JPH033239A - Etching method for polyimide resin film, wiring structure using the method, and processing method for material to be etched - Google Patents
Etching method for polyimide resin film, wiring structure using the method, and processing method for material to be etchedInfo
- Publication number
- JPH033239A JPH033239A JP13691989A JP13691989A JPH033239A JP H033239 A JPH033239 A JP H033239A JP 13691989 A JP13691989 A JP 13691989A JP 13691989 A JP13691989 A JP 13691989A JP H033239 A JPH033239 A JP H033239A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- polyimide resin
- film
- resin film
- organic solvent
- 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
- 229920001721 polyimide Polymers 0.000 title claims abstract description 102
- 238000005530 etching Methods 0.000 title claims abstract description 93
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims description 11
- 238000003672 processing method Methods 0.000 title description 3
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 52
- 229920000768 polyamine Polymers 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 230000006866 deterioration Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- 230000003313 weakening effect Effects 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 99
- 239000000243 solution Substances 0.000 description 33
- 229910052782 aluminium Inorganic materials 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 17
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002344 surface layer Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- -1 hydrazine hydride Chemical compound 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Weting (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野コ
本発明は、ポリイミド系樹脂膜のエツチング方法、それ
を用いた配線構造体および被エツチング材の処理方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method of etching a polyimide resin film, a wiring structure using the same, and a method of treating a material to be etched.
C従来の技術]
ポリイミド系樹脂は耐熱性、成形性、機械特性、寸法安
定性等が優れているために、配線基板の絶縁体として、
好ましく用いられている。C. Prior Art] Polyimide resins have excellent heat resistance, moldability, mechanical properties, dimensional stability, etc., so they are used as insulators for wiring boards.
Preferably used.
このポリイミド系樹脂のエツチング方法には、大別して
、酸素や四塩化フッ素などのガスを用いたドライエツチ
ングと、溶剤を使用するウェットエツチングがある。Etching methods for polyimide resins can be roughly divided into dry etching using a gas such as oxygen or fluorine tetrachloride, and wet etching using a solvent.
ドライエツチングは、真空状態に上記ガスを封入するた
めに、ウェットエツチングと比較して、装置が大がかり
となり、また1手間がかがるため、量産性に劣る。この
ため、実用的には、ウェットエツチングが採用されてい
る。Compared to wet etching, dry etching requires a larger apparatus and takes more time than wet etching because the gas is sealed in a vacuum state, and therefore is inferior in mass productivity. For this reason, wet etching is practically used.
ウェットエツチングは、従来、例えば特開昭56−12
5858号、同61−83235号公報等に記載されて
いるように、ポリイミド系樹脂膜の上に、ポジ型もしく
はネガ型のレジスト膜を作り、これをエツチングマスク
として、塩基性エツチング液を用いて、ポリイミド樹脂
膜を選択的にエツチングすることにより、行われている
。Wet etching is conventionally known as, for example, Japanese Patent Application Laid-open No. 56-12.
As described in No. 5858 and No. 61-83235, a positive or negative resist film is formed on a polyimide resin film, and this is used as an etching mask using a basic etching solution. This is done by selectively etching the polyimide resin film.
この時、ポリイミド系樹脂は、エツチング液と接触2反
応して表面層に変質層を生じ、この変質層がエツチング
液に溶解してエツチングが進行する。At this time, the polyimide resin comes into contact with the etching solution and reacts with the etching solution to form an altered layer on the surface layer, and this altered layer is dissolved in the etching solution to proceed with etching.
[発明が解決しようとする課題]
上記変質層は、強塩基性溶液によって、ポリイミド系樹
脂が分解、反応した結果生じた低分子量のポリイミド系
樹脂あるいはイミド環の開裂した樹脂と考えられる。こ
のような、低分子量のポリイミド系樹脂あるいはイミド
環の開裂した樹脂は、強塩基性溶液に浸されると必ず生
ずるものであり、エツチング後も除去されなかった変質
層は残っている。[Problems to be Solved by the Invention] The above-mentioned altered layer is considered to be a low molecular weight polyimide resin produced as a result of decomposition and reaction of the polyimide resin by a strong basic solution, or a resin in which the imide ring has been cleaved. Such low molecular weight polyimide resins or resins with cleaved imide rings are always produced when immersed in a strong basic solution, and even after etching, an altered layer that is not removed remains.
しかし、この変質層が残っていると、ポリイミド系樹脂
膜の絶縁膜としての信頼性が低下する。However, if this deteriorated layer remains, the reliability of the polyimide resin film as an insulating film decreases.
特に、多層配線構造体の層間絶縁膜として用いられる時
、エツチングによりパターン形成したポリイミド系樹脂
膜上に配線構造体の上層配線導体が形成されると、配線
導体が変質層と接触し、配線導体の腐食やポリイミド系
樹脂膜の絶縁特性等の信頼性低下を引き起こしやすく、
素子の信頼性を低下する。In particular, when used as an interlayer insulating film of a multilayer wiring structure, when the upper layer wiring conductor of the wiring structure is formed on a polyimide resin film patterned by etching, the wiring conductor comes into contact with the deteriorated layer, and the wiring conductor It is easy to cause corrosion of the polyimide resin film and decrease reliability of the insulation properties of the polyimide resin film.
Decreases device reliability.
このため、素子の信頼性が望まれる基板に使用するには
、不十分であり、特に、近年開発が進められている大型
計算機用等の薄膜多層基板では、致命的な欠陥となる。For this reason, it is insufficient for use in substrates where element reliability is desired, and is a fatal defect, particularly in thin-film multilayer substrates for large computers, etc., which have been developed in recent years.
そこで、本発明の第1の目的は、エツチング後もポリイ
ミド系樹脂の表面層に残存する変質層を除去することが
できる、ポリイミド系樹脂のエツチング方法を提供する
ことにある。第2の目的は、上記方法を用いた配線構造
体と被エツチング材の処理方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a method for etching a polyimide resin, which can remove the deteriorated layer remaining on the surface layer of the polyimide resin even after etching. A second object is to provide a method for treating a wiring structure and a material to be etched using the above method.
[課題を解決するための手段]
本発明の第1の目的は、
本発明の目的は、基板上に形成されたポリイミド系樹脂
膜に、レジスト膜パターンを形成し、該レジスト膜パタ
ーンをマスクとして、エツチング液にて前記ポリイミド
系樹脂膜を選択エツチングする方法において、前記エツ
チング液が前記ポリイミド樹脂膜上に生じる変質膜を、
有機溶剤にて、除去することを特徴とするポリイミド系
樹脂膜のエツチング方法によって達成される。[Means for Solving the Problems] A first object of the present invention is to form a resist film pattern on a polyimide resin film formed on a substrate, and use the resist film pattern as a mask. In the method of selectively etching the polyimide resin film with an etching solution, the etching solution removes a deteriorated film formed on the polyimide resin film,
This is achieved by an etching method for a polyimide resin film, which is characterized in that it is removed using an organic solvent.
他の見地によれば、本発明は、基板上に形成した絶縁膜
に、レジスト膜パターンを形成し、該レジスト膜パター
ンをマスクとして、第一のエツチング液にて前記絶a膜
をエツチングし、その後さらに、第二のエツチング液に
より絶縁膜露出部を処理することを特徴とする絶縁膜の
エツチング方法を提供する。According to another aspect, the present invention includes forming a resist film pattern on an insulating film formed on a substrate, and etching the insulating film with a first etching solution using the resist film pattern as a mask. There is also provided a method of etching an insulating film, characterized in that the exposed portion of the insulating film is further treated with a second etching solution.
前記第二のエツチング液は、第一のエツチング工程にお
いて接触により生じた絶縁膜露出部面部の変質層に対し
て、選択性を有することが好ましい。It is preferable that the second etching solution has selectivity to the altered layer on the exposed surface of the insulating film caused by contact in the first etching step.
さらに、本発明の第二の目的は、本発明の配線構造体は
、上記ポリイミド系樹脂膜のエツチング方法にてエツチ
ングされたポリイミド系樹脂膜が、層間絶縁膜として、
積層されている配線構造体によって達成される。Furthermore, a second object of the present invention is that the wiring structure of the present invention has a polyimide resin film etched by the above polyimide resin film etching method as an interlayer insulating film.
This is achieved by a stacked wiring structure.
他の見地によれば、本発明の配線構造体は、エツチング
により開口を形成した絶縁膜を有する配線構造体におい
て、前Rnm膜が、エツチングによる変質層を実質的に
含まないことを特徴とする配線構造体を提供する。According to another aspect, the wiring structure of the present invention includes an insulating film in which an opening is formed by etching, in which the previous Rnm film does not substantially contain a layer altered by etching. Provide a wiring structure.
本発明の被エツチング材の処理方法は、被エツチング材
がエツチングより、露出表面部に変質層を生じる場合に
一般的に用いることができる。The method of treating a material to be etched according to the present invention can be generally used when the material to be etched forms a deteriorated layer on the exposed surface portion due to etching.
本発明に用いられる有機溶剤は、変質層を除去する溶剤
であれば、特に、限定されることはないが、非プロトン
性極性溶剤および/またはポリアミンから選択されるこ
とが好ましい。The organic solvent used in the present invention is not particularly limited as long as it can remove the altered layer, but it is preferably selected from aprotic polar solvents and/or polyamines.
好ましく用いられる非プロトン性極性溶剤には、N−メ
チル−2−ピロリドン、N、N−ジメチルホルムアミド
、N、N−ジメチルアセトアミド、ジメチルスルホキシ
ド、N−アセチル−ε−カプロラクタム、1,3−ジメ
チル−2−イミダゾリジノン、1,2−ジメトキシエタ
ン、1.2−ジェトキシエタン、l−アセトキシ−2−
メトキシエタン、ジエチレングリコールジメチルエーテ
ル、トリエチレングリコールジメチルエーテル等が挙げ
られる。Preferably used aprotic polar solvents include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-acetyl-ε-caprolactam, 1,3-dimethyl- 2-imidazolidinone, 1,2-dimethoxyethane, 1,2-jethoxyethane, l-acetoxy-2-
Examples include methoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like.
また、ポリアミン類としては、エチレンジアミン、キシ
レンジアミン、トリメチレンジアミン、ヘキサメチレン
ジアミン等が挙げられる。Moreover, examples of polyamines include ethylene diamine, xylene diamine, trimethylene diamine, hexamethylene diamine, and the like.
なかでも、N−メチル−2−ピロリドン、N。Among them, N-methyl-2-pyrrolidone, N.
N−ジメチルアセトアミド、ジメチルスルホキシド、エ
チレンジアミンが好ましい。N-dimethylacetamide, dimethylsulfoxide and ethylenediamine are preferred.
有機溶剤は、単独あるいは数種類の混合系として用いる
。The organic solvent may be used alone or as a mixture of several types.
処理方法は、有機レジストの現像処理方法として周知の
ものである、浸漬処理、デイツプ処理、スプレー処理等
が挙げられる。Examples of the processing method include immersion processing, dip processing, spray processing, and the like, which are well-known development processing methods for organic resists.
浸漬処理は、ボrノイミド系樹脂膜がエツチングされた
基板を、処理液中に浸漬するものである。In the immersion treatment, the substrate on which the bonimide resin film has been etched is immersed in a treatment solution.
デイツプ処理は基板上に処理液を乗せ、スプレー処理は
基板上に処理液をスプレーで噴霧する。In dip processing, a processing liquid is placed on the substrate, and in spray processing, the processing liquid is sprayed onto the substrate.
これらの処理方法を、単独あるいは組み合わせて使用す
る。These treatment methods may be used alone or in combination.
本発明では、ポリイミド系樹脂膜の表面処理で用いた有
機溶剤を除去するために、洗浄および/または加熱を行
うことが好ましい。洗浄には、メチルアルコール、エチ
ルアルコール、イソプロピルアルコール等のアルコール
や水を用いる。加熱は、200〜450℃にて行う。In the present invention, in order to remove the organic solvent used in the surface treatment of the polyimide resin film, it is preferable to perform cleaning and/or heating. For cleaning, alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, or water is used. Heating is performed at 200 to 450°C.
このようにして、使用した、有機溶剤を樹脂膜中から除
くことにより、残留している有機溶剤が引き起こす、ポ
リイミド系樹脂膜の局所的脆弱化を防止できる。By removing the used organic solvent from the resin film in this manner, local weakening of the polyimide resin film caused by the remaining organic solvent can be prevented.
処理温度は、20℃以上、有機溶剤の沸点未満の範囲で
あることが好ましい。さらに、好ましくは30℃以上、
120℃以下である。 20℃未満の温度では、変質層
を十分に除去することができない。また、沸点を越える
と有機溶剤が揮発し、作業環境上、適さない。The treatment temperature is preferably in the range of 20° C. or higher and lower than the boiling point of the organic solvent. Furthermore, preferably 30°C or higher,
The temperature is 120°C or less. At temperatures below 20°C, the altered layer cannot be removed sufficiently. Moreover, if the boiling point is exceeded, the organic solvent will volatilize, making it unsuitable for the working environment.
ポリイミド系樹脂膜表面層の処理は、エツチング後、エ
ツチングマスクであるレジストを剥離する前に行っても
よいし、剥離する後に行ってもよい。The surface layer of the polyimide resin film may be treated after etching and before or after the resist, which is an etching mask, is peeled off.
しかしながら、この処理工程は、一般的には、レジスト
剥離後に1組み入れることが好ましい。However, it is generally preferable to incorporate this processing step after resist stripping.
これは、ポリイミド系樹脂膜が、レジスト剥離液に触れ
ることで、変質層表面での液交換が速く起こるために、
変質層の除去が効率良く進むためである。This is because when the polyimide resin film comes into contact with the resist stripping liquid, liquid exchange occurs quickly on the surface of the deteriorated layer.
This is because the removal of the altered layer proceeds efficiently.
本発明でいう配線基板は、単層あるいは多層どちらでも
構わない。The wiring board referred to in the present invention may be either a single layer or a multilayer.
変質層が、実質的に除去されているかは、IR。IR determines whether the altered layer has been substantially removed.
FT−IR等の検出手段を用いることができる。Detection means such as FT-IR can be used.
エツチング前および表面処理後において、ポリイミド構
造特有のC=○、C−N結合を示すピーク強度と、イミ
ド結合以外の結合、たとえば、芳香環のC=C結合、あ
るいは、変質層に特に強く見られる一NH−結合のピー
ク強度との相対強度の変化で判断する。表面処理後の相
対強度値が、エツチング前の相対強度値の374以上で
あるならば、実質的に除去されている。Before etching and after surface treatment, peak intensities showing C=○ and C-N bonds, which are unique to polyimide structures, and bonds other than imide bonds, such as C=C bonds in aromatic rings, or particularly strongly observed in altered layers, are observed. Judgment is made based on the change in intensity relative to the peak intensity of the -NH- bond. If the relative intensity value after surface treatment is 374 or more than the relative intensity value before etching, then it has been substantially removed.
また、変質層が実質的に除去されている配線基板の絶縁
破壊電圧は、250V/μm以上を示す。Further, the dielectric breakdown voltage of the wiring board from which the altered layer has been substantially removed is 250 V/μm or more.
(以下余白) ポリイミド系樹脂膜のエツチング液としては。(Margin below) As an etching solution for polyimide resin films.
ヒドラジンヒトラードとポリアミンの混合物から成る塩
基性溶剤が好適である。ポリアミンとしては、具体的に
エチレンジアミン、キシレンジアミン、トリメチレンジ
アミン、ヘキサメチレンジアミンが挙げられ、エチレン
ジアミン、キシレンジアミンは安価なので好適である。Basic solvents consisting of mixtures of hydrazine hydroxide and polyamines are preferred. Specific examples of the polyamine include ethylenediamine, xylenediamine, trimethylenediamine, and hexamethylenediamine, and ethylenediamine and xylenediamine are preferred because they are inexpensive.
配合割合はヒドラジンヒトラード90〜3o容量%と残
りがポリアミンであるものが望ましい、ヒドラジンヒト
ラードが90容量%より多いと、ポリイミド系樹脂膜が
膨潤し、パターン変形が発生しやすくなる。The blending ratio is preferably 90 to 3% by volume of hydrazine hydroxide and the remainder is polyamine. If hydrazine hydroxide is more than 90% by volume, the polyimide resin film will swell and pattern deformation will easily occur.
また30容量%より少ないとエツチング速度が低下し、
作業効率上適していない。Also, if it is less than 30% by volume, the etching speed will decrease,
Not suitable for work efficiency.
上記組成のエツチング液を用いてエツチングを行なう時
の液温は15℃〜60℃、好ましくは25℃〜50℃が
良い、液温が15℃未満であるとエツチング速度が著し
く低下し、作業効率上適していない、また、60℃を越
えるとパターン変形が発生しやすくなる。When performing etching using an etching solution with the above composition, the temperature of the solution should be 15°C to 60°C, preferably 25°C to 50°C. If the solution temperature is less than 15°C, the etching speed will drop significantly and the work efficiency will decrease. Moreover, if the temperature exceeds 60° C., pattern deformation tends to occur.
本発明で用いるレジスト膜としては、有機系又は無機系
のものが挙げられる。有機系レジストとしては、ポリイ
ミド系樹脂膜のエツチング液耐性を有するものであれば
、何れのものでも使用可能である。市販レジストとして
は、0DUR。The resist film used in the present invention may be organic or inorganic. Any organic resist can be used as long as it has resistance to etching solutions for polyimide resin films. As a commercially available resist, it is 0DUR.
OMR−83,0NNR(東京応化(株)爬)等が知ら
れている。OMR-83,0NNR (Tokyo Ohka Co., Ltd.) and the like are known.
上記有機系レジストをポリイミド系樹脂膜上に塗布する
方法としては、スピンナを用いたスピンコーティング法
、または浸漬、噴霧、印刷等の手段が用いられる。有機
系レジストは周知のフォトリソグラフィーによって、容
易に所望のパターンを形成することができる。As a method for applying the organic resist onto the polyimide resin film, a spin coating method using a spinner, dipping, spraying, printing, or other means is used. A desired pattern can be easily formed using an organic resist using well-known photolithography.
無機系レジストは金属材料をエツチングマスクとして用
いる。具体的には、アルミニウム、チタン、銅、銅−ニ
ッケル合金、クロム、タングステン、モリブデンなどが
材料として挙げられるが、ポリイミド系樹脂膜のエツチ
ング液耐性を有するものであれば、何れのものでも使用
可能である。Inorganic resist uses a metal material as an etching mask. Specifically, materials include aluminum, titanium, copper, copper-nickel alloy, chromium, tungsten, and molybdenum, but any material can be used as long as it is resistant to the etching solution of polyimide resin films. It is.
これらの金属材料は、蒸着法、スパッタリング法等によ
って膜形成が行なわれる。Films of these metal materials are formed by a vapor deposition method, a sputtering method, or the like.
さらに、フォトリソグラフィーによって、フォトレジス
トの所望のパターンを形成する。Furthermore, a desired pattern of photoresist is formed by photolithography.
[作 用]
塩基性のエツチング剤でエツチングされた、ポリイミド
系樹脂の表面石には、主として低分子量のポリイミド系
樹脂あるいはイミド環の開裂した樹脂からなる、変質層
が生じている。[Function] On the surface stone of polyimide resin etched with a basic etching agent, an altered layer consisting mainly of low molecular weight polyimide resin or resin with cleaved imide rings is formed.
本発明では、有機溶剤がこの変質層を溶解する。In the present invention, an organic solvent dissolves this altered layer.
こうして、変質層が引き起こす、配線導体の腐食等によ
る性能低下や、絶縁特性の低下を防止し、素子の信頼性
の向上を達成する。In this way, deterioration in performance due to corrosion of wiring conductors and the like and deterioration in insulation properties caused by the deteriorated layer are prevented, and the reliability of the element is improved.
有機溶剤としては、非プロトン性極性溶剤および/また
はポリアミンから選択される少なくとも1種類が好まし
く使用される。これらの溶剤は、ポリイミド系樹脂を侵
すことなく、変質層を選択的に除去することができる。As the organic solvent, at least one selected from aprotic polar solvents and/or polyamines is preferably used. These solvents can selectively remove the degraded layer without attacking the polyimide resin.
有機溶剤にて処理されたポリイミド系樹脂膜を洗浄およ
び/または加熱する場合には、有機溶剤が残留していな
い、樹脂膜を得ることができる。When a polyimide resin film treated with an organic solvent is washed and/or heated, a resin film in which no organic solvent remains can be obtained.
このようにして、残留有機溶剤によるポリイミド系樹脂
膜の局所的脆弱化を防止できる。In this way, local weakening of the polyimide resin film due to residual organic solvent can be prevented.
有機溶剤による処理が、20”C以上、有機溶剤の沸点
未満の条件内で、行われる場合には、効率良く変質層の
溶解除去が進む。また、有機溶剤が揮発しないため1作
業環境がよい。If the treatment with an organic solvent is carried out under conditions of 20"C or higher and below the boiling point of the organic solvent, the degraded layer can be efficiently dissolved and removed. Also, the organic solvent does not volatilize, so a single working environment is preferable. .
[実施例コ
実施例1
シリコンウェハ上に下部電極として、AQ蒸着膜を厚さ
2μm形成した後、その上に、日立化成工業(株)製の
登録商標PIQのポリイミド前駆体ワニスをスピン塗布
し、この基板を、200℃で30分間、続いて400℃
で60分間加熱して厚さ約5.0μmのポリイミド膜を
得た。[Example 1] After forming an AQ vapor-deposited film with a thickness of 2 μm as a lower electrode on a silicon wafer, a polyimide precursor varnish with the registered trademark PIQ manufactured by Hitachi Chemical Co., Ltd. was spin-coated thereon. , this substrate was heated at 200°C for 30 minutes, then at 400°C.
The mixture was heated for 60 minutes to obtain a polyimide film with a thickness of about 5.0 μm.
次に、上記基板をヒドラジンヒトラード−エチレンジア
ミン(無水)の70:30(容量%)混合溶液から成る
エツチング液に30℃で浸漬し、前述のポリイミド膜を
約2.2μm全面エツチングし、続いて純水で洗浄して
、エツチング時にエツチング液と反応して、ポリイミド
膜の表層に生成している変質層を含んだ、厚さ約2.8
μmのポリイミド膜を得た。Next, the above substrate was immersed in an etching solution consisting of a 70:30 (volume %) mixed solution of hydrazine hydroxide and ethylene diamine (anhydrous) at 30°C, and the entire surface of the polyimide film was etched by about 2.2 μm, and then The polyimide film has a thickness of approximately 2.8 cm, including a degraded layer formed on the surface layer of the polyimide film by washing with pure water and reacting with the etching solution during etching.
A μm polyimide film was obtained.
基板をさらに、N、N−ジメチルアセトアミドに100
℃で30分間浸漬して、続いて純水で洗浄し、エツチン
グ時にエツチング液と反応してポリイミド膜の表層に生
じた変質層を除去した。これにより、厚さ約2.0μm
のポリイミド膜を得た9次に、上記ポリイミド膜上に、
上部電極としてAQ膜を基板加熱をせずに室温で真空蒸
着して、厚さ3.5μmのAQ蒸着膜を形成した。The substrate was further diluted with N,N-dimethylacetamide at 100%
The polyimide film was immersed for 30 minutes at 0.degree. C. and then washed with pure water to remove a degraded layer that had formed on the surface of the polyimide film by reacting with the etching solution during etching. This results in a thickness of approximately 2.0 μm.
9 Next, on the polyimide film,
An AQ film was vacuum deposited as an upper electrode at room temperature without heating the substrate to form an AQ deposited film with a thickness of 3.5 μm.
上記の方法で100個の試験素子を製造し、これを用い
て絶縁破壊電圧を測定した。この結果。100 test elements were manufactured by the above method, and the dielectric breakdown voltage was measured using these. As a result.
試験素子の90%以上で上記ポリイミド膜が300V/
μm以上の破壊電圧を示した。In more than 90% of the test elements, the polyimide film had a voltage of 300V/
It exhibited a breakdown voltage of μm or more.
比較例
実施例1と同様に、厚さ2μmのAQ蒸着下部電極を形
成しているシリコンウェハ上に、PIQのポリイミド前
駆体ワニスをスピン塗布し、この基板を200℃で30
分間、続いて400℃で60分間加熱して厚さ約4.2
μmのポリイミド膜を得た。Comparative Example Similar to Example 1, a polyimide precursor varnish of PIQ was spin-coated onto a silicon wafer forming an AQ-deposited lower electrode with a thickness of 2 μm, and the substrate was heated at 200°C for 30 minutes.
4.2 minutes, then heated at 400℃ for 60 minutes to a thickness of approx.
A μm polyimide film was obtained.
次に、上記基板を、ヒドラジンヒトラード−エチレンジ
アミン(無水)の70:30(容量%)混合液から成る
エツチング液に30”Cで浸漬し、前述のポリイミド膜
を約2.2μ】全面エツチングし、続いて純水で洗浄し
て、エツチング時にエツチング液と反応してポリイミド
膜の表層に生じる変質層を含む、厚さ約2.0μmのポ
リイミド膜を得た。Next, the above substrate was immersed in an etching solution consisting of a 70:30 (volume %) mixture of hydrazine hydride and ethylene diamine (anhydrous) at 30"C, and the entire surface of the polyimide film was etched by about 2.2μ". Subsequently, the polyimide film was washed with pure water to obtain a polyimide film with a thickness of about 2.0 μm, including a degraded layer formed on the surface layer of the polyimide film by reaction with the etching solution during etching.
次に、上記ポリイミド膜上に上部電極としてAQ膜を基
板加熱をせずに室温で真空蒸着して、厚さ3.5μmの
A、Q蒸着膜を形成した。Next, an AQ film was vacuum-deposited as an upper electrode on the polyimide film at room temperature without heating the substrate to form an A, Q deposited film with a thickness of 3.5 μm.
上記の方法で100個の試験素子を製造し、これを用い
て絶縁破壊電圧を測定した。この結果、試験素子の90
%以上で上記ポリイミド膜の絶縁破壊電圧は100V/
μm以下の値しか示さなかった。100 test elements were manufactured by the above method, and the dielectric breakdown voltage was measured using these. As a result, 90% of the test element
% or more, the dielectric breakdown voltage of the polyimide film is 100V/
It showed only a value of less than μm.
実施例2〜4
変質層を除去する有機溶剤を、実施例2は、非プロトン
系溶剤であるN−メチル−2−ピロリドン、実施例3は
、同系のジメチルスルオキシドを用いた以外は、実施例
1と同様にして、試験素子を作製した。Examples 2 to 4 The organic solvent used to remove the altered layer was N-methyl-2-pyrrolidone, an aprotic solvent, in Example 2, and dimethyl sulfoxide, an aprotic solvent, in Example 3. A test element was produced in the same manner as in Example 1.
実施例4は、上記有機溶剤として、ポリアミンであるエ
チレンジアミンを用い、基板をエチレンジアミンに30
℃、30分間浸漬した以外は、実施例1と同様にして、
試験素子を作製した。In Example 4, ethylenediamine, which is a polyamine, was used as the organic solvent, and the substrate was immersed in ethylenediamine for 30 minutes.
The same procedure as in Example 1 was carried out except that the samples were immersed at ℃ for 30 minutes.
A test element was produced.
実施例2〜4で作製した試験素子を、実施例1と同様な
方法で、絶縁破壊電圧を測定し、試験素子の90%以上
が300V/μm以上の破壊電圧を示した。The dielectric breakdown voltage of the test elements produced in Examples 2 to 4 was measured in the same manner as in Example 1, and 90% or more of the test elements showed a breakdown voltage of 300 V/μm or more.
実施例5
実施例1と同様の方法で、変質層を含んだポリイミド膜
を得た後、実施例4と同様の方法で、基板を、ポリアミ
ンであるエチレンジアミンに100℃で30分間浸漬し
て、続いて純水で洗浄し、変質層を除去した。Example 5 After obtaining a polyimide film containing a degraded layer in the same manner as in Example 1, the substrate was immersed in ethylenediamine, which is a polyamine, for 30 minutes at 100° C. in the same manner as in Example 4. Subsequently, it was washed with pure water to remove the degraded layer.
さらに、この基板を350℃で30分間加熱して厚さ約
2.0μmのポリイミド膜を得た。Furthermore, this substrate was heated at 350° C. for 30 minutes to obtain a polyimide film with a thickness of about 2.0 μm.
次に、上記ポリイミド膜上に上部電極としてAQ膜を基
板加熱をせずに室温で真空蒸着して。Next, an AQ film was vacuum-deposited as an upper electrode on the polyimide film at room temperature without heating the substrate.
厚さ3.5μmのAn蒸着膜を形成した。An An vapor deposited film having a thickness of 3.5 μm was formed.
上記の方法で100個の試験素子を形成し、これを用い
て絶縁破壊電圧を測定した。この結果、実施例1と同様
に試験素子の95%以上で上記ポリイミド膜が300V
/μn1以上の破壊電圧を示した。100 test elements were formed by the above method, and dielectric breakdown voltage was measured using them. As a result, as in Example 1, more than 95% of the test elements showed that the polyimide film had a voltage of 300V.
It showed a breakdown voltage of /μn1 or more.
実施例6
第1図(a)に示すように、シリコンウェハ基板1上に
日立化成工業(株)製の登録商標PIQのポリイミド前
開体ワニスをスピン塗布し、上記基板を200”Cで3
0分間加熱して厚さ4μmのポリイミド膜を得た。この
操作を再度繰り返し、最後に400℃で60分間加熱し
1て厚さ8μmのポリイミド樹脂膜2を形成した。Example 6 As shown in FIG. 1(a), a polyimide pre-opening varnish with registered trademark PIQ manufactured by Hitachi Chemical Co., Ltd. was spin-coated on a silicon wafer substrate 1, and the substrate was heated at 200"C for 3
After heating for 0 minutes, a polyimide film with a thickness of 4 μm was obtained. This operation was repeated again and finally heated at 400° C. for 60 minutes to form a polyimide resin film 2 with a thickness of 8 μm.
次に、第1図(b)に示すように、ポリイミド樹脂膜2
上に東京応化工業(株)製のネガ型レジスト0NNR−
20(粘度140センチボイス)をスピン塗布し、上記
基板を100℃で30分間プリベークして厚さ2μmの
レジスト膜3を形成した。Next, as shown in FIG. 1(b), the polyimide resin film 2
On top is a negative resist 0NNR- manufactured by Tokyo Ohka Kogyo Co., Ltd.
20 (viscosity: 140 centivoice) was applied by spin coating, and the substrate was prebaked at 100° C. for 30 minutes to form a resist film 3 with a thickness of 2 μm.
次に、第1図(c)に示すように、所定のパターン形成
用ネガ型マスク(図示せず)を用いて、上記基板を密着
被覆し、500W高圧水銀灯を有する露光装置で露光し
た。続いて、東京応化工業(株)製の0NNR−20専
用現像液にて現像し、未露光部の除去、専用リンス液で
のリンスを行い、150℃で30分間ポストベークして
、50μm幅の抜きパターン3aを得た。Next, as shown in FIG. 1(c), the substrate was tightly coated using a predetermined pattern-forming negative mask (not shown), and exposed using an exposure apparatus equipped with a 500 W high-pressure mercury lamp. Subsequently, development was performed using a special developer for 0NNR-20 manufactured by Tokyo Ohka Kogyo Co., Ltd., the unexposed areas were removed, the product was rinsed using a special rinse solution, and post-baking was performed at 150°C for 30 minutes to form a 50 μm wide film. A punching pattern 3a was obtained.
次に、第1図(d)に示すように、レジストパターン3
aをエツチングマスクとして、エツチング液でポリイミ
ド系樹脂膜2を選択的にエツチング除去し、続いて純水
で洗浄した。この時のエツチング条件は、ヒドラジンヒ
トラード−エチレンジアミン(無水)の70:30(容
量%)混合溶液に30℃で50分間浸漬するものであっ
た。Next, as shown in FIG. 1(d), the resist pattern 3
Using a as an etching mask, the polyimide resin film 2 was selectively etched away with an etching solution, and then washed with pure water. The etching conditions at this time were immersion in a 70:30 (volume %) mixed solution of hydrazine hydroxide and ethylene diamine (anhydrous) at 30 DEG C. for 50 minutes.
次に、第1図(e)に示すように上記基板を東京応化工
業(株)製の商品名502(レジスト剥離液)に100
℃で10分間浸漬後、リンスして。Next, as shown in FIG. 1(e), the above substrate was coated with 502 (trade name) (resist stripping liquid) manufactured by Tokyo Ohka Kogyo Co., Ltd. for 100 min.
After soaking at ℃ for 10 minutes, rinse.
レジスト3を剥離した。Resist 3 was peeled off.
次に、上記基板を非プロトン性極性溶媒であるN、N−
ジメチルアセトアミドに100℃で30分間浸漬して、
続いて純水で洗浄し、エツチング時にエツチング液と反
応してポリイミド系樹脂膜の表層に生成している変質層
を除去し、信頼性を高めたポリイミド系樹脂膜を得た。Next, the above substrate was coated with an aprotic polar solvent such as N, N-
immersed in dimethylacetamide at 100°C for 30 minutes,
Subsequently, the film was washed with pure water to remove the degraded layer that had formed on the surface layer of the polyimide resin film by reacting with the etching solution during etching, thereby obtaining a polyimide resin film with improved reliability.
上記の方法で、100個の配線基板を製造し、これを用
いて#!A縁破壊電圧を測定した。この結果、90%以
上の配線基板が、300V/μ重以上の破壊電圧を示し
た。Using the above method, 100 wiring boards were manufactured and used to produce #! The A-edge breakdown voltage was measured. As a result, 90% or more of the wiring boards exhibited a breakdown voltage of 300 V/μ or more.
実施例7〜9
変質膜を除去する有@溶剤として、実施例7は、非プロ
トン性極性溶剤のN−メチル−2−ピロリドンを、実施
例8は、同系のジメチルスルオキシドを用いた以外は、
実施例6と同様にして、配線基板を製造した。Examples 7 to 9 Examples 7 to 9 used the aprotic polar solvent N-methyl-2-pyrrolidone as the solvent for removing the degraded film, and Example 8 used the same type of dimethyl sulfoxide. ,
A wiring board was manufactured in the same manner as in Example 6.
実施例9は、上記有機溶剤として、ポリアミンであるエ
チレンジアミンを用い、配線基板をエチレンジアミンに
30℃、40分間浸漬した以外は、実施例6と同様にし
て配線基板を製造した。In Example 9, a wiring board was manufactured in the same manner as in Example 6, except that ethylenediamine, which is a polyamine, was used as the organic solvent, and the wiring board was immersed in ethylenediamine at 30° C. for 40 minutes.
実施例7〜9で製造した配線基板を、実施例6と同様な
方法で、絶縁破壊電圧を測定し、実施例6と同様の結果
を得た。The dielectric breakdown voltages of the wiring boards manufactured in Examples 7 to 9 were measured in the same manner as in Example 6, and the same results as in Example 6 were obtained.
実施例10
第2図(a)に示すように、シリコンウェハ基板1上に
日立化成工業(株)製の登録商標PIQのポリイミド前
訃体ワニスをスピン塗布し、上記基板を200℃で30
分間加熱して厚さ4μmのポリイミド膜を得た。この操
作を再度繰り返し、最後に400℃で60分間加熱して
、厚さ8μmのポリイミド樹脂膜2を形成した。その上
に、ポリイミド樹脂膜2上にスパッタリングによって、
厚さ 0.8μmのアルミニウム膜4を形成した。Example 10 As shown in FIG. 2(a), a polyimide premortal varnish with registered trademark PIQ manufactured by Hitachi Chemical Co., Ltd. was spin-coated on a silicon wafer substrate 1, and the substrate was heated at 200°C for 30 minutes.
The mixture was heated for a minute to obtain a polyimide film with a thickness of 4 μm. This operation was repeated again and finally heated at 400° C. for 60 minutes to form a polyimide resin film 2 with a thickness of 8 μm. On top of that, by sputtering on the polyimide resin film 2,
An aluminum film 4 having a thickness of 0.8 μm was formed.
次に、第2図(b)に示すように、アルミニウム膜から
成るエツチングマスク形成の前処理として。Next, as shown in FIG. 2(b), as a pretreatment for forming an etching mask made of an aluminum film.
アルミニウム膜4上にフォトレジストとして東京応化工
業(株)製の商品名OMR−83(ネガ型レジスト)を
スピン塗布し、85°Cで30分間プリベークして厚さ
1.5μmのレジスト膜5を形成した。OMR-83 (a negative type resist) manufactured by Tokyo Ohka Kogyo Co., Ltd. is spin-coated as a photoresist on the aluminum film 4, and prebaked at 85°C for 30 minutes to form a resist film 5 with a thickness of 1.5 μm. Formed.
次に、第2図(c)に示すように、所定のパターン形成
用ネガ型マスク(図示せず)を用いて、周知のフォトリ
ソグラフィー技術によって、50μ11@の抜きパター
ン5aを得た。Next, as shown in FIG. 2(c), a punched pattern 5a of 50μ11@ was obtained by a well-known photolithography technique using a predetermined pattern-forming negative mask (not shown).
次いで、第2図(d)に示すように、上記フォトレジス
ト膜のパターン5aをマスクとして、アルミニウム膜4
をエツチングして、フォトレジスト膜のパターン5aを
アルミニウム膜4に転写し、アルミニウム膜パターン4
aを得た。アルミニウム膜4のエツチングは、上記基板
を、リン酸70容、硝酸25容、酢酸5容から成るエツ
チング液に浸漬して、アルミニウム膜4の露出部分を選
択的にエツチングして行なった。Next, as shown in FIG. 2(d), using the pattern 5a of the photoresist film as a mask, an aluminum film 4 is formed.
The pattern 5a of the photoresist film is transferred to the aluminum film 4 by etching.
I got a. Etching of the aluminum film 4 was carried out by immersing the substrate in an etching solution consisting of 70 volumes of phosphoric acid, 25 volumes of nitric acid, and 5 volumes of acetic acid, and selectively etching the exposed portions of the aluminum film 4.
次いで、第2図(e)に示すように上記基板を東京応化
工業(株)Ilの商品名5o2(レジスト剥離液)に、
100℃で10分間浸漬し、リンスして、レジスト膜の
パターン5aを剥離した。Next, as shown in FIG. 2(e), the above substrate was coated with Tokyo Ohka Kogyo Co., Ltd.'s Il trade name 5o2 (resist stripping liquid).
It was immersed at 100° C. for 10 minutes, rinsed, and the resist film pattern 5a was peeled off.
次いで、第2図(f)に示すように、アルミニウム膜パ
ターン4aをエツチングマスクとして、エツチング液で
ポリイミド系樹脂膜2を選択的にエツチング除去した後
、続いて純水で洗浄した。この時のエツチング条件は、
ヒドラジンヒトラード−エチレンジアミン(無水)の7
0:30(容量%)混合溶液に、30℃で50分間浸漬
するものであった。Next, as shown in FIG. 2(f), the polyimide resin film 2 was selectively etched away using an etching solution using the aluminum film pattern 4a as an etching mask, and then washed with pure water. The etching conditions at this time are
Hydrazine Hitleride-Ethylenediamine (Anhydrous) 7
It was to be immersed in a 0:30 (volume %) mixed solution at 30° C. for 50 minutes.
次に、上記基板を、非プロトン性極性溶媒であるN、N
−ジメチルアセトアミドに100℃で30分間浸漬して
、続いて純水で洗浄し、エツチング時にエツチング液と
反応してポリイミド系樹脂膜の表層に生成している変質
層を除去した。Next, the above substrate was treated with N, N, which is an aprotic polar solvent.
- It was immersed in dimethylacetamide at 100° C. for 30 minutes, and then washed with pure water to remove the altered layer that had formed on the surface layer of the polyimide resin film by reacting with the etching solution during etching.
次に、第2図(g)に示すように、上記基板を前述のア
ルミニウム膜エツチング液に浸漬してアルミニウム膜パ
ターン4aを除去して、変質層を除去した信頼性の高い
ポリイミド系樹脂膜を得た。Next, as shown in FIG. 2(g), the substrate is immersed in the aluminum film etching solution described above to remove the aluminum film pattern 4a, and a highly reliable polyimide resin film from which the deteriorated layer has been removed is formed. Obtained.
上記の方法で、100個の配線基板を製造し、これを用
いて絶縁破壊電圧を測定した。この結果、90%以上の
配線基板が、300V/μm以上の破壊電圧を示した。100 wiring boards were manufactured using the above method, and the dielectric breakdown voltage was measured using these. As a result, 90% or more of the wiring boards exhibited a breakdown voltage of 300 V/μm or more.
実施例12〜14
変質膜を除去する有機溶剤を、実施例12は、非プロト
ン性極性溶剤のN−メチル−2−ピロリドン、実施例1
3は、同系のジメチルスルオキシドを用いた以外は、実
施例11と同様にして配線基板を製造した。Examples 12 to 14 The organic solvent for removing the degraded film was N-methyl-2-pyrrolidone, an aprotic polar solvent in Example 12, and N-methyl-2-pyrrolidone in Example 1.
In Example 3, a wiring board was manufactured in the same manner as in Example 11 except that the same type of dimethyl sulfoxide was used.
実施例14は、上記有機溶剤として、ポリアミンである
エチレンジアミンを用い、配線基板をエチレンジアミン
に30℃、40分間浸漬した以外は、実施例11と同様
にして配線基板を製造した。In Example 14, a wiring board was produced in the same manner as in Example 11, except that ethylenediamine, which is a polyamine, was used as the organic solvent and the wiring board was immersed in ethylenediamine at 30° C. for 40 minutes.
実施例12〜14で製造した配線基板を、実施例11と
同様な方法で、絶縁破壊電圧を測定し、実施例11と同
様な結果を得た。The dielectric breakdown voltages of the wiring boards manufactured in Examples 12 to 14 were measured in the same manner as in Example 11, and the same results as in Example 11 were obtained.
実施例15
まず、第3図(a)に示すようにアルミナ基板6の上下
の電気的導通を得るために、あらかじめ基板内部の貫通
孔にタングステン柱8を設け、更にその表面に、ニッケ
ルメッキした導体層7を持つアルミナ基板6を準備した
。Example 15 First, in order to obtain electrical continuity between the upper and lower sides of the alumina substrate 6, as shown in FIG. An alumina substrate 6 having a conductor layer 7 was prepared.
上記基板上に、日立化成工業(株)製に登録商標PIQ
のポリイミド前睡体ワニスをスピン塗布し、上記基板を
200℃で30分間、次いで、350℃で30分間加熱
して厚さ4μmのポリイミド硬化膜を得た。この操作を
3回繰り返して、厚さ12 μ陽のポリイミド樹脂膜2
を形成した。On the above substrate, registered trademark PIQ manufactured by Hitachi Chemical Co., Ltd.
A polyimide preform varnish was applied by spin coating, and the substrate was heated at 200° C. for 30 minutes and then at 350° C. for 30 minutes to obtain a cured polyimide film with a thickness of 4 μm. Repeat this operation three times to form a polyimide resin film 2 with a thickness of 12 μm.
was formed.
次に、第3図(b)に示すように、導体層7の上部が開
口部となるポリイミド樹脂膜パターンを得た。この時の
パターン形成条件は、実施例6と同材料、同条件で、レ
ジスト膜を形成、パターン化し、次いで、導体層7の上
部が、開口部となるようにポリイミド樹脂膜をエツチン
グし、パターンを形成した。この時、レジスト膜の露光
には1:1投影露光装置を用いた。Next, as shown in FIG. 3(b), a polyimide resin film pattern was obtained in which the upper part of the conductor layer 7 was an opening. The pattern forming conditions at this time were to form and pattern a resist film using the same materials and under the same conditions as in Example 6, and then to etch the polyimide resin film so that the upper part of the conductor layer 7 becomes an opening, and to pattern it. was formed. At this time, a 1:1 projection exposure apparatus was used to expose the resist film.
また、ポリイミド樹脂膜のエツチング液も実施例6と同
材料を用いた。Furthermore, the same material as in Example 6 was used for the etching solution for the polyimide resin film.
続いて、非プロトン性極性溶媒であるN、N−ジメチル
アセトアミドに100℃で60分間浸漬して、続いて純
水で洗浄し、エツチング時に、エツチング液と反応して
ポリイミド系樹脂膜の表層に生成している変質層を除去
し、信頼性を高めたポリイミド樹脂膜パターンを得た。Next, it was immersed in N,N-dimethylacetamide, an aprotic polar solvent, at 100°C for 60 minutes, and then washed with pure water. During etching, it reacted with the etching solution and formed on the surface layer of the polyimide resin film. By removing the generated degraded layer, a polyimide resin film pattern with improved reliability was obtained.
次に、第3図(C)に示すように、基板全面に、厚さ3
μmのアルミニウム膜をスパッタリングにより形成し、
次いでレジストとして東京応化工業(株)製の商品名0
FPR(ポジ型レジスト)を用いてレジストパターン(
図示せず)を形成し、これをマスクとし、アルミエツチ
ング液としてリン酸75容、硝酸10容、酢酸15容か
ら成るエツチング液を用いてエツチングし、下地導体層
7との導通を有する、第1のアルミ配線層パターン9を
形成した。Next, as shown in FIG. 3(C), a thickness of 3.
A μm aluminum film is formed by sputtering,
Next, as a resist, product name 0 manufactured by Tokyo Ohka Kogyo Co., Ltd.
Resist pattern (
(not shown), and using this as a mask, etching is performed using an etching solution consisting of 75 volumes of phosphoric acid, 10 volumes of nitric acid, and 15 volumes of acetic acid as an aluminum etching solution. An aluminum wiring layer pattern 9 of No. 1 was formed.
次に、第3図(d)に示すように、アルミ配線層の上部
が選択的に開口部となるように、上記第3図(b)工程
と同様の方法によって、第2のポリイミド樹脂膜パター
ン2−2を形成した。そして、下部導体屡(第1のアル
ミ配線層パターン9)との導通を得るために、第2のポ
リイミド樹脂膜パターンの開口部上に、配線が位置する
ように、第2のアルミ配線層パターン9−2を、上記と
同様の方法によって、形成した。Next, as shown in FIG. 3(d), a second polyimide resin film is formed using the same method as in the step of FIG. 3(b) above so that the upper part of the aluminum wiring layer becomes a selective opening. Pattern 2-2 was formed. Then, in order to obtain conduction with the lower conductor layer (first aluminum wiring layer pattern 9), the second aluminum wiring layer pattern is placed so that the wiring is located above the opening of the second polyimide resin film pattern. 9-2 was formed by the same method as above.
これを繰り返して、アルミ配線層として9〜9−4から
なる4層、ポリイミド樹脂膜として2〜2−4からなる
4層の薄膜多層配線基板を作成した。This process was repeated to create a thin film multilayer wiring board having four layers consisting of 9 to 9-4 as the aluminum wiring layer and four layers consisting of 2 to 2-4 as the polyimide resin film.
上記の方法で、100個の配線基板を製造し、これを用
いて絶縁破壊電圧を測定した。この結果、90%以上の
配線基板が、300V/μm以上の破壊電圧を示した。100 wiring boards were manufactured using the above method, and the dielectric breakdown voltage was measured using these. As a result, 90% or more of the wiring boards exhibited a breakdown voltage of 300 V/μm or more.
[発明の効果コ
以上のように、本発明は、エツチング時に、エツチング
液と反応してポリイミド系樹脂膜の表面に生成する変質
層を除去する。[Effects of the Invention] As described above, the present invention removes the altered layer that is generated on the surface of the polyimide resin film by reacting with the etching solution during etching.
こうして、変質層が引き起こす、配線導体の腐食等によ
る性能低下や、絶縁特性の低下を防止し、素子の信頼性
の向上を達成できる。In this way, performance deterioration due to corrosion of wiring conductors and deterioration of insulation properties caused by the deteriorated layer can be prevented, and the reliability of the element can be improved.
従って、本発明を、半導体素子や薄膜多N基板等の絶縁
膜のエツチング工程に利用すれば、信頼性の高い絶#膜
を形成することができる。Therefore, if the present invention is applied to the etching process of an insulating film of a semiconductor element or a thin film multi-N substrate, a highly reliable insulating film can be formed.
第1図、第2図および第3図は、本発明を用いた配線基
板の製造工程を概説する断面図である。
1・・・基板、2・・・ポリイミド系樹脂膜、3・・・
レジスト、3a・・・レジストパターン、4・・・アル
ミニウム膜、4a・・・アルミニウム膜パターン、5・
・・レジスト、5a・・・レジストパターン、6・・・
アルミナ基板、7・・・ニッケル層、8・・・タングス
テン層、9・・・アルミ配線。FIG. 1, FIG. 2, and FIG. 3 are cross-sectional views outlining the manufacturing process of a wiring board using the present invention. 1... Substrate, 2... Polyimide resin film, 3...
Resist, 3a... Resist pattern, 4... Aluminum film, 4a... Aluminum film pattern, 5.
...Resist, 5a...Resist pattern, 6...
Alumina substrate, 7...nickel layer, 8...tungsten layer, 9...aluminum wiring.
Claims (1)
ト膜パターンを形成し、該レジスト膜パターンをマスク
として、エッチング液にて前記ポリイミド系樹脂膜をエ
ッチングする方法において、前記エッチング液により前
記ポリイミド樹脂膜上に生じる変質膜を、有機溶剤にて
、除去することを特徴とするポリイミド系樹脂膜のエッ
チング方法。 2、前記有機溶剤が、非プロトン性極性溶剤および/ま
たはポリアミンから選択される少なくとも1種類である
ことを特徴とする請求項1記載のポリイミド系樹脂膜の
エッチング方法。 3、前記有機溶剤にて処理されたポリイミド系樹脂膜が
、洗浄および/または加熱されることを特徴とする請求
項1または2記載のポリイミド系樹脂膜のエッチング方
法。 4、前記有機溶剤による処理が、20℃以上、有機溶剤
の沸点未満で行われることを特徴とする請求項1、2ま
たは3記載のポリイミド系樹脂膜のエッチング方法。 5、基板上に形成した絶縁膜に、レジスト膜パターンを
形成し、該レジスト膜パターンをマスクとして、第一の
エッチング液にて前記絶縁膜をエッチングし、その後さ
らに、第二のエッチング液により絶縁膜露出部を処理す
ることを特徴とする絶縁膜のエッチング方法。 6、前記第二のエッチング液は、第一のエッチング工程
において接触により生じた絶縁膜露出表面部の変質層に
対して、選択性を有することを特徴とする請求項5記載
の絶縁膜のエッチング方法。 7、請求項1、2、3または4記載のポリイミド系樹脂
膜のエッチング方法にてエッチングされたポリイミド系
樹脂膜が、層間絶縁膜として、積層されている配線構造
体。 8、エッチングにより開口を形成した絶縁膜を有する配
線構造体において、前記絶縁膜が、エッチングによる変
質層を実質的に含まないことを特徴とする配線構造体。 9、エッチング工程において、被エッチング材露出表面
部に生じた変質層を、該変質層に対して選択的に作用す
る有機溶剤により処理することを特徴とする被エッチン
グ材の処理方法。[Claims] 1. A method in which a resist film pattern is formed on a polyimide resin film formed on a substrate, and the polyimide resin film is etched with an etching solution using the resist film pattern as a mask. A method for etching a polyimide resin film, comprising removing a degraded film formed on the polyimide resin film by the etching solution using an organic solvent. 2. The method for etching a polyimide resin film according to claim 1, wherein the organic solvent is at least one selected from aprotic polar solvents and/or polyamines. 3. The method of etching a polyimide resin film according to claim 1 or 2, wherein the polyimide resin film treated with the organic solvent is washed and/or heated. 4. The method of etching a polyimide resin film according to claim 1, 2 or 3, wherein the treatment with the organic solvent is carried out at a temperature of 20°C or higher and lower than the boiling point of the organic solvent. 5. A resist film pattern is formed on the insulating film formed on the substrate, and using the resist film pattern as a mask, the insulating film is etched with a first etching solution, and then further insulated with a second etching solution. A method of etching an insulating film, characterized by processing an exposed part of the film. 6. Etching of an insulating film according to claim 5, wherein the second etching solution has selectivity to the altered layer on the exposed surface of the insulating film caused by contact in the first etching step. Method. 7. A wiring structure in which a polyimide resin film etched by the polyimide resin film etching method according to claim 1, 2, 3 or 4 is laminated as an interlayer insulating film. 8. A wiring structure having an insulating film in which an opening is formed by etching, wherein the insulating film does not substantially contain a layer altered by etching. 9. A method for treating a material to be etched, characterized in that, in the etching step, a degraded layer formed on the exposed surface of the material to be etched is treated with an organic solvent that acts selectively on the degraded layer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13691989A JPH033239A (en) | 1989-05-30 | 1989-05-30 | Etching method for polyimide resin film, wiring structure using the method, and processing method for material to be etched |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13691989A JPH033239A (en) | 1989-05-30 | 1989-05-30 | Etching method for polyimide resin film, wiring structure using the method, and processing method for material to be etched |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH033239A true JPH033239A (en) | 1991-01-09 |
Family
ID=15186643
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13691989A Pending JPH033239A (en) | 1989-05-30 | 1989-05-30 | Etching method for polyimide resin film, wiring structure using the method, and processing method for material to be etched |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH033239A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008307308A (en) * | 2007-06-18 | 2008-12-25 | Enomoto Co Ltd | Mounting structure of decorative board |
-
1989
- 1989-05-30 JP JP13691989A patent/JPH033239A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008307308A (en) * | 2007-06-18 | 2008-12-25 | Enomoto Co Ltd | Mounting structure of decorative board |
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