WO1999036151A1 - Method of purifying photoacid generators for use in photoresist compositions - Google Patents
Method of purifying photoacid generators for use in photoresist compositions Download PDFInfo
- Publication number
- WO1999036151A1 WO1999036151A1 PCT/US1999/000720 US9900720W WO9936151A1 WO 1999036151 A1 WO1999036151 A1 WO 1999036151A1 US 9900720 W US9900720 W US 9900720W WO 9936151 A1 WO9936151 A1 WO 9936151A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solution
- butylphenyl
- exchange resin
- amine
- tert
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/07—Processes using organic exchangers in the weakly basic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
Definitions
- the present invention relates to a process of removing trace levels of acidic impurities from a photoacid generator solution.
- the present invention is directed to a process of removing trace levels of acidic impurities from photoacid generator solutions by contacting the photoacid generating solution with an amine- containing ion exchange resin, as well as purified photoacid generator solutions made by the process.
- Photoresist compositions are used in microlithographic processes for making miniaturized electronic components such as in the fabrication of integrated circuits and printed wiring board circuitry.
- a thin coating or film of a photoresist composition is first applied to a substrate material, such as silicon wafers used for making integrated circuits or aluminum or copper plates of printed wiring boards.
- the coated substrate is then baked to evaporate any solvent in the photoresist composition and to fix the coating onto the substrate.
- the baked coated surface of the substrate is next subjected to an image-wise exposure of radiation. This radiation exposure causes a chemical transformation in the exposed areas of the coated surface. Visible light, ultraviolet (UV) light, electron beam, and X-ray radiant energy are radiation types commonly used today in microlithographic processes.
- the coated substrate is treated with a developer solution to dissolve and remove either the radiation-exposed or the unexposed area of the coated surface of the substrate.
- Two types of photoresist compositions are generally used-negative-working and positive-working.
- negative-working photoresist compositions When negative-working photoresist compositions are exposed image-wise to radiation, the areas of the resist composition exposed to the radiation become less soluble to a developer solution (e.g., a cross-linking reaction occurs) while the unexposed areas of the photoresist coating remain relatively soluble to a developing solution.
- a developer solution e.g., a cross-linking reaction occurs
- treatment of an exposed negative-working resist with a developer solution causes removal of the nonexposed areas of the resist coating and the creation of a negative image in the photoresist coating, and thereby uncovering a desired portion of the underlying substrate surface on which the photoresist composition was deposited.
- the now partially unprotected substrate may be treated with a substrate-etchant solution or plasma gases and the like.
- This etchant solution or plasma gases etch the portion of the substrate where the photoresist coating was removed during development.
- the areas of the substrate where the photoresist coating still remains are protected and thus, an etched pattern is created in the substrate material which corresponds to the photomask used for the image-wise exposure of the radiation.
- the remaining areas of the photoresist coating may be removed during a stripping operation, leaving a clean etched substrate surface.
- Positive-working photoresist compositions are currently favored over negative- working resists because the former generally have better resolution capabilities and pattern transfer characteristics.
- Chemically amplified photoresists are commonly employed today in advanced lithographic processes and generally contain a photoacid generator (also known as PAGs), a polymer and, optionally, a dissolution inhibitor. Either the polymer or the dissolution inhibitor or both have acid-labile groups attached thereof. In such systems, the photogenerated acid causes removal of acid-labile protecting groups on the polymer and/or dissolution inhibitor.
- the solubility of the deprotected areas in aqueous alkaline solutions is much greater than the areas having the protected polymer or dissolution inhibitor. This change in solubility upon exposure to incident radiation is the basis for positive working chemically amplified photoresists.
- U.S. Patent No. 5,500,127 issued to Carey et al. on March 19, 1996 and assigned to Rohm and Haas Co. discloses a method for removal of cationic and anionic contaminants from an organic solution of an acid catalyzed photoresist composition containing one or more acid labile components subject to reaction in the presence of a strong acid, the process comprising the steps of providing an organic solution containing one or more acid labile components, providing a weak acid cation exchange resin having a pK a such that the weak acid exchange groups on the resin do not react with acid labile components of the photoresist, providing a strong base anion exchange resin, and contacting the organic solution with the cation exchange resin and the anion exchange resin for a time sufficient to remove essentially all dissolved contaminants from solution without causing reaction between the acid labile components of the photoresist composition and the cation exchange resin.
- One aspect of the present invention is directed to a process of removing trace acidic impurities from an impure solution of photoacid generating compounds in a solvent, comprising: contacting an impure solution of at least one photoacid generating compound containing trace amounts of acidic impurities with an amine-containing ion exchange resin for a sufficient amount of time to remove substantially all of the acidic impurities from the impure solution, thereby producing a pure solution of at least one photoacid generating compounds substantially free of trace acidic impurities.
- the invention relates to a solution of at least one photoacid generating compound substantially free of trace acidic impurities made by the above process.
- photoacid generating compound refers to any photoacid generating compound conventionally used with photoresist compositions. Suitable photoacid generating compounds include onium salts, benzyl suifonate esters, disulfones, iminosulfonates, and the like. Specific examples of photoacid generating compounds include, but are not limited to, the following:
- R can be H or an alkyl group, such as methyl, ethyl, propyl, butyl, and the like, or an alkoxy group, such as methoxy, ethoxy, propoxy, butyoxy, and the like.
- R can be H or an alkyl group, such as methyl, ethyl propyl, butyl, and the like, or an alkoxy group, such as methoxy, ethoxy, propoxy, butyoxy, and the like;
- R' can be an alkyl group, such as methyl, ethyl propyl, butyl, and the like;
- R' can be an alkyl group, such as methyl, ethyl propyl, butyl, and the like;
- R can be H or an alkyl group, such as methyl, ethyl propyl, butyl, and the like, or an alkoxy group, such as methoxy, ethoxy, propoxy, butyoxy, and the like;
- E Benzylsulfonate ester compounds such as 2-nitro-6-
- the counterion (X " ) in any of the above-noted PAGs described above may be any acceptable counterion, for example SbF 6 " , PF 6 “ , AsF 6 “ , BF 4 “ , triflate (CF 3 SO 3 " ), alkyl suifonate, substituted or unsubstituted benzenesulfonate, dodecylbenzenesulfonate, camphorsulfonate, cyclohexylsulfonate, nitro-benzenesulfonate, and the like.
- PAGs useful according to the method of the invention include triphenylsulfonium triflate, triphenylsulfonium dodecylbenzenesulfonate, triphenyl-sulfonium-10-camphorsulfonate, triphenylsulfonium cyclo-hexylsulfonate, diphenyliodonium-4-methoxybenzenesulfonate, di(t-butylphenyl)iodonium-4- methoxybenzenesulfonate, bis(tert-butylphenyl)iodonium 10-camphorsulfonate, bis(tert-butylphenyl)iodonium cyclohexylsulfonate, bis(tert-butylphenyl)iodonium dodecylbenzenesulfonate, bis(tert-butylphenyl)iodonium methanesulfonate, bis
- trace acidic impurities refers to any acidic compound found in a solution of photoacid generating compounds in an undesirable amount, preferably greater than 15 parts per million (ppm).
- impure solution refers to photoacid generator solutions containing undesirable amounts of trace acidic impurities, preferably at levels greater than about 15 ppm.
- substantially free of trace acidic impurities refers to photoacid generating solutions that contain acceptable amounts of trace acidic impurities, preferably less than 15 ppm.
- pure solution refers to photoacid generator solutions that contain acceptable amounts of trace acidic impurities, preferably less than 15 ppm.
- an impure solution of at least one photoacid generating compound in a solvent is contacted with an amine- containing ion exchange resin to remove trace acidic impurities.
- this impure solution is prepared by dissolving one or more photoacid generating compounds in a suitable solvent or solvent mixture; however, other methods of making the impure solution are known in the art.
- Solvents useful for dissolution of the photoacid generating compounds include any solvent used conventionally in the preparation of photoresist component solutions.
- solvents examples include ethyl lactate, ethyl-3-ethoxypropionate (EEP), propylene glycol monomethyl ether acetate (PGMEA), methyl-3-methoxypropionate (MMP), 2-heptanone, diacetone alcohol, ethylene glycol monoethyl ether acetate, acetone, methanol, butanol, isopropanol, methylene chloride, chloroform, 2-butanone, and ethyl acetate, and the like. It will be appreciated by those skilled in the art that these solvents may be used in the present invention either alone or in any combination.
- the solid PAG content of the resulting impure photoacid generator solution is not critical.
- the amount of solid PAG may be from about 0.1% to about 25%, or higher, by weight; more preferably from about 1 % to about 10% by weight; based on the total photoacid generator solution weight.
- the sources of trace acidic impurities in solutions of photoacid generating compounds are thought to be the result of (1) unreacted acids that are not removed after synthesis of the photoacid generating compound; (2) decomposition of the photoacid generating compound over time or upon exposure to light or heat; and (3) acidic impurities present in the solvents of the photoacid generating solution.
- the trace acidic impurities that are present in the photoacid genenerating solution may be from any source.
- acidic impurities present in the photoacid generating solution depends on the source of the impurities.
- acidic impurities resulting from decomposition of the photoacid generating compound or synthesis of the photoacid generating compound are the corresponding acid (e.g., sulfonic acid).
- acidic impurities present in the solvents may be any acid soluble in the solvent (e.g. HCI, H 2 SO , lactic acid, acetic acid or substituted propionic acid and the like).
- trace acidic impurities in the PAG solution at levels greater than about 15 ppm adversely affect the performance and shelf-life of the photoresist solution.
- the impure photoacid generator solution may be made in any conventional method of mixing a solid photoacid generator with a solvent. Generally, it is preferred that the solid photoacid generating compound is added to a sufficient amount of solvent so that the solid photoacid generating compound is dissolved in the solvent. This step may be facilitated by agitation or other conventional mixing means.
- the impure photoacid generator solution is contacted with an amine-containing ion exchange resin to remove the trace acidic impurities present in the impure PAG solution.
- amine-containing ion exchange resin refers to anionic resins that contain an amine group.
- the amine-containing ion exchange resin is a highly porous structure based on polystyrene crosslinked with divinylbenzene and contains pendant polyamine functional groups.
- Particularly suitable amine-containing ion exchange resins include polyvinyl-pyridine, DIANION CR-20 (diethenyl benzene polymer with N-(2-aminethyl)-N-[(ethenyl-phenyl)methyl]-1 ,2-ethanediamine) (a particulate chelate resin with a cross-linked styrene-divinyl benzene copolymer bead having polyamine functional chelating groups and an average 1.2 micron particle diameter) available from Mitsubishi Kasei of Tokyo, Japan; and other macroreticular, weakly basic anion exchange resins such as AMBERLYST A-21 (styrene sulfonic acid-divinyl benzene cation exchange resin) available from Rohm and Haas.
- AMBERLYST A-21 styrene sulfonic acid-divinyl benzene cation exchange resin
- the photoacid generating solution may be contacted with the amine- containing ion exchange resin by any method known in the art, such as a column, or more preferably, batch techniques.
- a sufficient amount of amine- containing ion exchange resin is contacted with the PAG solution so that the PAG solution is substantially free of trace acidic impurities when the contacting step is complete.
- the amount of amine-containing ion exchange resin will range from about 0.5 wt% to about 50 wt%, more preferably about 1 wt% to about 25 wt%, and most preferably 1 wt% to about 10 wt%, all based on the total amount of solids in the PAG solution.
- the contacting treatment is usually conducted at room temperature with agitation.
- the impure photoacid generator solution is preferably contacted with the amine-containing ion exchange resin for a sufficient amount of time so that the acid photoacid generating solution is substantially free of trace acidic impurities.
- the preferred contacting time for contacting the impure photoacid generator solution with the amine-containing ion exchange resin by a batch mixing or rolling technique is from about 1 hour to about 24 hours, more preferably from about 2 hours to about 22 hours, and most preferably from about 4 hours to about 20 hours.
- the amine-containing ion exchange resin is next removed from the photoacid generating solution. Removal of the amine-containing ion exchange resin from the photoacid generating solution may be performed by any conventional procedure known in the chemical arts. Preferably, the amine- containing ion exchange resin is removed from the photoacid generating solution by gravity filtration, vacuum filtration, decantation, and centrifugation and the like. Through the utilization of the present process, trace acidic impurities in the photoacid generator solution are reduced to below 15 ppm, preferably below 10 ppm. Accordingly, pure resist component solutions such as PAG solutions can be prepared by the present process, which have an amount of acidic impurities under about 15 ppm.
- the PAG solutions have an amount of acidic impurities under about 10 ppm.
- the present invention is further described in detail by means of the following examples. However, this invention is not intended to be limited by these examples. All parts and percentages are shown by weight percent, and all temperatures are in degrees Celsius, unless explicitly stated otherwise.
- the dry crystals of crude Neutral Red were placed in another 500-mL amber bottle and 400 mL more of absolute ethanol were added.
- the bottle was rolled for at least 2 hours, 40 mL of 1.ON NaOH was added and the bottle was allowed to roll again for at least one hour.
- the slurry was filtered, and the liquid was added to 4.0 L of heavily agitated deionized water.
- the bright red/orange precipitate that formed was collected by filtration and dried in vacuum at 40°C until no weight change was observed (at least overnight).
- Purified Neutral Red Crystals as prepared above (6.25 mg.) were weighted into a 250 ml volumetric flask. Sufficient tetrahydrofuran (THF) to fill to the volumetric mark was added. The flask was then shaken to dissolve. The resulting solution was yellow in color, indicating no acid contamination.
- THF tetrahydrofuran
- Example 1 Treatment of Nitrobenzyl Suifonate.
- PGMEA propylene glycol monomethyl ether acetate
- DIANIONTM CR-20 diethenyl benzene polymer with N-(2-aminethyl)-N-[(ethenyl-phenyl)methyl]-1 ,2- ethanediamine
- This mixture was rolled at about 38 rpm for 19 hours. Following rolling, the solid ion exchange resin was removed from the solution by pressure filtration. The filtrate was evaluated for the presence of residual acidic compounds by the above-noted Neutral Red test, which gave a negative result, indicating less than 10 ppm acidic compounds in the filtrate solution.
- Example 2 Treatment of Bis(4-tert-butylphenyl)iodonium-4-methoxybenzenesulfonate.
- Example 3 Treatment of Triphenylsulfonium Dodecylbenzenesulfonate.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99902220A EP1054715A1 (en) | 1998-01-13 | 1999-01-13 | Method of purifying photoacid generators for use in photoresist compositions |
JP2000539913A JP2002509015A (en) | 1998-01-13 | 1999-01-13 | Method for purifying a photoacid generator for use in a photoresist composition |
KR1020007007647A KR20010034040A (en) | 1998-01-13 | 1999-01-13 | Method of purifying photoacid generators for use in photoresist compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/006,409 US6200480B1 (en) | 1998-01-13 | 1998-01-13 | Method of purifying photoacid generators for use in photoresist compositions |
US09/006,409 | 1998-01-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999036151A1 true WO1999036151A1 (en) | 1999-07-22 |
Family
ID=21720724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/000720 WO1999036151A1 (en) | 1998-01-13 | 1999-01-13 | Method of purifying photoacid generators for use in photoresist compositions |
Country Status (5)
Country | Link |
---|---|
US (1) | US6200480B1 (en) |
EP (1) | EP1054715A1 (en) |
JP (1) | JP2002509015A (en) |
KR (1) | KR20010034040A (en) |
WO (1) | WO1999036151A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5212046A (en) * | 1989-10-17 | 1993-05-18 | Shipley Company Inc. | Near UV photoresist |
US5350714A (en) * | 1993-11-08 | 1994-09-27 | Shipley Company Inc. | Point-of-use purification |
US5518628A (en) * | 1993-11-08 | 1996-05-21 | Shipley Company Inc. | Purification process |
US5702611A (en) * | 1997-01-14 | 1997-12-30 | Shipley Company, L.L.C. | Process for removing heavy metal ions by ion exchange |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4335000A (en) * | 1977-09-13 | 1982-06-15 | Pennwalt Corporation | Chromate ion removal from aqueous solutions |
US5446125A (en) * | 1991-04-01 | 1995-08-29 | Ocg Microelectronic Materials, Inc. | Method for removing metal impurities from resist components |
US5472616A (en) | 1993-10-27 | 1995-12-05 | Shipley Company, Inc. | Modified anion exchange process |
US5525315A (en) | 1993-12-07 | 1996-06-11 | Shipley Company, L.L.C. | Process for removing heavy metal ions with a chelating cation exchange resin |
US5500127A (en) | 1994-03-14 | 1996-03-19 | Rohm And Haas Company | Purification process |
-
1998
- 1998-01-13 US US09/006,409 patent/US6200480B1/en not_active Expired - Fee Related
-
1999
- 1999-01-13 KR KR1020007007647A patent/KR20010034040A/en not_active Application Discontinuation
- 1999-01-13 EP EP99902220A patent/EP1054715A1/en not_active Withdrawn
- 1999-01-13 JP JP2000539913A patent/JP2002509015A/en active Pending
- 1999-01-13 WO PCT/US1999/000720 patent/WO1999036151A1/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5212046A (en) * | 1989-10-17 | 1993-05-18 | Shipley Company Inc. | Near UV photoresist |
US5350714A (en) * | 1993-11-08 | 1994-09-27 | Shipley Company Inc. | Point-of-use purification |
US5518628A (en) * | 1993-11-08 | 1996-05-21 | Shipley Company Inc. | Purification process |
US5702611A (en) * | 1997-01-14 | 1997-12-30 | Shipley Company, L.L.C. | Process for removing heavy metal ions by ion exchange |
Also Published As
Publication number | Publication date |
---|---|
JP2002509015A (en) | 2002-03-26 |
EP1054715A1 (en) | 2000-11-29 |
US6200480B1 (en) | 2001-03-13 |
KR20010034040A (en) | 2001-04-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5521052A (en) | Metal ion reduction in novolak resin using an ion exchange catalyst in a polar solvent and photoresists compositions therefrom | |
KR100280757B1 (en) | Method for producing a developer with a low metal ion content | |
WO1994014858A1 (en) | Metal ion reduction in polyhydroxystyrene and photoresists | |
EP0863925B1 (en) | Metal ion reduction in photoresist compositions by chelating ion exchange resin | |
US5656413A (en) | Low metal ion containing 4,4'-[1-[4-[1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphe nol and photoresist compositions therefrom | |
EP0805828B1 (en) | Metal ion reduction in novolak resins solution in pgmea by chelating ion exchange resin | |
EP0754975B1 (en) | Process of reducing trace levels of metal impurities from resist components | |
EP0948756B1 (en) | A method for reducing metal ion contaminants in photoresist compositions containing an organic polar solvent by ion exchange | |
JP3924317B2 (en) | Metal ion reduction in novolak resin solution using anion exchange resin | |
KR19990045753A (en) | Fractional distillation of phenol formaldehyde condensates and photoresist compositions prepared therefrom | |
KR100412531B1 (en) | A method for fractionating phenol formaldehyde condensates and a photoresist composition prepared therefrom | |
US6200480B1 (en) | Method of purifying photoacid generators for use in photoresist compositions | |
EP0874284B1 (en) | Developer for a positive electron beam resist composition | |
KR100551936B1 (en) | Process for producing a photoresist composition having a reduced tendency to produce particles | |
KR910007227B1 (en) | Developer solution for positive-warking resist composition | |
JPH0446947B2 (en) | ||
JPH0317653A (en) | Photosensitive composition | |
JP2002501933A (en) | Method for producing photoactive compound and method for producing photoresist therefrom |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): JP KR |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1999902220 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020007007647 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2000 539913 Kind code of ref document: A Format of ref document f/p: F |
|
WWP | Wipo information: published in national office |
Ref document number: 1999902220 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020007007647 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1999902220 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1020007007647 Country of ref document: KR |