずれも良好で
あった。又クラックの発生も認められなかったアルミニ
ウム配線上ではｉ、ｏｏｏ人、溝部で１よ、ｏｏｏ 人
の膜厚であった。160″C for 110 minutes in the same manner as in Example 1, and further for 40 minutes.
Heat treatment was performed at 0'O for 80 minutes. The wafer was broken open and the filling and flattening properties of the grooves were examined using a retractable electron microscope (
As a result of observation at a magnification of 10,000 times, all were good. Moreover, the film thickness was 1,000 mm on the aluminum wiring, where no cracks were observed, and 1,000,000 mm in the groove.
実施例３
ＡＬＣＮ／ＢＭＩの二重結合の比を第１表のように変化
させて混合し、プレ重合した樹脂組成物５０％含むジメ
チルホルムアミド溶液を、実施例２の方法に準じて３イ
ンチウェハ上に３５０Ｏｒｐｍで回転塗布し、Ｌ ５
Ｑ ’Ｃ１１ｏ分更に４０Ｏ’Ｃで３０分加熱処理した
。上記処理を３〜４回くり返した後の耐クラツク性を測
定した結果は第１表のとおりであった。Example 3 A dimethylformamide solution containing 50% of a prepolymerized resin composition mixed with the double bond ratio of ALCN/BMI varied as shown in Table 1 was prepared on a 3-inch wafer according to the method of Example 2. Spin coat at 350 rpm on top, L 5
Q'C11o was further heat-treated at 40O'C for 30 minutes. Table 1 shows the results of measuring the crack resistance after repeating the above treatment 3 to 4 times.
第 １ 表
〈発明の効果〉
本発明により、特定の熱硬化性樹脂から得られる塗布が
で、耐熱性に優れ、平担性、かつ加工性に優れた半導体
用有機絶縁膜が提供される。Table 1 <Effects of the Invention> According to the present invention, an organic insulating film for semiconductors which can be coated from a specific thermosetting resin, has excellent heat resistance, flatness, and processability is provided.
Claims (1)
脂およびＮ，Ｎ′−ビスマレイミド化合物を、後者の二
重結合に対する前者の二重結合の比が０．２を越え３以
下となる割合で含有した熱硬化性樹脂からなることを特
徴とする半導体用有機絶縁膜。A thermosetting material containing an allyl etherified substituted phenolic novolak resin and an N,N'-bismaleimide compound in a ratio such that the ratio of the former double bond to the latter double bond is more than 0.2 and 3 or less. An organic insulating film for semiconductors characterized by being made of a synthetic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11168586A JPS62268132A (en) | 1986-05-15 | 1986-05-15 | Organic insulating film for semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11168586A JPS62268132A (en) | 1986-05-15 | 1986-05-15 | Organic insulating film for semiconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62268132A true JPS62268132A (en) | 1987-11-20 |
Family
ID=14567580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11168586A Pending JPS62268132A (en) | 1986-05-15 | 1986-05-15 | Organic insulating film for semiconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62268132A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02260425A (en) * | 1989-03-30 | 1990-10-23 | Toppan Printing Co Ltd | Electric element and manufacture thereof |
| US5189082A (en) * | 1991-09-26 | 1993-02-23 | Cheil Industries, Inc. | Imide epoxy resins for sealing semiconductor elements |
| US5210115A (en) * | 1991-02-28 | 1993-05-11 | Cheil Industries, Inc. | Allyl magnesium halide modified epoxy resin composition |
| WO2016104196A1 (en) * | 2014-12-25 | 2016-06-30 | 昭和電工株式会社 | Thermosetting resin composition |
| WO2016104195A1 (en) * | 2014-12-25 | 2016-06-30 | 昭和電工株式会社 | Thermosetting resin composition |
-
1986
- 1986-05-15 JP JP11168586A patent/JPS62268132A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02260425A (en) * | 1989-03-30 | 1990-10-23 | Toppan Printing Co Ltd | Electric element and manufacture thereof |
| US5210115A (en) * | 1991-02-28 | 1993-05-11 | Cheil Industries, Inc. | Allyl magnesium halide modified epoxy resin composition |
| US5189082A (en) * | 1991-09-26 | 1993-02-23 | Cheil Industries, Inc. | Imide epoxy resins for sealing semiconductor elements |
| WO2016104196A1 (en) * | 2014-12-25 | 2016-06-30 | 昭和電工株式会社 | Thermosetting resin composition |
| WO2016104195A1 (en) * | 2014-12-25 | 2016-06-30 | 昭和電工株式会社 | Thermosetting resin composition |
| JPWO2016104195A1 (en) * | 2014-12-25 | 2017-06-15 | 昭和電工株式会社 | Thermosetting resin composition |
| JPWO2016104196A1 (en) * | 2014-12-25 | 2017-06-22 | 昭和電工株式会社 | Thermosetting resin composition |
| CN107001547A (en) * | 2014-12-25 | 2017-08-01 | 昭和电工株式会社 | Compositions of thermosetting resin |
| US10160856B2 (en) | 2014-12-25 | 2018-12-25 | Showa Denko K.K. | Thermosetting resin composition |
| US10689493B2 (en) | 2014-12-25 | 2020-06-23 | Showa Denko K.K. | Thermosetting resin composition |
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