EP0662223A1 - Procede d'elimination d'agents photoresistants employant du m,m-dimethyle-bis(2-hydroxyethyle) hydroxyde d'ammonium quaternaire - Google Patents
Procede d'elimination d'agents photoresistants employant du m,m-dimethyle-bis(2-hydroxyethyle) hydroxyde d'ammonium quaternaireInfo
- Publication number
- EP0662223A1 EP0662223A1 EP93921680A EP93921680A EP0662223A1 EP 0662223 A1 EP0662223 A1 EP 0662223A1 EP 93921680 A EP93921680 A EP 93921680A EP 93921680 A EP93921680 A EP 93921680A EP 0662223 A1 EP0662223 A1 EP 0662223A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stripping
- complexing agent
- metal complexing
- weight percent
- choline
- 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.)
- Ceased
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
Definitions
- the present invention relates to a process for stripping photo ⁇ resists used in etching and plating operations for forming printed circuits wherein N,N-dimethyl-bis(2-hydroxyethyl) quaternary ammonium hydroxide is used as the stripping agent.
- choline [(CH ⁇ N+C ⁇ CH j OH] [OH]- has been used as a stripping agent for photo-resists.
- choline has the advantages of being an organic base which leaves no non-volatile residues, low toxicity, relatively low cost, easily made, being a strong base and being biodegradable.
- choline suffers the disadvantages of having a serious odor problem in use and of decomposing to give colored solutions and precipitates.
- the present invention involves the use of N,N-dimethyl-bis(2- hydroxyethyl) quaternary ammonium hydroxide (choline II) as a stripping agent for removal of unexposed areas of photo-resists prior to etching or plating.
- the choline II is used as a 0.1 to 15 wt % aqueous solution.
- Figure I is a graphic representation of the stripping agents described in Example 2 below.
- the choline II used in the present invention is prepared by reacting two moles of ethylene oxide with one mole of dimethyl amine.
- the preferred technique is to mix dimethyl amine with about twice the molar amount of ethylene oxide at 35° to 60° C under a pressure of 15 to 150 psi (3.5 to 35 KPa) at a rate of from 0.5 to 5 moles per hour after which time the reaction is substantially complete.
- choline II The stripping action of choline II on photo-resists has been found to be substantially identical with that of choline I. [(CH 3 ) 3 N + -CH 2 - CH 2 OH][OH] " which in spite of its disadvantages is widely used as a stripping agent for photo-resists. Further, the base strength of choline II is substantially identical with that of choline I.
- a 1 to 10% aqueous solution of choline ⁇ is used to perform the stripping process.
- the stripping process is carried out at 40° to 100°C for 0.1 to 10 minutes.
- the stripping solution contains from 0.5 to 10 wt % of a metal complexing agent such as monoethanol amine, ethylene diamime, or ethylene diamine tetraacetic acid.
- a metal complexing agent such as monoethanol amine, ethylene diamime, or ethylene diamine tetraacetic acid.
- the metal complexing agent serves to break the bond between the metal (copper) on the metal clad substrate and the photoresist, thereby facilitating removal of the photoresist from the metal clad substrate.
- ammonia (NH 3 ) exerts very significant favorable effects when added to the compositions of the invention. Even amounts as little as 0.1% by weight noticeably improve stripping speed, the sensitivity of stripping speed to changes in pH and the sensitivity of stripping speed to changes in temperature (i.e. the activation energy of stripping).
- compositions of the invention will consist of ternary mixtures of choline ⁇ bases or basic salts; ammonia; and a metal complexing agent.
- Metal complexing agents suitable for the purposes of this invention comprise those whose complexes with copper ⁇ ions have complexity constants of less than 10 -2 . That is, in the reaction,
- [Cu +2 ] [L] K, ⁇ 10- 2 [Cu L ⁇ +2+ ⁇ >] is less than 10" 2 .
- the symbol “L” signifies the ligand or metal complexing agent concentration in moles per liter
- [Cu +E ] stands for the concentration of cupric ions in moles per liter
- (Cu L +2 - l ) the concentration of cupric complexed ion.
- “1” is the valence (usually negative) of the ionized complexing agent in those cases where the complexing agent is a charged species.
- glycine H 2 N-C 2 H 4 -C-OH would have a charge of (-1) due to the ionization of the proton of its carboxylic acid group.
- ethylene diamine tetraacetic acid would have a charge of (-4), nitilo-triacetic acid a charge of (-3), etc.
- the choline II base component seems to function primarily via hydroysis of hydrolyzable species in the photo-resist.
- the photo-resists usually contain a multiplicity of linkages such as ester linkages, amide linkages, urethane linkages, ether linkages, products of aldol condensations, etc.
- Strong bases such as choline ⁇ furnish a high concentration of hydroxyl ions which catalyze the hydrolysis of such linkages.
- linkages in the photo-resist such as esters which form acidic groups upon hydrolysis
- strong bases such as choline II , can neutralize the acid group to form a salt.
- the logarithm of the rate of stripping (i.e. str i p i ng t i me ) is a linear function of the logarithm of the hydroxyl ion concentration with a slope of one.
- the activation energy for stripping is of the order of 20 kilocalories per mole, as expected for ester hydrolysis, or for amide hydrolysis.
- the role of the metal complexing agent is almost certainly to form complex ions with the copper surface atoms of the copper-coated, fiberglass laminate, thus weakening the attachment of such atoms to groups such as carboxylic acid groups in the photo-resist polymer. This in turn weakens the bond between the copper surface and the photo-resist polymer
- All basic stripping baths decrease their pH during use, due to pick up of CO 2 from the air, reaction with acid groups in the photo-resist, and loss of base via chemical decomposition, volitilization, mechanical carry-over and adsorption into the discarded photo-resist flakes.
- stripping rates are much faster (by factors ranging from 2-5) in the presence of the complexing agent. It can also be seen that the loss of stripping speed as the pH decreases is much lower than with choline ⁇ alone.
- the NH 3 molecule may be small enough to penetrate rapidly through the photo-resist polymer and start a process of swelling the polymer while simultaneously forming copper amine complexes with surface copper atoms on the copper-coated fiberglass laminate. Both of these actions may facilitate the attack by strong base and metal complexing agents.
- the photo-resists being stripped by the process of the present invention generally are polymer films which change their solubility upon exposure to light. Positive photo-resists become less soluble due to photo- induced cross-linking. Negative photo-resists become more soluble due to photo-induced depolymerization.
- photo-resists comprise a binder phase, a solubilizing or cross-linking polymer, a photo-sensitive group which catalyzes cross- linking reactions or depolymerization reactions when exposed to light and a dye to enhance light absorption.
- the binder phase is a phenol- formaldehyde resin, an epoxy resin, a polyamide, polyimide, polyurethane, etc.
- the solubilizing or cross-linking polymers are polyacrylic acid, polymethacrylic acid, maleic anhydride- vinyl copolymers or other polyacids.
- the photo-resist polymer films are bonded by heat and pressure to copper-plated fiber glass-resin laminate sheets.
- the photo-resist can be applied as a coating to a copper clad substrate.
- a copper clad substrate Silicon or gold plated alumina substrates are used for high quality electronics applications.
- the photo-resist is exposed to light through a pattern containing the shape of the desired electronic circuit. Exposed (negative resist) or unexposed (positive resist) areas are removed by developing with a mild developer solution. Then various other operations are conducted on mild developer solution. Then various other operations are conducted on exposed copper areas such as etching, plating, soldering of connections, or deposition of other patterns.
- the final step involves removing the "insoluble" protecting part of the photoresist film which is removed by a stripping agent.
- the stripping agent functions to remove the protective photo ⁇ resist by a combination of actions including one or more of hydrolysis, metal complexing, dissolving of photo-resist components, salt formation, swelling, solvation, and mechanical shearing forces.
- the features sought after in stripping agents generally are low temperature operation, tolerable working environment, i.e., odor-free and non-toxic, control of flake size, speed of stripping, predictable constant speed of stripping, clean stable bath, i.e., no color, no precipitates and no decomposition, no residues on the work piece, a low corrosion of copper plate and connectors, ease of disposal, i.e., low toxicity and biodegradability, and competitive price.
- N,N-dimethyl-2-hydroxyethyl/amine + acetaldehyde The N,N-dimethyl-2-hydroxyethyl amine is a non-volatile and non-smelly amine.
- the acetaldehyde is the same color forming precipitate formed by the degradation of choline I and the things which slow this problem when using choline I also work with choline II. These Hoffman degradation products of choline ⁇ do not undergo further degradation and the choline II remains odor free even after a month at 50°C. Examples
- Example 2 A plurality of stripping runs are made using an aqueous solution of N,N-dimethyl-bis(2-hydroxyethyl) quaternary ammonium hydroxide alone and in conjunction with equal weight amounts of monoethanolamine and/or ammonia. The pH of the resulting mixture was measured with a pH meter to the value reported in Figure I.
- the photo- resist being stripped is approximately 1.5 mils in thickness laminated to a copper clad, phenolic substrate reinforced with a woven glass fabric.
- the composition of the photo-resists are proprietory but generally contain the following:
- acrylic polyfunctional monomers such as pentaerythritol triacrylate.
- Photo initiator systems such as Michlers ketone, benzophenone, thioanthones, etc. ( 5%).
- Dyes such as malachite green or Victoria blue ( 0.1 %).
- Nitrillotriacetic acid (wt %) 1
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Procédé d'élimination d'agents photorésistants et bain aqueux utilisé dans le procédé. Ce procédé s'effectue dans des conditions de température comprises entre 40 et 100 °C pendant 0,1 à 10 minutes environ. Le bain aqueux renferme de 1 à 10 pour cent en poids de M,M-diméthyle-bis(2-hydroxyéthyle) hydroxyde d'ammonium quaternaire et de préférence de 0,5 à 10 pour cent en poids d'un agent complexant métallique tel que de l'amine de monoéthanol, de la diamine d'éthylène, du tétraacétique de diamine d'éthylène, de la mélanine, de l'acide nitrillotriacétique, de la morpholine, de l'acétonylacétone et de préférence de 0,1 à 5 pour cent en poids d'ammoniaque.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US95211292A | 1992-09-28 | 1992-09-28 | |
US952112 | 1992-09-28 | ||
PCT/US1993/008852 WO1994008276A1 (fr) | 1992-09-28 | 1993-09-23 | Procede d'elimination d'agents photoresistants employant du m,m-dimethyle-bis(2-hydroxyethyle) hydroxyde d'ammonium quaternaire |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0662223A1 true EP0662223A1 (fr) | 1995-07-12 |
Family
ID=25492598
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93921680A Ceased EP0662223A1 (fr) | 1992-09-28 | 1993-09-23 | Procede d'elimination d'agents photoresistants employant du m,m-dimethyle-bis(2-hydroxyethyle) hydroxyde d'ammonium quaternaire |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0662223A1 (fr) |
JP (1) | JPH08502367A (fr) |
AU (1) | AU4929993A (fr) |
WO (1) | WO1994008276A1 (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5472830A (en) * | 1994-04-18 | 1995-12-05 | Ocg Microelectronic Materials, Inc. | Non-corrosion photoresist stripping composition |
US5780406A (en) * | 1996-09-06 | 1998-07-14 | Honda; Kenji | Non-corrosive cleaning composition for removing plasma etching residues |
US6413923B2 (en) | 1999-11-15 | 2002-07-02 | Arch Specialty Chemicals, Inc. | Non-corrosive cleaning composition for removing plasma etching residues |
US6492308B1 (en) * | 1999-11-16 | 2002-12-10 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
JP2002241795A (ja) * | 2001-02-21 | 2002-08-28 | Tosoh Corp | 洗浄剤 |
US7923423B2 (en) | 2005-01-27 | 2011-04-12 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
SG158920A1 (en) | 2005-01-27 | 2010-02-26 | Advanced Tech Materials | Compositions for processing of semiconductor substrates |
US8685909B2 (en) | 2006-09-21 | 2014-04-01 | Advanced Technology Materials, Inc. | Antioxidants for post-CMP cleaning formulations |
US9074170B2 (en) | 2008-10-21 | 2015-07-07 | Advanced Technology Materials, Inc. | Copper cleaning and protection formulations |
JP2013011816A (ja) * | 2011-06-30 | 2013-01-17 | Tosoh Corp | レジスト剥離剤及びそれを用いた剥離方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA925252A (en) * | 1969-11-20 | 1973-05-01 | Paunovic Milan | Dual and multiple complexers for electroless plating baths |
CA1001581A (en) * | 1971-11-10 | 1976-12-14 | Canada Wire And Cable Limited | Plating copper on aluminum |
JPS52100234A (en) * | 1976-02-19 | 1977-08-23 | Sony Corp | Stripping solution of photosolubilizable light sensitive resin |
SU706815A1 (ru) * | 1978-04-17 | 1979-12-30 | Белорусский ордена Трудового Красного Знамени государственный университет им. В.И.Ленина | Медный физический про витель |
US4294911A (en) * | 1979-06-18 | 1981-10-13 | Eastman Kodak Company | Development of light-sensitive quinone diazide compositions using sulfite stabilizer |
JPS57176040A (en) * | 1981-04-22 | 1982-10-29 | Toshiba Corp | Preparation of photomask |
SU1203127A1 (ru) * | 1982-07-22 | 1986-01-07 | Уральский ордена Трудового Красного Знамени политехнический институт им.С.М.Кирова | Раствор дл очистки поверхности меди |
JPS6021526A (ja) * | 1983-07-18 | 1985-02-02 | Yotsukaichi Gosei Kk | 半導体表面処理方法 |
JPS60254043A (ja) * | 1984-05-30 | 1985-12-14 | Yotsukaichi Gosei Kk | ポジ型感光材料用現像剤 |
DE3638629A1 (de) * | 1986-11-11 | 1988-05-26 | Schering Ag | Mittel und verfahren zur entfernung von fotoresisten |
EP0367074A3 (fr) * | 1988-10-31 | 1991-06-12 | LeaRonal, Inc. | Préparation de circuits emprimés pour l'électroplacage |
DD293211A5 (de) * | 1990-03-01 | 1991-08-22 | Fotochem Werke Berlin Veb | Metallionenfreier entwickler zur hochkontrastentwicklung von positivfotoresists auf naphthochinondiazid/novolakbasis |
-
1993
- 1993-09-23 AU AU49299/93A patent/AU4929993A/en not_active Abandoned
- 1993-09-23 EP EP93921680A patent/EP0662223A1/fr not_active Ceased
- 1993-09-23 WO PCT/US1993/008852 patent/WO1994008276A1/fr not_active Application Discontinuation
- 1993-09-23 JP JP6509112A patent/JPH08502367A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9408276A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU4929993A (en) | 1994-04-26 |
JPH08502367A (ja) | 1996-03-12 |
WO1994008276A1 (fr) | 1994-04-14 |
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Legal Events
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STAA | Information on the status of an ep patent application or granted ep patent |
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18R | Application refused |
Effective date: 19961023 |