JPS63138734A - Pattern formation using three-layer resist - Google Patents
Pattern formation using three-layer resistInfo
- Publication number
- JPS63138734A JPS63138734A JP28417386A JP28417386A JPS63138734A JP S63138734 A JPS63138734 A JP S63138734A JP 28417386 A JP28417386 A JP 28417386A JP 28417386 A JP28417386 A JP 28417386A JP S63138734 A JPS63138734 A JP S63138734A
- Authority
- JP
- Japan
- Prior art keywords
- resin layer
- polyimide resin
- polyimide
- layer
- pattern
- 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
- 230000007261 regionalization Effects 0.000 title 1
- 229920001721 polyimide Polymers 0.000 claims abstract description 51
- 239000009719 polyimide resin Substances 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000002834 transmittance Methods 0.000 claims description 11
- 239000004642 Polyimide Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001312 dry etching Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- SNCJAJRILVFXAE-UHFFFAOYSA-N 9h-fluorene-2,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3CC2=C1 SNCJAJRILVFXAE-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910005091 Si3N Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000005360 phosphosilicate glass Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FIVTXMHPGUKRPQ-UHFFFAOYSA-N 1,2-diaminoxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3OC2=C1 FIVTXMHPGUKRPQ-UHFFFAOYSA-N 0.000 description 1
- JFOCEBKIPCVSGU-UHFFFAOYSA-N 1h-pyrrolo[2,3-d]imidazol-2-one Chemical group C1=CNC2=NC(=O)N=C21 JFOCEBKIPCVSGU-UHFFFAOYSA-N 0.000 description 1
- ITBFRZCTJQWRKV-UHFFFAOYSA-N 2,3-diaminofluoren-1-one Chemical compound C1=CC=C2C3=CC(N)=C(N)C(=O)C3=CC2=C1 ITBFRZCTJQWRKV-UHFFFAOYSA-N 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- SKKKJNPBIGQNEJ-UHFFFAOYSA-N 9h-fluorene-1,9-diamine Chemical compound C1=CC(N)=C2C(N)C3=CC=CC=C3C2=C1 SKKKJNPBIGQNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Landscapes
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、三層レジストによるパターン形成方法に関す
るものであり、ざらに詳しくは、ポリイミド系樹脂の微
細パターンを三層レジストにより形成する方法に関する
ものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for forming a pattern using a three-layer resist, and more specifically, relates to a method for forming a fine pattern of polyimide resin using a three-layer resist. It is something.
［従来の技術］
ポリイミド系樹脂を用いた三層レジストによるパターン
形成方法としては、Ｐｉｅｔｅｒ ｓ、ａｕｒｇｇｒａ
ａｒ、“）ｌｕｌｔｉｌａｙｅｒ−Ｒｅｓｉｓｔ Ｌｉ
ｔｈｏｇｒａｐｈｙ ” 、Ｓｅｍ１ｃＯｎｄｕｃｔｏ
ｒ Ｉｎｔｅｒｎａｔｉｏｎａｌ、 ｐｐ、５５（Ｊｕ
ｎｅ １９８３）などに記載の通り公知である。[Prior Art] As a pattern forming method using a three-layer resist using a polyimide resin, Pieter's, Aurgra
ar, “) ultillayer-Resist Li
thography”, Sem1cOnducto
r International, pp, 55 (Ju
ne 1983) and others.
従来のポリイミド系樹脂を用いた三層レジストによるパ
ターン形成工程は次の通りである。The conventional pattern forming process using a three-layer resist using a polyimide resin is as follows.
■ 基板上にポリイミド系樹脂層を形成する。■ Form a polyimide resin layer on the substrate.
通常、スピンナーによる塗布方法が用いられ、この被膜
により段差のめる基板が平坦化される。Usually, a coating method using a spinner is used, and this coating flattens the substrate on which the steps are to be covered.
■ 次にポリイミド系樹脂層の上に中間層として無機被
膜を形成する。無機被膜としては、ＳｉＯ２、Ｓｉ３Ｎ
４などが用いられる。この無機被膜はポリイミド系樹脂
層と最上層の感光性樹脂とを化学的に分離する役割と、
後の工程でポリイミド系樹脂をドライエツチングする時
のマスクとしての機能を有する。(2) Next, an inorganic film is formed as an intermediate layer on the polyimide resin layer. As the inorganic coating, SiO2, Si3N
4 etc. are used. This inorganic coating has the role of chemically separating the polyimide resin layer and the top layer photosensitive resin,
It functions as a mask when dry etching polyimide resin in a later process.
■ この無機被膜の上に感光性樹脂被膜を形成する。こ
の感光性樹脂はネカ、ポジどちらのタイプでも良いが、
通常、屏象度の点でポジタイプが好ましく用いられる。■ A photosensitive resin film is formed on this inorganic film. This photosensitive resin can be either negative or positive type, but
Generally, positive type is preferably used in terms of visibility.
■ 感光性樹脂を露光、現像し、パターンを形成する。■ Expose and develop photosensitive resin to form a pattern.
露光は通常、解像度の点からｑ線（４３６ｎｍの紫外線
）のステッパーが用いられる。For exposure, a q-line (ultraviolet light of 436 nm) stepper is usually used from the viewpoint of resolution.
■ 次に０項で得られた感光性樹脂のパターンを中間層
である無機被膜に転写する。転写は感光性樹脂のパター
ンをマスクにウェット又はドライで中間層をエツチング
することにより行われる。(2) Next, the pattern of the photosensitive resin obtained in Section 0 is transferred to the inorganic coating that is the intermediate layer. The transfer is performed by wet or dry etching of the intermediate layer using the photosensitive resin pattern as a mask.
■ このようにして得られた無機被膜をマスクにしてポ
リイミド系樹脂をドライエツチングするとポリイミド系
樹脂の微細パターンが得られる。(2) By dry etching the polyimide resin using the thus obtained inorganic film as a mask, a fine pattern of the polyimide resin can be obtained.
ドライエツチングとしてはりアクティブイオンエツチン
グ（ＲＩＥ）、プラズマエツチングなどが用いられる。As dry etching, active ion etching (RIE), plasma etching, etc. are used.
■ 最後にポリイミド系樹脂をマスクにして基板面をド
ライエツチングする。ドライエツチング後、ポリイミド
系樹脂は剥離される。■Finally, dry etching the substrate surface using polyimide resin as a mask. After dry etching, the polyimide resin is peeled off.
［発明が解決しようとする問題点］
この方法の問題点はポリイミド系樹脂のｑ線における透
過率が高いことである。これはステッパーで最上層の感
光性樹脂を露光する際、光がポリイミド系樹脂の被膜を
透過して基板面、特に段差面で反射し、解像度を低下さ
せる。その対策としてポリイミド系樹脂に染料を添加す
る方法が、前述した公知文献に記載されている。しかし
ながらポリイミド系樹脂に染料を添加する方法は以下に
示す欠点がある。[Problems to be Solved by the Invention] The problem with this method is that the polyimide resin has a high transmittance in the q-ray. This is because when the top layer of photosensitive resin is exposed with a stepper, light passes through the polyimide resin coating and is reflected on the substrate surface, particularly on the stepped surface, reducing resolution. As a countermeasure against this problem, a method of adding a dye to a polyimide resin is described in the above-mentioned known literature. However, the method of adding dye to polyimide resin has the following drawbacks.
■ ポリイミド系樹脂のキュア温度（３５０℃〜４００
℃）で染料が熱分解し、退色する。■ Cure temperature of polyimide resin (350℃~400℃
The dye thermally decomposes and fades at temperatures (℃).
■ 染料には半導体素子の信頼性を低下させる金属性不
純物が多く含まれており、容易に精製除去できない。■Dye contains many metallic impurities that reduce the reliability of semiconductor devices, and cannot be easily purified and removed.
本発明は、かかる問題点を解消せしめ、かつ解像度に優
れたポリイミド系樹脂の微細パターンを三層レジストに
より形成する方法を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to solve these problems and provide a method for forming a fine pattern of polyimide resin with excellent resolution using a three-layer resist.
［問題点を解決するための手段］
かかる本発明の目的は、基板上にポリイミド系樹脂層、
無機被膜および感光性樹脂層を順次形成し、ついで該感
光性樹脂層、無機被膜およびポリイミド系樹脂層をこの
順序でパターン加工する三層レジストのパターン形成方
法において、該ポリイミド系樹脂層として、膜厚２μｍ
での４３６ｎｍの紫外線透過率が５０％以下であるポリ
イミド系樹脂を用いることを特徴とする三層レジストに
よるパターン形成方法により達成される。[Means for Solving the Problems] The object of the present invention is to provide a polyimide resin layer on a substrate,
In a three-layer resist pattern forming method in which an inorganic coating and a photosensitive resin layer are sequentially formed, and then the photosensitive resin layer, the inorganic coating and the polyimide resin layer are patterned in this order, the polyimide resin layer is formed by forming a film. Thickness 2μm
This is achieved by a pattern forming method using a three-layer resist, which is characterized by using a polyimide resin whose ultraviolet transmittance at 436 nm is 50% or less.
本発明でいう基板とは半導体素子用に通常使用されるも
ので、例えばシリコンウェハが好ましく用いられる。The substrate referred to in the present invention is one commonly used for semiconductor devices, and for example, a silicon wafer is preferably used.
本発明でいう無機被膜としては、Ｓｉｏ２ 、Ｓｉ３Ｎ
４、ＰＳＧ（リンケイ酸ガラス）、ＴｉＯ２などが挙げ
られ、特にＣＶＤ法のＳｉｏ２が好ましく用いられる。The inorganic coating referred to in the present invention includes Sio2, Si3N
4, PSG (phosphosilicate glass), TiO2, etc., and CVD method Sio2 is particularly preferably used.
膜厚は数百人〜数μの範囲が好ましく用いられる。The film thickness is preferably in the range of several hundred to several microns.
本発明でいう感光性樹脂とは、ｑ線に感度を有するもの
であれば良く、解像度の点からキノンジアジド系のポジ
タイプのフォトレジストが好ましく用いられる。The photosensitive resin referred to in the present invention may be any resin as long as it is sensitive to q-rays, and a quinonediazide-based positive type photoresist is preferably used from the viewpoint of resolution.
本発明でいうポリイミド系樹脂とは、イミド環を有する
ポリマをいい、その他の環状構造、例えば、イミダゾピ
ロロン環、イソインドロキナゾリン環などを含んでいて
も良い。The polyimide resin in the present invention refers to a polymer having an imide ring, and may also contain other cyclic structures such as an imidazopyrrolone ring and an isoindoquinazoline ring.
本発明においては、かかるポリイミド系樹脂のうち、膜
厚２μｍでの４３６ｎｍの紫外線（ｇ線）透過率が５０
％以下の特性を有するものが用いられる。In the present invention, among such polyimide resins, the transmittance of ultraviolet rays (g-line) at 436 nm at a film thickness of 2 μm is 50
% or less is used.
該紫外線透過率が５０％を上まわる場合には、解像度の
向上効果が期待できない。If the ultraviolet transmittance exceeds 50%, no improvement in resolution can be expected.
本発明で使用可能なポリイミド系樹脂としては、例えば
、ジアミノフルオレン、ジアミノキサントンまたはジア
ミノフルオレノンと芳香族テトラカルボン酸無水物から
誘導されるポリイミド等を挙げることができる。２，７
−ジアミノフルオレンとピロメリット酸二無水物、２，
７−ジアミノフルオレンとベンゾフェノンテトラカルポ
ン酸二無水物、２，７−ジアミノフルオレンと３．３−
。Examples of polyimide resins that can be used in the present invention include polyimides derived from diaminofluorene, diaminoxanthone, or diaminofluorenone and aromatic tetracarboxylic acid anhydrides. 2,7
-diaminofluorene and pyromellitic dianhydride, 2,
7-diaminofluorene and benzophenone tetracarboxylic dianhydride, 2,7-diaminofluorene and 3.3-
.
４．４′−ビフェニルテトラカルボン酸二無水物、２．
７−ジアミノフルオレンとビフェニルエーテルテトラカ
ルボン酸二無水物から誘導されるポリイミド系樹脂が良
好な紫外線遮蔽特性を示し、特に好ましいが、これらに
限定されない。4.4'-biphenyltetracarboxylic dianhydride, 2.
Polyimide resins derived from 7-diaminofluorene and biphenyl ether tetracarboxylic dianhydride exhibit good UV-shielding properties and are particularly preferred, but not limited thereto.
また本発明の方法に用いられるポリイミド系樹脂に該当
するポリマは、ホモポリマであっても良いし、ヘテロポ
リマであっても良い。Further, the polymer corresponding to the polyimide resin used in the method of the present invention may be a homopolymer or a heteropolymer.
好ましい紫外線透過率は、４０％以下、より好ましくは
３０％以下である。The preferred ultraviolet transmittance is 40% or less, more preferably 30% or less.
［発明の効果］
本発明は基板上にポリイミド系樹脂層、無機被膜、感光
性樹脂層からなる三層レジストのパターン形成方法にお
いて、該ポリイミド系樹脂として露光機の紫外線（４３
５ｎｍ ）を良く遮蔽する特性を有するものを用いたの
で、高解像度の微細パターンを確実に得ることができる
。また、本発明によれば第３成分として染料をポリイミ
ド系樹脂に添加する方法の欠点であるキュア時の退色を
解消できるのみならず、半導体素子の信頼性に悪影響を
及ぼす金属性不純物も原料段階で容易に精製除去できる
利点がある。[Effects of the Invention] The present invention provides a method for forming a pattern on a three-layer resist consisting of a polyimide resin layer, an inorganic coating, and a photosensitive resin layer on a substrate.
Since a material having a property of effectively blocking 5 nm) was used, a fine pattern with high resolution can be reliably obtained. In addition, according to the present invention, not only can discoloration during curing, which is a drawback of the method of adding dye as a third component to polyimide resin, can be eliminated, but also metallic impurities, which have a negative impact on the reliability of semiconductor devices, can be eliminated from the raw material stage. It has the advantage of being easily purified and removed.
次に実施例に基づいて本発明の詳細な説明する。Next, the present invention will be explained in detail based on examples.
実施例１
メタノールで再結晶した２、７−ジアミツフルオレン１
９．６３（ｌを蒸溜したジメチルアセトアミド２７０ｇ
に溶解しアミン溶液を調合した。無水酢酸で再結晶した
ピロメリット酸二無水物２１．８１ｇを粉末でアミン溶
液に添加後、３０’Ｃで５時間攪拌し、粘度１６．４ポ
アズ／２５℃のワニスを１ｑた。このワニスを１μｍの
メンブレンフィルターでろ過し、塗布液を作製した。Example 1 2,7-Diamitsufluorene 1 recrystallized from methanol
270 g of dimethylacetamide distilled from 9.63 (l)
An amine solution was prepared by dissolving it in After adding 21.81 g of pyromellitic dianhydride recrystallized from acetic anhydride as a powder to the amine solution, the mixture was stirred at 30'C for 5 hours to obtain 1q of varnish having a viscosity of 16.4 poise/25°C. This varnish was filtered through a 1 μm membrane filter to prepare a coating solution.
次にアルミ配線を施したシリコンウェハにスピンナでこ
の塗布液を塗布し、１００°Ｃ１２００’Ｃ１３５０℃
で各々３０分熱処理して膜厚２μｍのポリイミド樹脂の
被膜を形成した。なお使用したシリコンウェハは接着性
改善のため、γ−アミノプロピルトリエトキシシランで
処理したものを用いた。Next, apply this coating solution to a silicon wafer with aluminum wiring using a spinner, and heat it at 100°C, 1200°C, and 1350°C.
Each was heat-treated for 30 minutes to form a polyimide resin film with a thickness of 2 μm. The silicon wafer used was treated with γ-aminopropyltriethoxysilane to improve adhesion.
ついでこのポリイミド樹脂の被膜の上にＣＶＤ法により
、５ｉｏｚ層を１５００人形成した。さらにスピンナで
シップレイ社製のポジ型感光性樹脂 ＡＺ−１４００を
１μｍの膜厚になるよう塗布した。続いて日本光学■製
のステッパー（ｇ線用） Ｎ５Ｒ−１５０５Ｇ３Ａを用
いて露光後、シップレイ社製現像液 ＨＦ−３１４で現
像し、感光性樹脂のパターンを得た。っいで１４０℃で
３０分ベーキングした後、これをマスクに弗酸／弗化ア
ンモニウムの１７１０の緩衝液で５ｉ０２膜をエツチン
グした。次に０２プラズマでポリイミド樹脂をエツチン
グした。このようにして解像度１．５μｍの微細なポリ
イミドのパターンを得た。得られたパターンをマスクに
シリコンウェハの表面をエツチングした後、ポリイミド
樹脂を０２プラズマで完全に除去した。ポリイミドを除
去後のウェハの表面には金属性の不純物が残存していな
かった。Next, 1,500 5ioz layers were formed on this polyimide resin film by CVD. Further, using a spinner, a positive photosensitive resin AZ-1400 manufactured by Shipley was applied to a film thickness of 1 μm. Subsequently, after exposure using a stepper (for g-line) N5R-1505G3A manufactured by Nippon Kogaku, it was developed with a developer HF-314 manufactured by Shipley to obtain a photosensitive resin pattern. After baking at 140° C. for 30 minutes, the 5i02 film was etched with a 1710 buffer solution of hydrofluoric acid/ammonium fluoride using this as a mask. Next, the polyimide resin was etched using 02 plasma. In this way, a fine polyimide pattern with a resolution of 1.5 μm was obtained. After etching the surface of the silicon wafer using the obtained pattern as a mask, the polyimide resin was completely removed using 02 plasma. No metallic impurities remained on the surface of the wafer after polyimide was removed.
また、ポリイミド樹脂の紫外線透過率を測定するため、
別途パイレックスガラス板に上記ワニスを塗布し、１０
０℃、２００℃、３５０°Ｃで各々３０分熱処理し、ポ
リイミド樹脂の被膜を形成した。被膜は溌い黄色を呈し
、この被膜の紫外−可視スペクトルを測定（日立製作新
製３２３型自記分光光度計使用）したところ、膜厚２μ
ｍで４３６ｎｍの透過率が５％と良く光を遮蔽すること
がわかった。In addition, to measure the ultraviolet transmittance of polyimide resin,
Separately, apply the above varnish to a Pyrex glass plate, and
Heat treatment was performed at 0°C, 200°C, and 350°C for 30 minutes each to form a polyimide resin film. The film had a bright yellow color, and when the ultraviolet-visible spectrum of this film was measured (using a new model 323 self-recording spectrophotometer manufactured by Hitachi), the film thickness was 2 μm.
It was found that the transmittance at 436 nm at m was 5%, and the light was well blocked.
なお金属性の不純物の残査の分析は、西独ＡＴＯＭＩ
ＫＡ社製二次イオン質量分析装置Ａ−ＤＩＤＡ３０ＯＯ
を用いて行なった。Analysis of residual impurities in money attributes is carried out by West German ATOMI.
KA secondary ion mass spectrometer A-DIDA30OO
This was done using
比較例１
ジアミン成分として４，４−−ジアミノジフェニルエー
テルを用いた以外は実施例１と全く同様に実施した。得
られたポリイミドのパターンの解像度は２．５μｍであ
った。また、この被膜の紫外−可視スペクトルを測定し
たところ、膜厚２μｍで４３６ｎｍの透過率は６０％で
あった。透過率の値より、解像度の低下は露光時の基板
面での反射光の影響を受けていることがわかる。Comparative Example 1 The same procedure as in Example 1 was carried out except that 4,4-diaminodiphenyl ether was used as the diamine component. The resolution of the resulting polyimide pattern was 2.5 μm. Further, when the ultraviolet-visible spectrum of this film was measured, the transmittance at 436 nm was 60% at a film thickness of 2 μm. From the transmittance value, it can be seen that the decrease in resolution is affected by the light reflected on the substrate surface during exposure.
比較例２
メタノールで再結晶した４、４−−ジアミノジフェニル
エーテル２０．０２ｊｊを蒸溜したジメチルアセトアミ
ド２７０ｇに溶解し、アミン溶液を調合した。Comparative Example 2 20.02jj of 4,4-diaminodiphenyl ether recrystallized from methanol was dissolved in 270g of distilled dimethylacetamide to prepare an amine solution.
無水酢酸で再結晶したピロメリット酸二無水物２１．８
１ｇを粉末でアミン溶液に添加後、３０℃で５時間攪拌
し、粘度１３．Ｏポア１フ２５°Ｃのワニスを１７た。Pyromellitic dianhydride recrystallized from acetic anhydride 21.8
After adding 1 g of powder to the amine solution, the mixture was stirred at 30°C for 5 hours until the viscosity was 13. O pore 1 was filled with varnish at 25°C.
このワニスに染料としてメチルバイオレット６．３ｇを
添加し、１μｍのメンブランフィルタ−でろ過した。こ
のワニスをパイレックスガラス板に塗布し、１００℃、
２００℃、３５０℃で各々３０分熱処理した基板と、１
００℃、２００℃で各々３０分熱処理した基板を作製し
た。３５０℃まで熱処理した基板は色調が赤から淡い黄
色に退色し、４３６ｎｍの透過率（膜厚２μｍ）も５８
％と染料を添加した効果が無−かった。一方２００℃ま
で熱処理した基板は赤色の色調を呈し、４３６ｎｍの遮
敵効果が良好であったので、この熱処理条件で実施例１
と同様にアルミ配線を施したシリコンウェハに塗布し、
ポリイミドのパターンを形成した。得られたポリイミド
のパターンは１．５μｍと良好な解像度を示したが、０
２プラズマで除去後、金属性の不純物が残存していた。6.3 g of methyl violet was added as a dye to this varnish, and the mixture was filtered through a 1 μm membrane filter. This varnish was applied to a Pyrex glass plate and heated to 100℃.
A substrate heat-treated at 200°C and 350°C for 30 minutes each, and 1
Substrates were prepared by heat treatment at 00°C and 200°C for 30 minutes each. The color tone of the substrate heat-treated to 350°C faded from red to pale yellow, and the transmittance at 436 nm (film thickness 2 μm) also decreased to 58
% and the addition of dye had no effect. On the other hand, the substrate heat-treated to 200°C exhibited a red color and had a good shielding effect at 436 nm.
Similarly, apply it to a silicon wafer with aluminum wiring,
A polyimide pattern was formed. The obtained polyimide pattern showed a good resolution of 1.5 μm, but
After removal using 2 plasma, metallic impurities remained.
実施例１、比較実施例１〜２の効果より、本発明の方法
を用いると、キュア時の退色が無いので高解像度の微細
パターンが得られ、かつ半導体素子に悪影響を及ぼす金
属性不純物も基板表面に残存しないことがわかる。From the effects of Example 1 and Comparative Examples 1 and 2, when the method of the present invention is used, a fine pattern with high resolution can be obtained because there is no discoloration during curing, and metallic impurities that have an adverse effect on semiconductor devices can be removed from the substrate. It can be seen that it does not remain on the surface.
Claims (1)
脂層を順次形成し、ついで該感光性樹脂層、無機被膜お
よびポリイミド系樹脂層をこの順序でパターン加工する
三層レジストのパターン形成方法において、該ポリイミ
ド系樹脂層として、膜厚２μｍでの４３６ｎｍの紫外線
透過率が５０％以下であるポリイミド系樹脂を用いたこ
とを特徴とする三層レジストによるパターン形成方法。A method for forming a three-layer resist pattern, in which a polyimide resin layer, an inorganic coating, and a photosensitive resin layer are sequentially formed on a substrate, and then the photosensitive resin layer, the inorganic coating, and the polyimide resin layer are patterned in this order, A pattern forming method using a three-layer resist, characterized in that a polyimide resin having a UV transmittance of 50% or less at 436 nm at a film thickness of 2 μm is used as the polyimide resin layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28417386A JPS63138734A (en) | 1986-12-01 | 1986-12-01 | Pattern formation using three-layer resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28417386A JPS63138734A (en) | 1986-12-01 | 1986-12-01 | Pattern formation using three-layer resist |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63138734A true JPS63138734A (en) | 1988-06-10 |
Family
ID=17675124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28417386A Pending JPS63138734A (en) | 1986-12-01 | 1986-12-01 | Pattern formation using three-layer resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63138734A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0714762A (en) * | 1993-04-27 | 1995-01-17 | Internatl Business Mach Corp <Ibm> | Manufacture of circuit element by photolithography, thermostatic polyimide film, mixed polyimide and semiconductor device |
| US5519246A (en) * | 1992-02-28 | 1996-05-21 | Mitsubishi Denki Kabushiki Kaisha | Nonvolatile memory apparatus using an ultraviolet impermeable resin film |
-
1986
- 1986-12-01 JP JP28417386A patent/JPS63138734A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5519246A (en) * | 1992-02-28 | 1996-05-21 | Mitsubishi Denki Kabushiki Kaisha | Nonvolatile memory apparatus using an ultraviolet impermeable resin film |
| JPH0714762A (en) * | 1993-04-27 | 1995-01-17 | Internatl Business Mach Corp <Ibm> | Manufacture of circuit element by photolithography, thermostatic polyimide film, mixed polyimide and semiconductor device |
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