JPH0451518A - Formation of polyimide pattern - Google Patents
Formation of polyimide patternInfo
- Publication number
- JPH0451518A JPH0451518A JP16088790A JP16088790A JPH0451518A JP H0451518 A JPH0451518 A JP H0451518A JP 16088790 A JP16088790 A JP 16088790A JP 16088790 A JP16088790 A JP 16088790A JP H0451518 A JPH0451518 A JP H0451518A
- Authority
- JP
- Japan
- Prior art keywords
- pattern
- polyimide precursor
- film
- chromate
- copper wiring
- 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.)
- Granted
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 69
- 229920001721 polyimide Polymers 0.000 title claims abstract description 69
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 30
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 13
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 37
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- OWMBTIRJFMGPAC-UHFFFAOYSA-N dimethylamino 2-methylprop-2-enoate Chemical compound CN(C)OC(=O)C(C)=C OWMBTIRJFMGPAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
Landscapes
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、感光性ポリイミドを用いて、現像残膜のない
ポリイミド・パターンを銅配線上に形成する方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method of forming a polyimide pattern on copper wiring using photosensitive polyimide without developing a residual film.
［従来の技術］
ポリイミド前駆体に感光性を付与した感光性ポリイミド
前駆体を用いてポリイミド・パターンを形成することは
、例えば特公昭５９−５２８２２号公報の記載の通り公
知である。かかる感光性材料は、電子デバイス実装基板
において、多層配線の層間絶縁層として有用である。こ
の用途では、下部配線と外部リードの導通のために絶縁
層にスルーホール（接続孔）を形成する必要がある。[Prior Art] It is known to form a polyimide pattern using a photosensitive polyimide precursor obtained by imparting photosensitivity to the polyimide precursor, as described in, for example, Japanese Patent Publication No. 59-52822. Such photosensitive materials are useful as interlayer insulating layers of multilayer wiring in electronic device mounting boards. In this application, it is necessary to form a through hole (connection hole) in the insulating layer for electrical conduction between the lower wiring and the external lead.
スルーホールは、通常次の４つの工程を経て形成される
。Through holes are usually formed through the following four steps.
（１）下部配線形成済みの基板に感光性ポリイミド前駆
体の膜を形成する、
（２）スルーホール部をマスクして露光する、（３）現
像液でスルーホール部（未露光部）の感光性ポリイミド
前駆体を溶解除去する、（４）熱処理することによりイ
ミド化する。(1) Forming a film of photosensitive polyimide precursor on the substrate on which the lower wiring has been formed, (2) Masking and exposing the through-hole area, (3) Exposure of the through-hole area (unexposed area) with a developer. and (4) imidization by heat treatment.
［発明が解決しようとする課題］
しかしながら、ポリアミド酸型感光性ポリイミド前駆体
を用い、この方法で銅配線上にスルーホールを形成しよ
うとすると、銅と感光性ポリイミド前駆体構造中のカル
ボキシル基との反応のため、本来現像液で感光性ポリイ
ミド前駆体が除去されるべきスルーホール部に、現像残
膜が生じ、上・下記線間の導通が不良となる問題があっ
た。この現像残膜は、ポリイミドのエツチング剤もしく
はプラズマで処理を行っても、容易に除去できないため
、予め銅配線上に、銅と感光性ポリイミド前駆体との反
応を防止するため、スパッタリングなどにより金属クロ
ムなどの薄膜を設け、これをエツチング除去する方法が
一般的に採用されている。[Problems to be Solved by the Invention] However, when attempting to form through holes on copper wiring using this method using a polyamic acid type photosensitive polyimide precursor, the copper and carboxyl groups in the photosensitive polyimide precursor structure Due to this reaction, an undeveloped film is formed in the through-hole area where the photosensitive polyimide precursor should originally be removed by the developing solution, resulting in poor conductivity between the upper and lower lines. This residual film cannot be easily removed even by treatment with a polyimide etching agent or plasma. Therefore, in order to prevent the reaction between the copper and the photosensitive polyimide precursor, the metal is coated on the copper wiring by sputtering or other means to prevent the reaction between copper and the photosensitive polyimide precursor. A commonly used method is to provide a thin film of chromium or the like and remove it by etching.
しかし、かかる従来の方法は、工程が煩雑でコストが高
くなるという問題があった。However, such conventional methods have the problem of complicated steps and high costs.
本発明は、かかる従来技術の欠点に鑑み創案されたもの
で、その目的とするところは、銅配線上における現像残
膜の発生を確実に防止することのできるポリイミド・パ
ターンの形成方法を提供することにある。The present invention was devised in view of the drawbacks of the prior art, and its purpose is to provide a method for forming a polyimide pattern that can reliably prevent the occurrence of undeveloped film on copper wiring. There is a particular thing.
［課題を解決するための手段］
かかる本発明の目的は、ポリアミド酸型感光性ポリイミ
ド前駆体を用い、銅配線上にポリイミド・パターンを形
成する方法において、
Ａ、銅配線上にクロメート処理する、
Ｂ、銅配線上に感光性ポリイミド前駆体の膜を形成する
、
Ｃ，パターン状の光を照射し、ついで現像する、Ｄ、得
られたポリイミド前駆体のパターンを加熱することによ
り、ポリイミド・パターンに変換する、
の各工程から成ることを特徴とするポリイミド・パター
ンの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 method for forming a polyimide pattern on a copper wiring using a polyamic acid type photosensitive polyimide precursor, which includes: A. chromate treatment on the copper wiring; B. Forming a photosensitive polyimide precursor film on the copper wiring C. Irradiating patterned light and then developing D. Heating the resulting polyimide precursor pattern to form a polyimide pattern This is achieved by a method for forming a polyimide pattern characterized by comprising the following steps:
本発明でいう銅配線とは、基板上に設けられた金属銅ま
たは銅の合金からなるパターン状または全面に形成され
た層を意味する。基板上への銅層の形成は通常、電界鍍
金、スパッタリング、真空蒸着などにより行われ、また
パターン層の形成はフォトリソグラフィ方式など公知の
方法により行うことができる。The term "copper wiring" as used in the present invention refers to a patterned or all-over layer made of metallic copper or a copper alloy provided on a substrate. The formation of the copper layer on the substrate is usually performed by electrolytic plating, sputtering, vacuum evaporation, etc., and the formation of the pattern layer can be performed by a known method such as photolithography.
本発明におけるクロメート処理とは、無水クロム酸、重
クロム酸塩またはクロム酸塩などの水溶液中に基板を浸
漬させ、六価のクロム、三価のクロムおよび結晶水から
なる複塩の皮膜を銅配線上に形成するものである。重ク
ロム酸塩およびクロム酸塩としては、水溶液中で電離す
るものであればどのような塩でも良く、好例としては重
クロム酸ナトリウム、重クロム酸カリウム、クロム酸カ
リウム、クロム酸ナトリウムなどが挙げられる。Chromate treatment in the present invention refers to immersing a substrate in an aqueous solution of chromic anhydride, dichromate, or chromate to form a double salt film consisting of hexavalent chromium, trivalent chromium, and crystal water on copper. It is formed on the wiring. As dichromate and chromate, any salt may be used as long as it ionizes in aqueous solution, and good examples include sodium dichromate, potassium dichromate, potassium chromate, and sodium chromate. It will be done.
クロメート処理液の濃度としては、無水クロム酸または
重クロム酸塩あるいはクロム酸塩の０．５〜１０％水溶
液が好ましい。より好ましくは、１〜２％水溶液がよい
。浸漬時間は１０〜２００秒が好ましい。より好ましく
は３０〜６０秒である。The concentration of the chromate treatment solution is preferably chromic anhydride, dichromate, or a 0.5 to 10% aqueous solution of chromate. More preferably, a 1-2% aqueous solution is used. The immersion time is preferably 10 to 200 seconds. More preferably, it is 30 to 60 seconds.
なおりロメート処理後は、基板を水洗し乾燥することが
好ましい。After the naoriromate treatment, it is preferable to wash the substrate with water and dry it.
本発明におけるポリイミド前駆体としては、ピロメリッ
ト酸二無水物、３．３−．４．４”−ベンゾフェノンテ
トラカルボン酸二無水物、３，３４．４′−ビフェニル
テトラカルボン酸二無水物、１． ２． ５． ６−ナ
フタレンテトラカルボン酸二無水物、シクロブタンテト
ラカルボン酸二無水物などのテトラカルボン酸二無水物
と、４゜４′−ジアミノジフェニルエーテル、３．３＝
ジアミノジフエニルスルホン、４．４−−ジアミノジフ
ェニルメタン、ビス（３−アミノプロピル）テトラメチ
ルジシロキサン、メタフェニレンジアミン、パラフェニ
レンジアミンなどのジアミンとを非プロトン性極性溶媒
中で反応させて得られるポリアミド酸が挙げられるが、
これらに限定されない。Examples of the polyimide precursor in the present invention include pyromellitic dianhydride, 3.3-. 4.4''-benzophenonetetracarboxylic dianhydride, 3,34.4'-biphenyltetracarboxylic dianhydride, 1. 2. 5. 6-naphthalenetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride tetracarboxylic dianhydride such as 4゜4'-diaminodiphenyl ether, 3.3=
Polyamide obtained by reacting diamines such as diaminodiphenylsulfone, 4.4-diaminodiphenylmethane, bis(3-aminopropyl)tetramethyldisiloxane, metaphenylenediamine, paraphenylenediamine in an aprotic polar solvent. Examples include acids,
Not limited to these.
非プロトン性極性溶媒の好ましい例としては、Ｎ−メチ
ル−２−ピロリドン、Ｎ、Ｎ−ジメチルアセトアミド、
Ｎ、Ｎ−ジメチルホルムアミドなどが挙げられるが、こ
れらに限定されない。Preferred examples of aprotic polar solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide,
Examples include, but are not limited to, N,N-dimethylformamide and the like.
本発明で用いるポリアミド酸型感光性ポリイミド前駆体
とは、前記のごときポリアミド酸に感光性化合物を導入
したものをいう。ポリイミド前駆体を感光化するために
使用される感光性化合物としては、ビスアジド、ビニル
基を有するアミノ化合物など公知のものが挙げられる。The polyamic acid type photosensitive polyimide precursor used in the present invention refers to a polyamic acid as described above into which a photosensitive compound is introduced. Examples of the photosensitive compound used to photosensitize the polyimide precursor include known compounds such as bisazide and amino compounds having a vinyl group.
具体的な感光性ポリイミド前駆体の組成としては、たと
えば特公昭５９−５２８２２号公報に記載されているも
のを挙げることができる。Specific examples of the composition of the photosensitive polyimide precursor include those described in Japanese Patent Publication No. 59-52822.
クロメート処理された銅配線上に感光性ポリイミド前駆
体の膜を形成する方法としては、公知の塗膜形成方法が
採用できる。たとえばスピナによる方法が好例として挙
げられる。As a method for forming a film of a photosensitive polyimide precursor on the chromate-treated copper wiring, a known coating film forming method can be employed. A good example is the method using a spinner.
パターン状の光を照射する方法としては、感光性ポリイ
ミド前駆体の膜上にマスクを置き、光を照射する公知の
方法が例として挙げられる。感光性ポリイミドの感光性
の面から、通常光源としては、紫外光が用いられる。An example of a method for irradiating patterned light is a known method in which a mask is placed on a film of a photosensitive polyimide precursor and light is irradiated. In view of the photosensitivity of photosensitive polyimide, ultraviolet light is usually used as the light source.
現像は感光性ポリイミド前駆体の組成に応じた最適の現
像液で行うのが好ましい。通常、Ｎ−メチル−２−ピロ
リドン、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ、Ｎ−ジメ
チルホルムアミドなどのポリイミド前駆体の溶媒か、あ
るいはこれらの溶媒と、メタノールやエタノールなどの
ポリイミド前駆体の非溶媒との混合溶媒を、現像液とし
て用いることができる。The development is preferably carried out using an optimal developer depending on the composition of the photosensitive polyimide precursor. Typically, a solvent for the polyimide precursor such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, or a combination of these solvents and a non-solvent for the polyimide precursor such as methanol or ethanol is used. A mixed solvent of can be used as a developer.
ポリイミド前駆体のポリイミドへの変換は、２００°Ｃ
〜４００℃で熱処理することにより行うことができる。Conversion of polyimide precursor to polyimide is carried out at 200°C.
This can be done by heat treatment at ~400°C.
熱処理時間は５分から３０分ぐらいで良い。熱処理は単
一温度で行ってもよいし、段階的に、あるいは連続的に
昇温しながら行ってもよい。スルーホール部のクロメー
ト処理皮膜は、熱処理すると接触抵抗が大きくなるので
、過硫酸アンモニウム水溶液などで表面をエツチングす
るか、プラズマ処理などの手法で除去するのが望ましい
。The heat treatment time may be about 5 minutes to 30 minutes. The heat treatment may be performed at a single temperature, or may be performed while increasing the temperature stepwise or continuously. Since the contact resistance of the chromate-treated film on the through-hole portion increases when heat-treated, it is desirable to remove the surface by etching the surface with an aqueous ammonium persulfate solution or using a method such as plasma treatment.
［発明の効果］
本発明の形成方法によれば、銅配線上にポリイミド・パ
ターンを形成する場合に、現像残膜の無いポリイミド・
パターンを確実に形成でき、銅配線上に形成されるスル
ーホールにおける電気的接続の導通不良の問題を解決し
得る。[Effects of the Invention] According to the forming method of the present invention, when forming a polyimide pattern on a copper wiring, a polyimide pattern with no residual film after development can be formed.
A pattern can be reliably formed, and the problem of electrical connection failure in through holes formed on copper wiring can be solved.
［実施例コ
実施例１
シリコンウェハー上に、スパッタリングにより３．０μ
ｍの銅層を形成させた後、フォトリソグラフィ方式によ
り、所望の配線パターンを得た。[Example Example 1 3.0μ was deposited on a silicon wafer by sputtering.
After forming a copper layer of m thickness, a desired wiring pattern was obtained by photolithography.
次に１％の重クロム酸カリウム水溶液中に４５秒間浸漬
させ、引上げた後蒸留水で水洗し、乾燥した窒素を当て
ることにより乾燥させた。クロメート処理膜（クロメー
ト処理により得られた皮膜）の膜厚は約０．１μｍであ
った。一方４，４゛ジアミノジフェニルエーテル２０．
０ｇを２００ＣＣのＮ−メチル−２−ピロリドンに溶解
し、室温（約１８℃）で撹拌しながら、３．３−．４゜
４′−ベンゾフェノンテトラカルボン酸二無水物３２．
２ｇを粉体で仕込み、室温で１時間撹拌し、更に５５℃
で２時間撹拌を続けた。この溶液に、ジメチルアミノエ
チルメタクリレート３１．４ｇおよびミヒラーズ・ケト
ン０．９４ｇを８５ｇのＮ−メチル−２−ピロリドンに
溶解した溶液を添加、混合することにより、感光性ポリ
イミド前駆体の溶液を得た。得られた感光性ポリイミド
前駆体の溶液を、クロメート処理した銅配線パターン上
にスピナにより塗布した。８０℃で１時間乾燥を行った
後、露光量３００ｍＪ／ｃｍ２で露光し、Ｎ−メチル−
２−ピロリドン、キシレンおよび水の７＋３：１の混合
液で現像を行った後、イソプロピルアルコールでリンス
しポリイミド前駆体パターンを形成した。このとき、ス
ルーホール部に現像残膜の形成は無かった。その後１２
０℃で１時間キュアし、さらに４００℃まで５°Ｃ／ｍ
ｉｎで昇温し４００℃に１時間保ちポリイミド・パター
ンを得た。その後１０％の過硫酸アンモニウム水溶液で
スルーホール部のクロメート処理膜をエツチングした。Next, it was immersed in a 1% potassium dichromate aqueous solution for 45 seconds, pulled up, washed with distilled water, and dried by applying dry nitrogen. The thickness of the chromate-treated film (film obtained by chromate treatment) was about 0.1 μm. On the other hand, 4,4゛diaminodiphenyl ether 20.
3.3-. 4゜4'-benzophenonetetracarboxylic dianhydride 32.
Add 2g of powder, stir at room temperature for 1 hour, and then heat to 55°C.
Stirring was continued for 2 hours. A solution of 31.4 g of dimethylaminoethyl methacrylate and 0.94 g of Michler's ketone dissolved in 85 g of N-methyl-2-pyrrolidone was added to this solution and mixed to obtain a solution of a photosensitive polyimide precursor. . The obtained photosensitive polyimide precursor solution was applied onto a chromate-treated copper wiring pattern using a spinner. After drying at 80°C for 1 hour, it was exposed to light at an exposure dose of 300 mJ/cm2, and N-methyl-
After developing with a 7+3:1 mixture of 2-pyrrolidone, xylene and water, the film was rinsed with isopropyl alcohol to form a polyimide precursor pattern. At this time, there was no development residual film formed in the through-hole area. then 12
Cure at 0°C for 1 hour, then further heat at 5°C/m to 400°C.
The temperature was raised to 400° C. for 1 hour to obtain a polyimide pattern. Thereafter, the chromate-treated film in the through-hole portion was etched with a 10% ammonium persulfate aqueous solution.
このようにして得られたポリイミド・パターンの膜厚は
１０μｍであった。またスルーホール部の電気伝導性を
調べたところ、導通性は良好であった。The film thickness of the polyimide pattern thus obtained was 10 μm. Furthermore, when the electrical conductivity of the through-hole portion was examined, the conductivity was found to be good.
比較例１
シリコンウェハー上に、実施例１と全く同様にして配線
パターンを得た後、実施例１と同じ感光性ポリイミド前
駆体を、スピナにより塗布した。Comparative Example 1 After obtaining a wiring pattern on a silicon wafer in exactly the same manner as in Example 1, the same photosensitive polyimide precursor as in Example 1 was applied using a spinner.
その後、実施例１と同じ条件で乾燥、露光、現像、リン
スを行いポリイミド前駆体パターンを形成した。このと
き、スルーホール部に現像残膜の形成か見られた。その
後１２０°Ｃで１時間キュアし、さらに４００℃まで５
°Ｃ／ｍｉｎで昇温し１時間４００℃に保ちポリイミド
・パターンを得た。このようにして得られたポリイミド
・パターンの膜厚は１０μｍであり、スルーホール部の
現像残膜の膜厚は約０． ５μｍであった。またスルー
ホール部の電気伝導性を調べたところ、導通不良であっ
た。Thereafter, drying, exposure, development, and rinsing were performed under the same conditions as in Example 1 to form a polyimide precursor pattern. At this time, it was observed that a development residual film was formed in the through-hole area. Afterwards, cure at 120°C for 1 hour, then heat to 400°C for 5
The temperature was raised at a rate of °C/min and kept at 400 °C for 1 hour to obtain a polyimide pattern. The film thickness of the polyimide pattern obtained in this way is 10 μm, and the film thickness of the undeveloped film at the through-hole portion is approximately 0.0 μm. It was 5 μm. Furthermore, when the electrical conductivity of the through-hole portion was examined, it was found that there was poor conductivity.
実施例２
シリコンウェハー上に、真空蒸着により０．２μｍの銅
層を形成させ、さらに電解鍍金により２゜８μｍの銅層
を形成させた後、フォトリソグラフィ方式により所望の
配線パターンを得た。次に１％の重クロム酸カリウム水
溶液中に４５秒間浸漬させ、引上げた後蒸留水で水洗し
、乾燥した窒素を当てることにより乾燥させた。クロメ
ート処理膜の膜厚は約０．１μｍであった。このクロメ
ート処理した銅配線パターン上に、実施例１と同じ感光
性ポリイミド前駆体を、スピナにより塗布した。その後
、実施例１と同じ条件で乾燥、露光、現像、リンスを行
いポリイミド前駆体パターンを形成した。このとき、ス
ルーホール部に現像残膜の形成は無かった。その後１２
０℃で１時間キュアし、さらに４００℃まで５°Ｃ／ｍ
ｉｎで昇温し１時間４００’Ｃに保ちポリイミド・パタ
ーンを得た。その後１０％の過硫酸アンモニウム水溶液
でスルーホール部のクロメート処理膜をエツチングした
。このようにして得られたポリイミド・パターンの膜厚
は１０μｍであった。またスルーホールの電気伝導性を
調べたところ、導通性は良好であった。Example 2 A 0.2 μm thick copper layer was formed on a silicon wafer by vacuum deposition, and a 2.8 μm thick copper layer was further formed by electrolytic plating, and then a desired wiring pattern was obtained by photolithography. Next, it was immersed in a 1% potassium dichromate aqueous solution for 45 seconds, pulled up, washed with distilled water, and dried by applying dry nitrogen. The thickness of the chromate-treated film was approximately 0.1 μm. The same photosensitive polyimide precursor as in Example 1 was applied onto this chromate-treated copper wiring pattern using a spinner. Thereafter, drying, exposure, development, and rinsing were performed under the same conditions as in Example 1 to form a polyimide precursor pattern. At this time, there was no development residual film formed in the through-hole area. then 12
Cure at 0°C for 1 hour, then further heat at 5°C/m to 400°C.
The temperature was raised to 400'C for 1 hour to obtain a polyimide pattern. Thereafter, the chromate-treated film in the through-hole portion was etched with a 10% ammonium persulfate aqueous solution. The film thickness of the polyimide pattern thus obtained was 10 μm. Furthermore, when the electrical conductivity of the through holes was examined, the conductivity was found to be good.
比較例２
シリコンウェハー上に、実施例２と全く同様にして配線
パターンを形成した後、実施例１と同じ感光性ポリイミ
ド前駆体を、スピナにより塗布した。その後、実施例１
と同じ条件で乾燥、露光、現像、リンスを行いポリイミ
ド前駆体パターンを形成した。このとき、スルーホール
部に現像残膜の形成が見られた。その後１２０°Ｃで１
時間キュアし、さらに４００℃まで５°Ｃ／ ｍ ｉ
ｎで昇温し１時間４００℃に保った。このようにして得
られたポリイミド・パターンの膜厚は１０μｍであり、
スルーホール部の現像残膜の膜厚は約０．５μｍであっ
た。またスルーホール部の電気伝導性を調べたところ、
導通不良であった。Comparative Example 2 After forming a wiring pattern on a silicon wafer in exactly the same manner as in Example 2, the same photosensitive polyimide precursor as in Example 1 was applied using a spinner. After that, Example 1
Drying, exposure, development, and rinsing were performed under the same conditions as above to form a polyimide precursor pattern. At this time, formation of a development residual film was observed in the through-hole area. Then 1 at 120°C
Cure for an additional 5°C/mi to 400°C.
The temperature was raised at 400° C. for 1 hour. The film thickness of the polyimide pattern thus obtained was 10 μm,
The thickness of the undeveloped film in the through-hole portion was approximately 0.5 μm. We also investigated the electrical conductivity of the through-hole section and found that
There was poor continuity.
実施例３
シリコンウェハー上に、実施例２と全く同様にして配線
パターンを形成した後、１％の無水クロム酸水溶液中に
４５秒間浸漬させ、引上げた後蒸留水で水洗し、乾燥し
た窒素を当てることにより乾燥させた。クロメート処理
膜の膜厚は約０． １μｍであった。一方４，４′−ジ
アミノジフェニルエーテル２０．０ｇを２００ｃｃのＮ
−メチル−２−ピロリドンに溶解し、室温（約１８°Ｃ
）で撹拌しながら、３．３−．４．４−−ビフェニルテ
トラカルボン酸二無水物２９．４ｇを粉体で仕込み、室
温で１−時間撹拌し、更に５５℃で３時間撹拌を続けた
。この溶液に、ジメチルアミノメタクリレート３１．４
ｇおよびミヒラーズ・ケトン０．９４ｇを８５ｇのＮ−
メチル−２−ピロリドンに溶解した溶液を添加、混合す
ることにより、感光性ポリイミド前駆体の溶液を得た。Example 3 After forming a wiring pattern on a silicon wafer in exactly the same manner as in Example 2, it was immersed in a 1% aqueous chromic acid anhydride solution for 45 seconds, pulled up, washed with distilled water, and rinsed with dry nitrogen. It was dried by blowing. The thickness of the chromate treatment film is approximately 0. It was 1 μm. On the other hand, 20.0 g of 4,4'-diaminodiphenyl ether was added to 200 cc of N
-Methyl-2-pyrrolidone and room temperature (approximately 18°C).
) while stirring at 3.3-. 29.4 g of 4.4-biphenyltetracarboxylic dianhydride was charged as a powder, stirred at room temperature for 1 hour, and continued stirring at 55° C. for 3 hours. Add 31.4 ml of dimethylamino methacrylate to this solution.
g and 0.94 g of Michler's ketone to 85 g of N-
A solution of a photosensitive polyimide precursor was obtained by adding and mixing a solution dissolved in methyl-2-pyrrolidone.
得られた感光性ポリイミド前駆体の溶液を、クロメート
処理した銅配線パターン上にスピナによりに塗布した。The resulting photosensitive polyimide precursor solution was applied onto a chromate-treated copper wiring pattern using a spinner.
その後、実施例１と同じ条件で乾燥、露光、現像、リン
スを行いポリイミド前駆体パターンを形成した。このと
き、スルーホール部に現像残膜の形成は無かった。その
後１２０℃で１時間キュアし、さらに４００℃まで５６
Ｃ／ｍｉｎで昇温し１時間、４００℃に保ちポリイミド
・パターンを得た。その後１０％の過硫酸アンモニウム
水溶液でスルーホール部のクロメート処理膜をエツチン
グした。このようにして得られたポリイミド・パターン
の膜厚は１０μｍであった。またスルーホール部の電気
伝導性を調べたところ、導通性は良好であった。Thereafter, drying, exposure, development, and rinsing were performed under the same conditions as in Example 1 to form a polyimide precursor pattern. At this time, there was no development residual film formed in the through-hole area. Afterwards, cure at 120℃ for 1 hour, and then heat to 400℃ for 56 hours.
The temperature was raised at a rate of C/min and kept at 400° C. for 1 hour to obtain a polyimide pattern. Thereafter, the chromate-treated film in the through-hole portion was etched with a 10% ammonium persulfate aqueous solution. The film thickness of the polyimide pattern thus obtained was 10 μm. Furthermore, when the electrical conductivity of the through-hole portion was examined, the conductivity was found to be good.
比較例３
シリコンウェハー上に、実施例２と全く同様にして配線
パターンを形成した後、実施例３と同じ感光性ポリイミ
ド前駆体を、スピナにより塗布した。その後、実施例１
と同じ条件で乾燥、露光、現像、リンスを行いポリイミ
ド前駆体パターンを形成した。このとき、スルーホール
部に現像残膜の形成が見られた。その後１２０℃で１時
間キュアし、さらに４００℃まで５℃／ｍｉｎで昇温し
１時間４００℃に保った。このようにして得られたポリ
イミド・パターンの膜厚は１０μｍであり、スルーホー
ル部の現像残膜の膜厚は約０． ５μｍであった。また
スルーホール部の電気伝導性を調べたところ、導通不良
であった。Comparative Example 3 After forming a wiring pattern on a silicon wafer in exactly the same manner as in Example 2, the same photosensitive polyimide precursor as in Example 3 was applied using a spinner. After that, Example 1
Drying, exposure, development, and rinsing were performed under the same conditions as above to form a polyimide precursor pattern. At this time, formation of a development residual film was observed in the through-hole area. Thereafter, it was cured at 120°C for 1 hour, and further heated to 400°C at a rate of 5°C/min, and maintained at 400°C for 1 hour. The film thickness of the polyimide pattern obtained in this way is 10 μm, and the film thickness of the undeveloped film at the through-hole portion is approximately 0.0 μm. It was 5 μm. Furthermore, when the electrical conductivity of the through-hole portion was examined, it was found that there was poor conductivity.
Claims (1)
配線上にポリイミド・パターンを形成する方法において
、 Ａ、銅配線上にクロメート処理する、 Ｂ、銅配線上に感光性ポリイミド前駆体の膜を形成する
、 Ｃ、パターン状の光を照射し、ついで現像する、Ｄ、得
られたポリイミド前駆体のパターンを加熱することによ
り、ポリイミド・パターンに変換する、 の各工程から成ることを特徴とするポリイミド・パター
ンの形成方法。[Claims] 1. A method for forming a polyimide pattern on copper wiring using a polyamic acid type photosensitive polyimide precursor, comprising: A. chromate treatment on the copper wiring; B. photosensitive polyimide on the copper wiring. It consists of the following steps: forming a precursor film; C. irradiating patterned light and then developing; D. converting the obtained polyimide precursor pattern into a polyimide pattern by heating. A method for forming a polyimide pattern, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16088790A JP2876721B2 (en) | 1990-06-19 | 1990-06-19 | Method of forming polyimide pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16088790A JP2876721B2 (en) | 1990-06-19 | 1990-06-19 | Method of forming polyimide pattern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0451518A true JPH0451518A (en) | 1992-02-20 |
| JP2876721B2 JP2876721B2 (en) | 1999-03-31 |
Family
ID=15724515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16088790A Expired - Lifetime JP2876721B2 (en) | 1990-06-19 | 1990-06-19 | Method of forming polyimide pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2876721B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0675378A (en) * | 1992-07-24 | 1994-03-18 | Internatl Business Mach Corp <Ibm> | Reflection preventing coating composition and manufacture thereof |
| US5422228A (en) * | 1992-08-05 | 1995-06-06 | Fujitsu Limited | Method of producing thin film multi-layered substrate |
-
1990
- 1990-06-19 JP JP16088790A patent/JP2876721B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0675378A (en) * | 1992-07-24 | 1994-03-18 | Internatl Business Mach Corp <Ibm> | Reflection preventing coating composition and manufacture thereof |
| US5422228A (en) * | 1992-08-05 | 1995-06-06 | Fujitsu Limited | Method of producing thin film multi-layered substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2876721B2 (en) | 1999-03-31 |
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