EP1129390A1 - Composition d'appret permettant de coller des photoresines sur des substrats - Google Patents

Composition d'appret permettant de coller des photoresines sur des substrats

Info

Publication number
EP1129390A1
EP1129390A1 EP98957486A EP98957486A EP1129390A1 EP 1129390 A1 EP1129390 A1 EP 1129390A1 EP 98957486 A EP98957486 A EP 98957486A EP 98957486 A EP98957486 A EP 98957486A EP 1129390 A1 EP1129390 A1 EP 1129390A1
Authority
EP
European Patent Office
Prior art keywords
photoresist
substrate
priming
priming composition
polyelectrolyte
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Withdrawn
Application number
EP98957486A
Other languages
German (de)
English (en)
Inventor
Andrew Michael Thompson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP1129390A1 publication Critical patent/EP1129390A1/fr
Withdrawn legal-status Critical Current

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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Definitions

  • This invention relates to priming compositions for use in cleaning substrates and promoting adhesion between photoresists and various metallic and non-metallic substrates. This invention further relates to articles manufactured with the priming compositions, and to methods of treating substrates and bonding photoresists to the treated substrates.
  • the coating of substrates with positive-type photoresist (photochemical degradation) or negative-type photoresist (photochemical crosslinking) for the purpose of recording positive or negative information through photolithography is known.
  • This technique is practiced in the manufacture of, for example, semiconductors, optical media (e.g., compact discs), holography, and other related microelectronic components. It is also known in this industry to use primers to treat the substrates in an effort to improve adhesion between a subsequently applied layer of photoresist and the substrate.
  • Improvement in adhesion is performed with the intention of providing advantageous properties, such as prevention of delamination and undercutting, as well as the significant reduction, if not elimination, of adhesion failure caused by the generation of nitrogen gas during exposure of the photoresist (a phenomena generally known as popping).
  • primers desirably reduce jitter and improved block error rate.
  • HMDS hexamethyldisilane
  • Other common priming agents include, but are not limited to, titanates, SnCl 2 , and various silane (Si n H n+2 ) compounds.
  • HMDS is believed to form a bridge bond, or crosslinking, between the photoresist and the substrate, thereby improving adhesion.
  • HMDS has several drawbacks that deprecate this advantage. For example, HMDS is insufficiently tolerant to water so that the presence of moisture between the substrate and HMDS may result in adhesion failure. As a consequence, additional processing steps, such as baking, often require complete drying of the substrates prior to the application of HMDS.
  • silanes require the presence of reactive hydroxyl groups on the surface of the substrate to form covalent bonds. Silanes are therefore ineffective at priming many substrates, especially metal substrates on which hydroxyl groups are not available for bonding. Yet another drawback of silanes and titanates is that they tend to be hazardous materials, posing health and safety hazards and increasing costs associated with their use.
  • Sensitizing agents such as stannous chloride
  • substrates for example, glass
  • any physical modification to the substrate is considered undesirable in almost all microlithography applications.
  • an object of this invention to achieve the above- discussed advancement in the art by the provision of an improved primer composition that is non-hazardous, yet sufficiently versatile to bond metallic and non-metallic substrates to a positive or negative photoresist.
  • a priming composition which may be coated on a substrate and is capable of creating covalent bonds with both the substrate and a subsequently applied photoresist to thereby link the substrate to the photoresist.
  • the priming composition comprises at least one water-soluble polymer having a plurality of substituents derived from cyclic ethers.
  • the backbone of the polymer may be formed, by way of example and without limitation, from tertiary amines or quaternary ammonium compounds.
  • the backbone may be derived from one or more compounds containing cyclic nitrogen- containing rings, such as aziridines and imidazoles.
  • the cyclic ethers are grafted onto nitrogen atoms of the backbone.
  • the cyclic ether is preferably an epoxide, such as ethylene oxide and/or epichlorohydrin.
  • Representative polymers include hydroxyethylated polyethylene imine and polyethylene imine epichlorohydrin.
  • the polyelectrolyte is water soluble, it allows for greater versatility with respect to ingredients that may be included in the priming composition.
  • the priming composition optionally may include one or more of the following, in any combination: at least one alcohol capable of increasing the stability and wetting properties of the priming composition; at least one member selected from the group consisting of alcohol ethers and ether acetates; at least one non-ionic surfactant; and/or at least one detergency enhancing agent.
  • the pH of the priming composition may be modified to provide optimum performance through the addition of an organic acid. For example, for polyethylene imine - epichlorohydrin, the pH is preferably between about 3.5 and about 7.
  • Some materials may be incompatible with certain embodiments of this invention and generally should be avoided. These materials include the following: mercaptans; strong oxidizing or reducing agents (although such agents may be added in diluted form); dextran sulfates and other sulfates or phosphate compounds that may be bound to any free amines. With regard to phosphate and sulfate compounds, these compounds may provide some benefit when added in a polyprotic acid form so as to act as counter ions to the polyelectrolyte.
  • Other incompatible materials include ionic constituents, such as anionic wetting agents which may reactive with the ether rings and interfere with the charge density site on which the cyclic ether is grafted.
  • Another object of the invention is to provide microelectronic components having improved physical and performance properties comprising a photoresist bonded to a substrate with the inventive priming composition.
  • microelectronic components comprising: a substrate, such as silicon, glass, indium tin oxide, gallium arsenate, nickel, and the like; an effective amount of a film of the priming composition of the invention carried on and bonded to at least one surface of the substrate; and a layer of a negative or positive photoresist bonded to the substrate by the priming composition described above.
  • a further object is to provide an economical method of applying the embodiments of the inventive priming composition to a substrate prior to coating with a photoresist in a more flexible and efficient manner than presently known.
  • a method of cleaning or cleansing at least one surface of a substrate and bonding of a photoresist layer subsequently applied to the cleaned surface generally comprises: washing at least one surface of a substrate (e.g., silicon, glass, indium tin oxide, nickel, and gallium arsenate) with an effective amount of the priming composition of the invention sufficient to bind the polyelectrolyte to the substrate via covalent bonds; optionally rinsing the washed surface with an aqueous solution sufficient to remove contaminants and leave a thin film of priming composition on the cleaned surface; applying a layer of photoresist to the cleaned surface; and curing the layer of photoresist under conditions which cause the film of priming composition to form covalent bonds with the photoresist and thereby link the substrate to the photoresist. Still a further object is to provide an economical method of applying the inventive priming composition to the substrate at the same time the photoresist is
  • these and other objects are achieved by premixing the inventive priming composition with a photoresist precursor composition to form a pre-primed photoresist composition.
  • the priming composition by pre- dissolved in a solvent compatible with the photoresist. This variation allows for the elimination of separate priming and photoresist coating steps.
  • the priming composition comprises at least one water-soluble polyelectrolyte having a plurality of substituents derived from cyclic ethers.
  • the priming composition may optionally include one or more of the following, in any combination: at least one alcohol capable of increasing the stability and wetting properties of the priming composition; at least one member selected from the group consisting of alcohol ethers and ether acetates; at least one non-ionic surfactant; and at least one detergency enhancing agent.
  • the backbone of the polyelectrolyte may be any polymer, including a homopolymer, copolymer, or terpolymer, which provides sites onto which a cyclic ether compound may be grafted so as to be reactive with the substrate or photoresist.
  • the backbone may be comprised of tertiary amine moieties.
  • ethylene imine which may be formed from aziridine monomers.
  • Other cyclic nitrogen containing monomers may be used in addition to or as an alternative for the aziridine monomers to prepare the backbone of the polyelectrolyte include pyrrolidine and imidazoles.
  • the polyethylene imine backbone may be reacted or cross-linked with various substances.
  • the polyethylene imine backbone may be cross-linked with 1 ,2-dibromoethane, l,8-dichloro-3,6-dioxaoctane and 1 ,4-dichlorobutane to provide varying degrees of adhesive retention of photoresist to the substrate.
  • Cationic polyamines that exhibit photoresist priming functions may be created through modifying the polyamine with carboxymethylated, N-methylated, and N-phosphonomethylated derivatives.
  • the backbone may also contain quaternary ammonium moieties.
  • Such backbones include, for example, polyamine homopolymers generally known as polyDADMAC's, such as polydimethyldiallylammonium chloride. These quaternary ammonium polymers are widely available commercially as flocculating and compelling agents used in waste water treatment. Two examples of quaternary ammonium products are PURIFLOC sold by Dow Chemical of Midland, MI and CAT-FLOC sold by Calgon of Pittsburgh, PA. Other specialized quaternary ammonium compounds are also available from Polyscience, Inc.
  • the polyelectrolyte may have a relatively high average molecular weight, although this is not essential. It is believed that the adhesion characteristic of the polyelectrolyte increases as the distance between the tertiary or quaternary nitrogen is reduced. This may be significant where the polymer catalyzation is the result of reacting aziridine monomers with various fatty acids such as, but not limited to, lauric, oleic, and stearic acids.
  • cyclic ethers mean compounds having at least one non- aromatic ring with at least one oxygen atoms contained in the non-aromatic ring.
  • Preferred cyclic ethers are epoxides.
  • Representative epoxides include, without limitation, alkylene oxides, such as ethylene oxide and propylene oxide; halide-containing compounds such as epichlorohydrin and trichlorobutylene (TCBO); and glycidyl compounds such as glycidol.
  • Cyclic ethers other than epoxides such as tetrahydrofuran (THF), as well as cyclic ethers having rings containing two or more oxygen atoms, such as 1,4-dioxane, may also be used.
  • cyclic ether also encompasses oxygen-containing ether rings having one or more heteroatoms, such as nitrogen atoms.
  • tertiary amine polyelectrolytes include hydroxyalkyl- substituted polyamines, such as hydroxyl ethylated polyethylene imine (“HEPEI”), which is polyethylene imine grafted with ethylene oxide and having the following general structure: R
  • HEPEI hydroxyl ethylated polyethylene imine
  • R may be a continuation of the polymer, a hydrogen atom (H), or a substituent derived from ethylene oxide.
  • HEPEI is preferred where the priming composition is used on a silicone substrate.
  • the backbone of the HEPEI may be prepared from aziridine monomers; the grafted substituents may be prepared from epoxide monomers.
  • HEPEI is readily available commercially from several manufacturers, including Polysciences, Inc. of Warrington, Pa.
  • the polymer is generally available with an average molecular weight of 5000 to 100,000. While the present invention is not intended to be limited by such theory, it is not believed that the number of repeating units has a direct impact on the ability of the polyelectrolyte to promote adhesion to photoresist.
  • PEIECH polyethylene imine-epichlorohydrin
  • HEPEI is mixed, such as by conventional blending, with PEIECH for purposes of promoting adhesion over a broad range of substrates. While both HEPEI and PEIECH promote adhesion of photoresist to glass, HEPEI is preferred for this substrate as the chloride counter ion utilized by PEIECH has been found to cause rare instances of corrosion of the stainless steel processing equipment. Additionally, HEPEI has been found to be easier to filter to the submicron level with minimal filter loading.
  • Both HEPEI and PEIECH are very effective in small concentrations, making them very economical as well as minimizing the introduction of any associated contaminants into the sensitive microlithography process.
  • the preferred embodiment of the HEPEI variation of the primer contains 0.5 - 1.0 % by volume of the active polymer, while the variation using PEIECH is used from 0.5 - 5.0 % by volume.
  • Mixed polymer matrices may use a volume ratio of HEPEI to PEIECH ranging from about 1:1 to about 1:5, and a volume ratio of polyelectrolyte to water of about 1:10. Increasing the amount of HEPEI above 1.0% by volume in a single polymer embodiment or above a 1:1 volume ratio in a mixed polymer variation has been found not to increase the adhesive value of the primer.
  • alcohol includes one or more mono-hydroxyl alcohols, polyalcohols, polymeric alcohols or other alcohol equivalents that function to charge-stabilize the priming composition.
  • the priming composition preferably comprises a polyhydroxy alcohol (or polyol), more preferably dihydroxy alcohols commonly known as glycols.
  • suitable glycols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, and hexamethylene glycol and mixtures thereof.
  • Suitable polyalcohols that can be used include polyvinyl alcohol (PVA) or derivatives thereof.
  • Lower molecular weight glycols such as ethylene glycol and propylene glycol, are preferred because they provide reactive functional groups that provide charge-stabilizing characteristics, which increases the hydrophilicity of the substrate. While this component is not essential to the immediate function of the polyelectrolyte in promoting adhesion, it is highly desirable for promoting long-term stability of the polymer in an aqueous solution.
  • propylene glycol In situations in which propylene glycol is used as the primary solvent for thinning the photoresist, it is preferred that propylene glycol also be used as the primary charge stabilizing alcohol, since propylene glycol will exhibit improved compatibility between the hydrophilic alcohol and the often hydrophobic photoresist resins, such as cresol formaldehyde and novolak (phenol-formaldehyde). In addition, propylene glycol poses lower health and safety hazards than other acceptable alcohols. The use of propylene glycol was found most effective when the invention was made up at an initial concentration by volume of 1 : 1 polyelectrolyte to alcohol. Using this ratio, the polyelectrolyte, in this case HEPEI, was easily dissolved.
  • the concentrate could then be diluted with water without the occurrence of precipitation of the polymer. Where other components are to be added to the polyelectrolyte, they will be most successfully incorporated after dilution. While making up a priming composition containing 5 vol% HEPEI and 5 vol% propylene glycol incurred precipitation or clouding of the solution, a concentrated solution containing 50 vol% HEPEI and 50 vol% propylene glycol by volume could be diluted to 10 vol% (containing 5 vol% HEPEI and 5 vol% propylene glycol) in water with no loss of stability. The balance of these concentrations may be optimized solely for maintaining solubility of the polyelectrolyte in an aqueous solution, and does not affect the immediate functionality of the adhesion promoter itself.
  • alcohol ethers include one or more alcohol ethers, especially an alkyl ether of a hydroxy alcohol, such as ethylene glycol and alcohol derivatives of glycol monomethyl ether acetate.
  • alkyl ethers known as carbitols.
  • propylene glycol derivatives especially propylene glycol monomethyl ether or its ether acetate are preferred.
  • the propylene glycol derivatives are generally preferred over the ethylene glycol derivatives as they do not demonstrate the adverse health and reproductive effects of ethylene glycol ethers.
  • propylene glycol monomethyl ether is also preferred as it is commonly used as a solvent in photoresist.
  • Diethylene glycol monomethyl ether has also been shown to provide excellent charge stabilizing characteristics for both HEPEI and PEIECH based and mixed photoresist adhesion promoters.
  • monoalkyl ethers of monoethylene glycol as illustrated by monomethyl ether of ethylene glycol, monoethyl ether of ethylene glycol and n-butyl ether of ethylene glycol and mixtures thereof as well as mixtures thereof with the alkyl ethers of diethylene glycol.
  • PEGs Polyethylene glycols (PEGs) of the formula HOCH 2 CH 2 (OCH 2 CH 2 ) n OH where n ranges from 200-50,000 can also be used.
  • crown ethers including ethyl, n-butyl ethers, or other compounds may be used where the compound has similar solvating characteristics suitable for satisfying the dielectric constant, pKa of the removable protons, etc. of the polyelectrolyte.
  • the charge stabilizing characteristics may be satisfied through the addition of a suitable counter- ion, such as chloride. Counter-ions may be added in the form of a salt or other compound in which the anion is readily dispersed in water to stabilize the charge of the cationic amine.
  • the presence of an ether does not adversely affect the adhesion capabilities of the primer, the charge stabilizing characteristics they provide significantly enhance the solubility of polyamine, preventing precipitation or flocculation which may be commercially undesirable.
  • a wetting agent or compound capable of acting as a wetting agent is not essential to the function of the bonding properties of the polyelectrolyte, it may be desirable to add such a surface agent where the primer is used on extremely hydrophobic substrates, or where the adhesion promoter is designed to work as both a cleaning agent and a primer.
  • the wetting agent used is a nonionic surfactant that will not cross-link or otherwise interfere with the surface charge of the polyelectrolyte.
  • Higher molecular weight polymeric surfactants may be more efficient at providing film coverage and substrate absorption than lower molecular weight monomeric wetters.
  • a mixture of alkylaryl polyether and octylphenoxypolyethoxy ethanol, sold under the trade name TRITON CF-10, provides excellent wetting of hydrophobic surfaces, yet is very low foaming thus allowing a broader range of application methods, including ultrasonic agitation or washing.
  • polyethylene glycol mono [4-(l,l,3,3- tetramethylbutyl)phenyl] ether is preferred.
  • the latter is available under the trade name TRITON X-100. Both TRITON CF-10 and TRITON X-100 can be effective at relatively low concentrations of 1% by volume or less.
  • polymeric wetting agents such as polyethylene glycol (PEG), polyvinyl alcohol (PVA) polyvinylpyrrolidone (PVP), hydroxypropylcellulose (HPC) or any other polymer or copolymer with reactive hydroxyl sites.
  • PEG polyethylene glycol
  • PVA polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • HPC hydroxypropylcellulose
  • any component capable of enhancing the hydrophilicity of the substrate may be suitable.
  • Detergency enhancing agents may be added to enhance the cleaning action of the primer.
  • the addition of this agent facilitates the elimination of separate wet chemical cleaning and priming stages.
  • Salt additives such as sodium sulfate, sodium chloride, ammonium chloride, and/or ammonium bifluoride may be used. It should be noted that such additives may also serve the function of charge stabilizing the polyelectrolyte in solution.
  • organic acids or bases it is possible, but not essential, to add organic acids or bases in order to obtain a pH level optimum for the performance of the polyelectrolyte.
  • acetic acid is added after dilution of the polyelectrolyte matrix to achieve an optimum pH of 4.0-7.0.
  • certain organic acids, such as citric acid are avoided where the known substrate material is a metal normally chelated by the acid. Any strong oxidizer would also be avoided due to its degrading effect on the active polyelectrolyte.
  • the substrate can be precleaned before application of the present priming composition, if desired, but it is not necessary. Suitable precleaning techniques and agents are known to those skilled in the art, and include ion and plasma etching of the substrate and washing of the substrate with chlorinated and non-chlorinated organic solvents.
  • the priming composition of the invention whether used as a concentrate or in diluted form can be applied to a stationary or moving substrate to be coated with a photoresist in any known manner, for example, by spraying, brushing, immersing, or other known means.
  • the priming composition can be applied to a substrate by spin coating.
  • the priming composition is applied by spraying, for example, to a rotating substrate, optionally followed by rinsing the rotating substrate with water or other suitable diluent to remove contaminants and excess priming composition from the surface of the substrate.
  • the substrate is dried by spinning the substrate and then a coat of photoresist is applied to a priming composition-coated side of the substrate.
  • the priming composition can also be applied to a substrate by brush cleaning. According to this procedure, a side of a rotating or stationary substrate is cleaned by brushing and scrubbing the substrate in the presence of the inventive priming composition, followed by rinsing the brushed and scrubbed substrate with water or other diluent, drying, and then applying a coating of photoresist to the brushed and scrubbed substrate.
  • the priming composition can also be applied to a substrate prior to coating the substrate with a photoresist by immersion in a vessel containing the priming composition.
  • the priming composition can be agitated by mechanical, ultrasonic or megasonic (degas) or other suitable means during immersion of the substrate into the priming composition.
  • the substrate is rinsed with water or other diluent, dried and then the dried substrate is coated with a layer of photoresist.
  • the temperature obtained during applying the priming composition to the substrate is usually ambient although higher or lower temperatures, e.g., 20-55°C, can be used.
  • the amount of priming composition applied to a substrate is sufficient to provide a thin layer of the priming composition on a side of a substrate to be coated with photoresist.
  • the priming composition may be dissolved into a charge-solvating solution which is compatible with the photoresist to create a self -priming photoresist.
  • the cyclic ether substituent of the polyelectrolyte bonds with the photoresist resin prior to application to the substrate.
  • Substrates that can be used according to the invention include silicon, glass, indium tin oxide (ITO), gallium arsenate (GaAs), nickel, or other suitable substrates that provide a base for positive and negative photoresists. Where metal substrates are used, it is believed that oxygen- metallic bonds formed between the substrate and the oxygen atoms of the cyclic ether ring.
  • a positive or negative photoresist can be applied to a substrate having a layer of the inventive priming composition in any manner known in the art and then subjected to photochemical treatment to cure and bond the photoresist to the substrate.
  • Photoresists used in optical media mastering generally comprise photo-active compounds combined in a resin media.
  • This resin media typically includes as constituents alkali-soluble terpene phenols reacted with an aldehyde and/or ketone in the presence of an acidic catalyst.
  • the aldehyde is typically formaldehyde, p-formaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenyl-acetaldehyde or furfural.
  • the ketone is usually acetone or cyclohexanone.
  • the final resist is applied to a substrate in a solvent media of ethylene glycol or propylene glycol, with propylene glycol monomethyl ether acetate preferred for its toxicological advantages.
  • the dominant photoresist in the compact disc industry is a product called Shipley 1800 series where the last two digits refer to the coating thickness in microns when applied by spin coating at 4000 rpm. Actual coating thickness appears to be irrelevant in relationship to the present invention as bonding is only required at the matrix interface in order to obtain the desire priming results.
  • the Shipley 1800 series resist is comprised of the photo-active compounds and a cresol formaldehyde resin in a propylene glycol solvent.
  • HMDS hexamethyldisilane
  • Silanes are deposited either by vapor deposition in which a substrate is placed in a chamber where the silane is vaporized, or through spin coat application where the silane is dispensed onto a rotating substrate until coated, then spun dry.
  • the instant priming composition is a complete cleaning and adhesion promoting composition for use with photoresists on various substrates.
  • the priming composition of the invention accomplishes the tasks of acting as an anti-static agent so that charged contaminants, such as dust particles, may be easily removed by rinsing and bond promoting through providing covalent bond sites for the adhesion of the substrate and subsequently applied photo-resist.
  • the invention priming composition provides a number of advantages and the first real alternative to HMDS, silanes, titanates, and organic salt adhesive promoters .
  • the present invention provides several advantages over the compositions now employed in the art. For example, because cleaning and adhesion are performed within a single step, processing time is faster and associated cost savings may be realized by the elimination of multi-step processes.
  • the inventive composition reduces delamination and under cutting in HF etch, and, in the case of priming optical storage media, reduces or eliminates micro-adhesion failures and associated jitter, block error rate, and replication release patterns. Additionally, the inventive priming composition substantially eliminates the use of hazardous volatile solvents, thereby making waste treatment much easier and inexpensive and extending shelf life. As noted above, the need for dehydration baking steps is largely reduced by the use of the inventive priming composition.
  • macro-adhesion describes the ability of the priming agent to reduce failure by environmental factors such as handling, temperature fluctuations, thermodynamics, compressive stress of the photoresist.
  • Micro-adhesion describes the ability of the priming agent to reduce delamination and undercutting of the photoresist at the matrix interface, as may occur during exposure to developing or etching solutions during processing.
  • compositions were evaluated for the ability of each to provide both macro- and micro-adhesion of cresol formaldehyde to glass substrates.
  • Macro-adhesion was evaluated through visual examination of glass slides which were primed, coated with photoresist and exposed to ultrasonic agitation.
  • a first sample of the inventive priming composition comprised 1 % by volume ethoxylated polyethylenimine (HEPEI), 7.5 mL/L propylene glycol monomethyl ether, and 2.5 mL/L propylene glycol.
  • the pH was modified to 7.0 using acetic acid, and was filtered to 0.2 microns. Glass slides were primed by immersion in the priming agent, followed immediately by spin drying at 500 rpm for three minutes.
  • a second sample of the inventive priming composition comprised 5% by volume epichlorohydrin cross linked with polyethylenimine (PEIECH), 7.5 mL/L propylene glycol monomethyl ether, and 2.5 mL/L propylene glycol.
  • PEIECH polyethylenimine
  • the pH was modified to 7.0 using acetic acid, and was filtered to 0.2 microns. Glass slides were primed by immersion in the priming agent, followed immediately by spin drying at 500 rpm for three minutes.
  • HMDS(V) A first comparative sample (HMDS(V)) was prepared by vapor deposition of glass slides in HMDS (hexamethyldisilane) under a seal hood for 30 minutes.
  • HMDS(S) hexamethyldisilane
  • Control As a control sample, a glass slide was treated with deionized water, then filtered to 0.2 microns. Process Parameters:
  • Test groups were evaluated at five minute intervals for presence of photoresist after exposure to ultrasonic agitation, using DI water maintained at 50°C. This temperature was selected as this is the typical operating temperature of a sulfamate nickel electroforming bath which would be used for creating nickel compact disc master from recorded photoresist. Slides were tested one at a time with placement in identical positions to reduce variability of ultrasonic field exposure. 6. To reduce variability, batch processing was used in all spin dry and baking operations. Evaluation of Macro- Adhesion: Test slides were evaluated after each 5 minute interval of exposure to ultrasonic agitation. Presence of photoresist was evaluated by placing the slide against a template divided into 5 x 13 - 4 millimeter cells and observing under ultraviolet light.
  • the results are shown in graphical form in the FIGURE as percent failure by time interval for each test group.
  • the inventive primers showed a significant reduction in adhesion failure over both the control group and HMDS.

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

L'invention se rapporte à une composition concentrée d'apprêt qui peut être déposée sur un substrat et joue le rôle de composition favorisant l'adhésion en vue du collage d'une photorésine appliquée ultérieurement sur le substrat. La composition contient, en tant qu'ingrédient principal, un polyélectrolyte ayant des substituants dérivés d'éthers cycliques, de préférence de l'épichlorohydrine et/ou de l'oxyde d'éthylène. Cette composition d'apprêt peut être appliquée sur un substrat fixe ou mobile, sous forme de concentré ou sous forme diluée dans un milieu aqueux, par brossage, pulvérisation ou immersion et analogue.
EP98957486A 1998-11-12 1998-11-12 Composition d'appret permettant de coller des photoresines sur des substrats Withdrawn EP1129390A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/023243 WO2000029907A1 (fr) 1998-11-12 1998-11-12 Composition d'appret permettant de coller des photoresines sur des substrats

Publications (1)

Publication Number Publication Date
EP1129390A1 true EP1129390A1 (fr) 2001-09-05

Family

ID=22268211

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98957486A Withdrawn EP1129390A1 (fr) 1998-11-12 1998-11-12 Composition d'appret permettant de coller des photoresines sur des substrats

Country Status (5)

Country Link
EP (1) EP1129390A1 (fr)
JP (1) JP2002530697A (fr)
AU (1) AU1373399A (fr)
CA (1) CA2349578A1 (fr)
WO (1) WO2000029907A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8476099B2 (en) 2010-07-22 2013-07-02 International Business Machines Corporation Methods for improved adhesion of protective layers of imager microlens structures by forming an interfacial region
ES2617778T3 (es) * 2010-09-02 2017-06-19 Qiagen Gmbh Método para aislar un ácido nucleico diana que incluye ácidos nucleicos diana pequeños, con alto rendimiento

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060656A (en) * 1973-04-02 1977-11-29 Teijin Limited Support for photosensitive resin
JPS5837532B2 (ja) * 1973-04-02 1983-08-17 帝人株式会社 カンコウセイジユシヨウシジバン
JPS52106736A (en) * 1976-03-04 1977-09-07 Hitachi Ltd Copying paper for electronic photography
US4483913A (en) * 1983-07-18 1984-11-20 Polychrome Corporation Planographic printing plate
JPS60186835A (ja) * 1984-03-06 1985-09-24 Toyobo Co Ltd 感光性積層体
US4732858A (en) * 1986-09-17 1988-03-22 Brewer Science, Inc. Adhesion promoting product and process for treating an integrated circuit substrate
US4950583A (en) * 1986-09-17 1990-08-21 Brewer Science Inc. Adhesion promoting product and process for treating an integrated circuit substrate therewith
JPH0682214B2 (ja) * 1986-12-26 1994-10-19 東レ株式会社 水なし平版印刷版
JPH0740133B2 (ja) * 1987-02-17 1995-05-01 富士写真フイルム株式会社 湿し水不要感光性平版印刷版
JPH043066A (ja) * 1990-04-20 1992-01-08 Fuji Photo Film Co Ltd 転写記録媒体
JPH0493840A (ja) * 1990-08-03 1992-03-26 Konica Corp 湿し水不要の感光性平版印刷版
DE4239661A1 (de) * 1992-11-26 1994-06-01 Basf Lacke & Farben Lichtempfindliches Aufzeichnungsmaterial
US5425805A (en) * 1994-03-02 1995-06-20 Scitex Digital Printing, Inc. Waterfast dyes for ink jet recording fluids
DE4423140A1 (de) * 1994-07-01 1996-01-04 Hoechst Ag Hydrophiliertes Trägermaterial und damit hergestelltes Aufzeichnungsmaterial
JPH11344803A (ja) * 1998-05-29 1999-12-14 Cycolor System Kk 乾式画像形成材料及び乾式画像形成方法
JP3852889B2 (ja) * 1998-09-24 2006-12-06 富士写真フイルム株式会社 フォトレジスト用反射防止膜材料組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0029907A1 *

Also Published As

Publication number Publication date
JP2002530697A (ja) 2002-09-17
AU1373399A (en) 2000-06-05
WO2000029907A1 (fr) 2000-05-25
CA2349578A1 (fr) 2000-05-25

Similar Documents

Publication Publication Date Title
EP1634916B1 (fr) Sous-couche d'hydroxy-amine thermodurcissable pour gravure A 193 NM
EP0256031B1 (fr) Procede permettant de developper des reserves en poly(anhydride methacrylique)
US5482566A (en) Method for removing etching residue using a hydroxylamine-containing composition
KR100962740B1 (ko) 개선된 스핀 보울 상화성을 갖는 반사 방지 코팅 조성물
CN101523296B (zh) 精细图案形成方法及用于此法的抗蚀基板处理溶液
JP4459857B2 (ja) リソグラフィー用洗浄液及びそれを用いたレジストパターン形成方法
EP2975462B1 (fr) Composition de formation de motif de résine fin et procédé de formation de motif mettant en oeuvre cette composition
JP2001517728A (ja) 水性リンス組成物及びそれを用いた方法
KR100858594B1 (ko) 레지스트 패턴 형성방법 및 복합 린스액
KR20070058560A (ko) 리소그래피용 린스액과 레지스트패턴 형성방법
US6492092B1 (en) Hydroxy-epoxide thermally cured undercoat for 193 NM lithography
US6361921B1 (en) Priming composition for bonding photoresists on substrates
US11131932B2 (en) Cleaning liquid, and method of cleaning substrate provided with metal resist
WO2000029907A1 (fr) Composition d'appret permettant de coller des photoresines sur des substrats
JP4512092B2 (ja) 感光性樹脂除去用シンナー組成物
EP2053465A1 (fr) Composition liquide de traitement de résine photosensible positive et développeur liquide
US6121218A (en) Priming composition for bonding photoresists on substrates
WO2000031781A1 (fr) Procede relatif a la formation d'un motif de resist
JP4917969B2 (ja) 反射防止膜形成用組成物、及びこれを用いたレジストパターン形成方法
DE3780387T2 (de) Herstellungsverfahren einer integrierten schaltung.
KR101866722B1 (ko) 상면 반사 방지막 형성용 조성물 및 이를 사용하는 패턴 형성 방법
JPS58188132A (ja) レジストと基板との密着性強化方法
KR20080044643A (ko) 레지스트 박리액 조성물, 이를 이용한 박리방법, 및 그조성물의 재생 방법
US20240087905A1 (en) Wafer Edge Protection Film Forming Method, Patterning Process, And Composition For Forming Wafer Edge Protection Film
US7208454B2 (en) Cleaning solution for removing anti-reflective coating composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010522

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20041027

17Q First examination report despatched

Effective date: 20041027

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: METHOD FOR BONDING PHOTORESISTS ON SUBSTRATES

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20090814