EP1057080A1 - Resist stripping process - Google Patents
Resist stripping processInfo
- Publication number
- EP1057080A1 EP1057080A1 EP99905603A EP99905603A EP1057080A1 EP 1057080 A1 EP1057080 A1 EP 1057080A1 EP 99905603 A EP99905603 A EP 99905603A EP 99905603 A EP99905603 A EP 99905603A EP 1057080 A1 EP1057080 A1 EP 1057080A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- ammonium
- resist
- source
- hydroxide
- 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.)
- Withdrawn
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
Definitions
- the present invention is in the field of printed wi ⁇ ng board fab ⁇ cation. More specifically, the present invention relates to a process for removing or stnppmg resist mate ⁇ al from the p ⁇ nted wiring board following plating or etching process steps.
- PWB p ⁇ nted wiring boards
- etching subtractive
- plating additive
- the resist- coated panel is exposed to electromagnetic energy, such as visible light or ultraviolet (UN) radiation, which is projected through a pattern.
- the pattern defines artwork corresponding to a positive or negative image of the metallic traces to be formed on the board.
- Exposed portions of the negative-type resist undergo a chemical change which allows them to remain on the board.
- the unexposed portions of the resist are developed off, (i.e., removed).
- the exposed areas of the resist are rendered soluble in the developing solution.
- the soluble areas are removed, leaving the patterned unexposed areas of resist on the board.
- the resist image may be defined or patterned using a screen printing process.
- an electron beam or laser ablation can be used to define a pattern in the resist.
- the PWB surface will be exposed to plating or etching steps depending upon the specific board type and the particular manufacturing technique selected. Following this exposure, it is normally necessary to remove the photopolymer resist layer to allow further processing. The removal step is accomplished using a resist st ⁇ pping process.
- stripping composition consists of a mixture of aliphatic or cyclic organic, (i.e., carbon containing), amines, organic quaternary ammonium hydroxides and organic solvents. Sometimes inorganic alkali metal hydroxides are also used as secondary alkalinity carriers.
- U.S. Patent No. 5,545,353 describes a photoresist stripper composition containing an organic polar solvent, an alkanolamine and a thiocarboxylic acid as a corrosion inhibitor.
- U.S. Patent No. 5,556,482 teaches a method of stripping photoresist with a composition comprising organic polar solvents, basic amines and an inhibitor.
- 4,904,571 discloses a method for removing photoresist in solution comprising alcohols, ethers, ketones, chlorinated chlorocarbons, aromatic hydrocarbons, alkali metal hydroxides, carbonates, phosphates, pyrophosphates, borohydrides and organic amine borane compounds.
- the organic part of the stripper containing amine and a solvent mixture, acts as the primary stripping agent.
- Such compositions are known to offer high performance, (i.e. high speed), long life and small stripped resist particle size.
- the organic part of the stripper composition consists of volatile organic compounds (hereafter VOCs). Due to increasingly stringent government environmental laws and regulations, the printed wiring board industry currently is under heavy pressure to reduce VOC emissions.
- VOCs are typically defined as any volatile compound of carbon, (excluding methane, carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, ammonium carbonate and exempt compounds), which participates in atmospheric photochemical reactions. VOCs react photochemically in the troposphere with nitrogen oxides (NO x ) in the presence of ultraviolet radiation from sunlight and atmospheric oxygen to form ground-level ozone — the - -> - pnmary component of "smog", which is a mixture of NO x , peroxyacyl nitrate (CH 3 COONO 2 ), VOCs and ozone. As a result, VOCs are regulated as "ozone precursors"
- the present invention relates to processes for removing or st ⁇ pping resist mate ⁇ al from the p ⁇ nted wi ⁇ ng board following plating or etching process steps More specifically, the present invention relates to a process for removing resist patterns from a substrate which comp ⁇ ses the steps of providing a substrate having a patterned or layered resist on a surface, providing a VOC-free resist st ⁇ pping solution which includes a source of an ammonium ion, and exposing the substrate to the st ⁇ pping solution for a time sufficient to remove all patterned or layered resist from the surface.
- ammonium ions have been found to be very effective m stripping resist patterns or layers.
- the present invention provides a simple photoresist st ⁇ pping process that does not use VOCs, and as such, the invention eliminates a significant source of environmental contamination.
- resist st ⁇ ppmg One of the steps of the PWB manufactu ⁇ ng process that is being targeted for VOC emission reduction, and eventual elimination, is resist st ⁇ ppmg
- a source of ammonium ions such as ammonia gas or ammonium hydroxide.
- Ammonia-based compounds are already used in the PWB industry, and ammonium hydroxide is used extensively in ammomacal etchants for vanous copper etching processes.
- the etching step is a step just preceding resist st ⁇ pping in mnerlayer production or subsequent to resist st ⁇ pping in outerlayer manufactu ⁇ ng
- Ammonia is very soluble in aqueous solutions and once dissolved, depending on pH. it can react with hydrogen (hydromum) ions to form ammonium ions This reaction occurs if hydrogen ions are readily available, such as at low pH In alkaline solution, where hydrogen ions are not readily available, the ammonia remains in its gaseous form At a pH of greater than about 9 3 (at 25°C), 50% of ammonia is in the form of the ammonium ion, whereas at a pH of about 12, almost 100% of ammonia remains in gaseous form At elevated temperatures, the equihbnum is shifted further toward gas - 4 - Conventional resist st ⁇ ppers are normally used under conditions at which the pH is greater than about 1 1 and the temperature is in the range of about 120-130°F (about 49-54°C) At these conditions, virtually all of the ammonia would stay in gaseous form and volatilize in a matter of hours As such, ammonia gas was never commercially utilized as a p
- U.S Patent No 4,078,102 desenbes a process for stnppmg resist in a mixture of an aldehyde or a ketone as pnmary resist stripper agent and an activator, containing an alcoholic solution of ammonium, alkali and alkali earth metal hydroxides in proportion of 0.005 to 0.1 mole activator to 1 mole of aldehyde or ketone
- the patent suggests a saturated isopropyl alcohol solution of sodium hydroxide (alkalinity earner) and cyclohexanone (pnmary resist stnpper) in proportion 0 006-0.01 to 1
- alkalinity earner sodium hydroxide
- pnmary resist stnpper cyclohexanone
- the concept behind current invention is to provide a fully aqueous VOC-free resist stnppmg process utilizing ammonia gas or other source of ammonium ions as a pnmary resist stnppmg agent without utilizing any volatile organic matenals
- the invention also relates to a method to maintain constant and sufficiently high ammonium ion concentration m alkaline solutions (pH>9) at elevated temperatures, (i.e , 80-140°F)
- Optional bath components include non-volatile inhibitors to prevent corrosion of metal surfaces exposed to the stnppmg solution, and antifoammg or defoammg agents to control foam generation if the solution is subjected to high agitation to enhance the stnppmg action
- ammonium ion concentration can be easily maintained at a constant level by utilizing any of the following methods: a) continuously feeding an ammonium hydroxide solution into the stripper solution; b) continuously feeding an alkaline ammonium salt (carbonate, carbamate, silicate, formate, phosphate, sulfite, etc.), which will convert into ammonium gas at pH>12 and 120-
- the stripping solution can be applied to the developed photoresist using any of a wide variety of methods known in the art.
- the board containing the developed photoresist may simply be immersed into a bath of the stripping solution.
- the stripping solution may be sprayed onto the board. It is noted that the methods described herein to apply the stripping solution to the developed photoresist are not intended to limit the invention in any way.
- the source of the ammonium ions is not intended to be limited to those species described above, but rather may be any ammonium ion source that can be used without introducing VOCs into the process.
- it is desirable to maintain the stripping solution at a caustic pH both for the stripping ability of the caustic and for the ability of the caustic solution to convert ammonium ions into a source of ammonia gas.
- the invention is not intended to be limited strictly to those compounds. Rather, virtually any source of alkalinity can be used provided that it does not introduce VOCs into the process.
- a copper-clad panel was hot-roll laminated using DuPont Riston 9020 dry film, exposed and developed in 1% sodium carbonate solution.
- a resist stripping solution containing 20 grams per liter of potassium hydroxide and 10 milliliters per liter of ammonium hydroxide (30% aqueous solution) was provided. The stripping solution was heated to about 125°F (about - 6 - 51.7°C) and the panel was immersed into the solution. In less than 60 seconds, all the resist was completely removed from the surface of the panel.
- Example 2
- a copper-clad panel was hot-roll laminated using Dynachem Laminar GA dry film, exposed and developed in 1% sodium carbonate solution.
- a resist stripping solution containing 50 grams per liter of sodium hydroxide and 20 grams per liter of ammonium bicarbonate was provided. The stripping solution was heated to about 130°F (about 54.4°C) and the panel was immersed into the solution. In less than 60 seconds, all the resist was completely removed from the surface of the panel.
- a copper-clad panel was hot-roll laminated using DuPont Riston 9015 dry film, exposed and developed in 1% sodium carbonate solution.
- a resist stripping solution containing 25 grams per liter of lithium hydroxide and 15 grams per liter of ammonium carbamate was provided. The stripping solution was heated to about 120°F (about 48.9°C) and the panel was immersed into the solution. In less than 60 seconds, all the resist was completely removed from the surface of the panel.
- Example 1 Three copper-clad panels were hot-roll laminated using DuPont Riston 9020 dry film, exposed and developed in 1% sodium carbonate solution.
- the stripping solution from Example 1 was heated to about 125°F (about 51.7°C) and the first panel was immersed into the solution. In less than 60 seconds, all the resist was completely removed from the surface of the panel.
- the solution was stirred at about 125°F (about 51.7°C) for 2 hours to volatilize ammonia.
- the second panel was immersed into the solution. After 60 seconds, the resist was not completely removed from the surface of the second panel.
- Ten milliliters of 30% ammonium hydroxide were added to the stripping solution, and the third panel was immersed into the solution. In less than 60 seconds, all the resist was completely removed from the surface of the third panel. Comparative Example 1
- a copper-clad panel was hot-roll laminated using DuPont Riston 9020 dry film, exposed and developed in 1% sodium carbonate solution.
- a resist stripping solution containing 20 grams per liter of potassium hydroxide was provided. The stripping solution was heated to about 125°F (about 51.7°C) and the panel was immersed into the solution. After 60 seconds, the resist was not removed from the surface of the panel. - 7 - Comparative Example 2
- a copper-clad panel was hot-roll laminated using DuPont Riston 9020 dry film, exposed and developed in 1% sodium carbonate solution.
- a resist stripping solution containing PC-4077 Resist Stripper (available from Alpha Metals PC Fab Division) 10% (by vol.) was provided. The stripping solution was heated to about 125°F (about 51.7°C) and the panel was immersed into the solution. After 60 seconds, the resist was completely removed from the surface of the panel.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US3115498A | 1998-02-26 | 1998-02-26 | |
US31154 | 1998-02-26 | ||
PCT/US1999/002160 WO1999044101A1 (en) | 1998-02-26 | 1999-02-01 | Resist stripping process |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1057080A1 true EP1057080A1 (en) | 2000-12-06 |
Family
ID=21857911
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99905603A Withdrawn EP1057080A1 (en) | 1998-02-26 | 1999-02-01 | Resist stripping process |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1057080A1 (en) |
JP (1) | JP2002505448A (en) |
KR (1) | KR20010041221A (en) |
CN (1) | CN1129036C (en) |
TW (1) | TW407449B (en) |
WO (1) | WO1999044101A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3328250B2 (en) * | 1998-12-09 | 2002-09-24 | 岸本産業株式会社 | Resist residue remover |
WO2000044034A1 (en) * | 1999-01-25 | 2000-07-27 | Speedfam-Ipec Corporation | Methods and cleaning solutions for post-chemical mechanical polishing |
KR20030007288A (en) * | 2002-11-29 | 2003-01-23 | (주) 라모스테크놀러지 | Digital player which possesses a e-mail facility and method for processing it |
KR100582202B1 (en) * | 2003-10-13 | 2006-05-23 | 엘지.필립스 엘시디 주식회사 | Fabrication apparatus and method of thin film transistor array substrate |
US8338087B2 (en) * | 2004-03-03 | 2012-12-25 | Advanced Technology Materials, Inc | Composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate |
CN102221791B (en) * | 2011-04-29 | 2014-09-03 | 西安东旺精细化学有限公司 | Photoresist stripper composition |
US8975008B2 (en) * | 2012-05-24 | 2015-03-10 | Rohm And Haas Electronic Materials Llc | Method of removing negative acting photoresists |
TWI595332B (en) * | 2014-08-05 | 2017-08-11 | 頎邦科技股份有限公司 | Method for photoresist stripping |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD143920A1 (en) * | 1979-05-24 | 1980-09-17 | Uwe Jungstand | EXTRACTS FOR REMOVING POSITIVE PICTURES |
JPS60203944A (en) * | 1984-03-28 | 1985-10-15 | Mitsubishi Gas Chem Co Inc | Method for removing positive type photoresist |
-
1999
- 1999-02-01 EP EP99905603A patent/EP1057080A1/en not_active Withdrawn
- 1999-02-01 JP JP2000533792A patent/JP2002505448A/en active Pending
- 1999-02-01 WO PCT/US1999/002160 patent/WO1999044101A1/en not_active Application Discontinuation
- 1999-02-01 CN CN99804505A patent/CN1129036C/en not_active Expired - Fee Related
- 1999-02-01 KR KR1020007009310A patent/KR20010041221A/en not_active Application Discontinuation
- 1999-02-08 TW TW088101903A patent/TW407449B/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO9944101A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1999044101A1 (en) | 1999-09-02 |
KR20010041221A (en) | 2001-05-15 |
TW407449B (en) | 2000-10-01 |
CN1129036C (en) | 2003-11-26 |
CN1298496A (en) | 2001-06-06 |
JP2002505448A (en) | 2002-02-19 |
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Legal Events
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