JPH06506308A - Photodefinable interlevel dielectric - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Photodefinable interlevel dielectric Advance technique town Materials used in the present invention to provide separation of conductive layers in microelectronic circuits Regarding. In particular, the present invention can be photopolymerized so that multilayer structures are desired. The present invention relates to polymeric materials on which dielectric layers can be formed. Such a layer is are insulators, have good chemical resistance and of course the substrate on which they are placed. Must be glued onto the body.

Polyimide has superior temperature and chemical resistance compared to many other polymers. Polyimide has been used for such dielectrics because of its polyimide Literature and patents disclosing the use of (incorporated herein by reference) by the inventor of the present invention. Disadvantages of polyimides, namely that they contain large amounts of volatile substances during curing. release quality, absorb moisture, have poor adhesion and relatively high expansion rate It has been argued that it has The above U.S. patent is an invention with improved properties. Interlevel Other polymers, i.e. dial Vinyl benzyl ether or alkyl condensation product of dehyde and phenol ether is disclosed and claimed.

The present invention relates to other polymers found to provide useful interlevel dielectrics. Regarding.

In U.S. Pat. No. 4,855.375, the inventors of the present invention The combination of bisphenol and formaldehyde has applicability in making laminates. Disclosed oligomers that are ethers. In U.S. Patent No. 4,816.498 The above U.S.A. is a condensation product of dialdehyde and 3 to 4 moles of phenol. Other groups of oligomeric condensation products different from patent 4,855,375 are disclosed. It is. These oligomers are also vinylbenzyl ethers and alkyl ethers. etherified to provide a mixture with They are for electronic applications can be used to make laminates. Both such oligomers is interlevel, as will be seen in the following description. It has now been discovered that it is useful as an electric material. Related polymers are PCT/US No. 9 1109391 and PCT/US9 1109392 There is.

Genuine skin q summary! The present invention provides a method for forming a predetermined pattern from a polymer on a substrate and a method for doing so. It includes a dielectric layer made of

Such patterns are created by coating a prepolymer onto a substrate and applying a masking pattern. The exposed areas are irradiated to make the prepolymer insoluble, and the unirradiated areas of the coating are The screened portions are then selectively dissolved to leave an insoluble light-irradiated prepolymer. The irradiated prepolymer is then cured to form an infusible glass in a predetermined pattern. It is formed by forming a sliver-like solid.

This prepolymer is an oligomeric condensation product of dihydric phenol and formaldehyde. or 3 to 4 mol of said oligomer and dialdehyde. a second prepolymer which is an ether of the oligomeric condensation product of Either a mixture of

The first oligomer has the formula (In the formula, the repeating unit Q is the structure has, and n is an integer from 1 to lO, S is O or 1, Each X is independently CH. ,C(CHs)t,O,S,Son,CO#yo and OC. selected from the group consisting of H, O, Each R, and R8 are independently hydrogen, alkyl having 1 to 10 carbon atoms. and alkoxy moieties, phenyl and phenoxy moieties). , a and b are independently 0 or an integer from 1 to 4, and Z is CZ or Br. can be, E is a vinylbenzyl moiety, with at least 50% of all E being vinylbenzyl. alkyl having 1 to 10 carbon atoms is selected from the group consisting of benzyl; ) has.

In a preferred embodiment, E is at least 70% vinylbenzyl and the remaining E is vinylbenzyl. Lopil, and X is C (CHs) g Force 1 again number C (CHs) t and CO.

The second oligomer comprises (a) a proportion of 1 mole of dialdehyde and (b) a proportion of from about 3 to about 4 moles. It is an ether of an oligomeric condensation product with a proportion of phenol, and the Dialdehyde is OHC (CL), CHO (however, m & yo 0 force/matabanyo (an integer from 1 to 6), cyclopentanedialdehyde, phthalaldehyde, iso Phthalaldehyde, terephthalaldehyde, hexahydrophthalaldehyde, nocloheptane dialdehyde, hexahydroisophthalaldehyde, -N xahi selected from the group consisting of droterephthalaldehyde and cyclooctanedialdehyde. Phenol has the structural formula R, C, H□OH (where R5 is hydrogen or 1 to about 1 an alkyl group containing 0 carbon atoms) and the oligomeric condensation The phenolic residue of the synthesis product has a vinylbenzyl to base moiety ratio of about 1:1 to about 6: 1, vinylebenzyl, an alkyl moiety containing 1 to 10 carbon atoms, 5 to Randomly from cycloalkyl moieties containing lO carbon atoms and benzyl etherified with one or more selected substituents to provide an ether moiety; Ru.

Company Natsudan and Baseball Omega Kiho 1 Kinsho Cliff In U.S. Pat. No. 4,855,375, the inventors of the present invention discovered that dihydric phenols and Preparation and use of ethers of oligomeric condensation products with formaldehyde disclosed composite articles, particularly laminates for electronic applications. These compositions are Interlevel (int -erlevel) can be used as dielectrics, yet they have low water absorption, low dielectric constant, low coefficient of thermal expansion, high glass transition temperature, high thermal stability, high It has a high solids coverage and is photochemically curable and heat curable. to produce little or no volatile compounds during the curing process. has now been found. There are two prepolymers used to form the pattern. It is of the type. The first is the formula %formula% They are oligomeric esters that are the condensation products of dihydric phenols and formaldehyde. arises from terization. The product may be a mixture of oligomers with different molecular weights. The number of repeating units Q, n, will vary from 1 to 10, preferably n is 1 or an integer from 1 to 6, and the average number of n is about 3.

Repeating unit Q itself is a structure has. The fusion can occur on the same ring as in the structure on the right or on the structure on the left. It should be noted that they can occur on different rings, such as in structures. Repeat The aromatic rings in the repeating unit Q are either directly bonded or separated by an intervening moiety each of the 0 moieties X are separated, i.e. S is O or 1, methylene (CHs) , isopropylidene (C(CHz)J, oxygen, sulfur, sulfonyl (SO), carbon Bonyl (CO) or dioxyphenylene group (OC, H, O) (However, in this The two oxygens are either para or meta to each other, preferably Or X is C(CHs)t or both C(CH,) and CO.

Each of the aromatic rings! May have substituents or may not be substituted at all.

Therefore, R and R8 are independently hydrogen, hydrogen containing 1 to 10 carbon atoms; alkyl moieties, phenyl moieties, alkoxy moieties containing 1 to 10 carbon atoms; , and moieties such as phenoxy (C-HsO). suitable al Examples of kill moieties are methyl, ethyl, propyl, butyl, pentyl, hexyl, hepyl. tyl, octyl, nonyl and decyl moieties. Variables that are R, -R, =H Although highly desirable, methyl and tert-butyl groups are preferred. It is a part.

Basic resins can be modified into flame retardants by introducing halogen atoms into the aromatic ring. Wear. Thus, Z may be a halogen atom, especially bromine, and an aromatic ring. When is halogenated, a and b are integers from 1 to 4. Polyhalogenated substances is preferred as a flame retardant and therefore a and b are 2.3 or 4. is recommended.

The oligomeric condensation product has practical advantages in the interlevel dielectric resin of the present invention. Numerous phenolic hydroxyl groups, all end-capped as ether groups, It has a syl group. In the best case, if the ether moiety E is vinylbenzyl, then immediately T-Structure (However, this may be a meta or para isomer and is usually a meta isomer.) and para isomer). all vinylben It is desirable to have a phenolic hydroxyl end-capped with a diyl moiety. However, in terms of cost, it is preferable that slightly less than all of the ether groups are vinylbenzyl. however, a somewhat lower dielectric constant is usually sacrificed. E part is small (tomo) 50% should be vinylbenzyl moiety, but better performance properties occurs when 70-100% of the ether groups are vinylbenzyl and the best prepolymer mer products occur when 95-100% of such groups are vinylbenzyl. Ru. However, for many applications less than full vinylbenzyl groups are required. End-capping is acceptable but all hydroxyl groups should be capped .

When the ether group contains a group other than vinylbenzyl, E has 1 to 10 carbon atoms. It is a containing alkyl group or a benzyl group. When E is an alkyl group primary alkyl groups are preferred, especially primary lower alkyl groups having 1 to 4 carbon atoms. Alkyl groups are preferred; therefore, the most desirable alkyl groups are methyl, ethyl , 1-propyl, 1-butyl and 1-methyl-1-propyl. other a Alkyl groups are 1-pentyl, 1-hexyl, 1-hebutyl, 1-octyl, 1-no Nyl, 1-decyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2゜3 -dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-methyl-1-butyl Consisting of Nchiru et al.

Preferable l! , E is small (both 70% vinylbenzyl and The remaining E is propyl.

The second type of oligomer has a proportion of 1 mole of certain dialdehyde and about 3 to about 4 moles. It is an ether of an oligomeric condensation product with phenol in a proportion of 1. Even more special Qualitatively, the ether moiety is a vinylbenzyl moiety, containing from 1 to 10 carbon atoms. alkyl moieties, cycloalkyl moieties having from 5 to about 10 carbon atoms and benzyl moieties; The vinyl benzyl part is randomly selected from among the vinyl benzyl parts. The ratio of the ether moieties is at least 1:1 and can be as large as 6:1.

The phenolic oligomer has a proportion of 1 mole of the selected dialdehyde and 3 to 4 moles. In the practice of this invention, more than 4 moles of the condensation product with phenol in a proportion of (a proportion of phenol can be used but not more than 4 moles of phenol) The phenol will react with the dialdehyde.

One class of dialdehydes that can be used in the present invention is HC (CH,).

Linear terminal alkylene dial of CHO (where m is 0 or an integer from 1 to 6) It is dehyde. Such dialdehydes are glyoxal, malondialdehyde , succindialdehyde, glutaraldehyde, adiph aldehyde), pimelaldehyde and and sebacaldehyde (sebacalde-byde). Particularly preferred are the aldehydes which are 4 and in the practice of this invention glyoxal (m-0) is particularly preferred.

Other aldehydes that can be used in the preparation of oligomeric condensation products are Cyclopentanedialdehyde, phthalaldehyde, isophthalaldehyde, tele Phthalaldehyde, hexahydrophthalaldehyde (i.e., the aromatic ring is reduced counterpart of phthalaldehyde reduced to a xane ring), cycloheptane Includes dialdehydes and cyclooctanedialdehydes.

The oligomer contains 1 mole of the dialdehyde and 3 to about 4 mole of phenol. It is a condensation product with Phenol has the general structural formula R1C,H,OH (however, R 3 is hydrogen or an alkyl group having from 1 to about 8 carbon atoms). most Also desirable is the phenol itself, i.e. when R3 is hydrogen. Ru.

When R1 is an alkyl group, the alkyl group contains 1 to about 4 carbon atoms. is most preferred and cresol is the other preferred species when R1 is a methyl group. It is a phenol.

The condensation product is an analog to phenol-formaldehyde resin. That is, , the product results from the condensation of 2 molar proportions of phenol with each aldehyde group.

“Monomer” production using phenol and glyoxal to illustrate the reaction In the simplest case where the product can be viewed as a product, it has the structure (in the formula , almost exclusively ortho and to the condensation point of phenol and glyoxal. It is very different and almost completely different. However, one molecule of the above product has four phenolic groups and any one of these is glyoxer. This glyoxal can then react with other molecules of phenol. Further condensation with three molecules gives the structural formula. The above oligomeric product is a glioma of 2. This oligomer of zero order resulting from a molar ratio of phenol to xal of 7 is Glyoxal can react with other molecules and this glyoxal other molecule reacts with three additional phenols to give a ratio of 10 to 3 glyoxal. Structural formula with molar ratio of phenolic groups of The next higher oligomer with . In a similar manner, then The oligomer has a phenol to glyoxal molar ratio of 13:4, followed by oligomers with a high ratio of 16:5, etc., in which case the limiting molar ratio is 3:1. Ru. Ratios lower than 3:1 are never achieved without internal cyclization, i.e. One molecule of Sahl is reacted with at least two phenolic moieties of the oligomer. It is necessary to state that this is necessary. Condensation of “monomers” in a similar manner The product has a phenol-glyoxal limiting ratio of 4:1.

The condensation product is itself a phenol as mentioned above and is a mixture of oligomers. It is a compound. This mixture is characterized by the number of phenolic moieties per molecule. The present invention contains from 4 to about 60 phenolic moieties per molecule, and more usually 1 Concerning condensation products having from 4 to about 22 phenolic moieties per molecule. The product is A mixture of oligomers, preferred mixtures having an average of about 5 to about 5 oligomers per molecule. It is characterized by having 8 phenolic moieties.

More specifically, the dialdehyde is glyoxal and the phenol is fluorine. In the case of phenol itself, each oligomeric product has about 400 to 6000 More preferably, it has a molecular weight of about 400 to 2,200. oligomeric products can be characterized by an average molecular weight of about 500 to about 800. .

The thermosetting resin of the present invention is an ether of the above oligomeric condensation product. In one variation, the phenolic condensation product makes the final resin even more flame retardant. halogenated prior to ether formation. Increased flame retardancy is particularly important for halogen is chlorine or bromine and the use of brominated products is preferred. Halo The gene is introduced at the ortho and para positions to the phenolic hydroxyl group. Ru. One phenol if all ortho and rose positions are available A maximum of 3 halogen atoms per moiety can be introduced. sometimes maximum Although lower halogen content is advantageous, in many cases maximum halogen content It is desirable to collect oligomeric condensation products, but in the former case , there is at least one chlorine or bromine atom per phenolic moiety It will be clear that substantially all of the phenol condensation products (approximately 99.5 %) of the hydroxyls are capped to convert them to ether moieties. Aete Each of the ether moieties has a ratio of vinylbenzyl to all other ether moieties of at least 1 :1 and 6:1 for the first type of oligomer, which height may be vinylbenzyl, alkyl containing 1 to 10 carbon atoms, as defined above; , cycloalkyl and benzyl moieties of 5 to 10 carbon atoms. chosen randomly.

The prepolymer is produced by an acid-catalyzed condensation reaction of dihydric phenol with formaldehyde. Virtually all phenolic hydrogen can then be removed by converting these into ethers. It can be made by end-capping droxyl. acid catalyzed condensation reaction In reaction, it is preferable to avoid the formation of terminal hydroxyl methylene groups (-CH!O). However, end-capping by ether formation converts phenol condensation products into halo in basic medium. any such as by reacting with a furkyl or benzyl halide. This can be done by any suitable means.

The resulting thermosetting oligomers are cured with associated crosslinks by various curing means. Can be polymerized. If curing is carried out by thermal means, it will generally be approximately in air at a temperature of 100-300°C and more specifically about 120-300°C. or automatically by heating the oligomer resin in an inert atmosphere. . Curing can also be performed using azo-bis-isobutyronitrile, benzoyl peroxide, di-butyronitrile, can be effected by chemical means using free radical initiators such as chil peroxide etc. In the present invention, curing is carried out in the presence of a sensitizer or photoinitiator or irradiation, especially with visible or ultraviolet light, followed by heat curing. to form an infusible, insoluble glassy solid.

Mouth hotdefinable This oligomer can be used as a passivating agent to induce interlevel As an electric body, the device Dave means to provide dielectric isolation (insulator isolation trench) Can be used as, as high temperature solder mask, photoresist etc. Ru. Many of the following will mainly describe their uses as interlevel dielectrics. However, those skilled in the art will know how to use the materials of the invention in other applications as well. You will recognize it from this description.

The oligomer is applied as a coating to a suitable substrate. The coating has a thickness of 2 to 15 μm. For most parts, it is preferred to have, most preferably 5-10 μm. The substrates used are silicon wafers, integrated circuit silicon chips, printed circuit boards or or a ceramic substrate. Photosensitive oligomers are made by spin coating. By spray coating, by using a doctor knife or evenly coat the coating. can be applied by any other conventional technique known in the art to obtain can. If the viscosity is transiently high, a solution of the resin in a suitable solvent should be used. Can be done. Oligomers are polar aprotic solvents, aromatic hydrocarbons, halogenated carbonized The present invention is soluble in a wide class of solvents including hydrogen, ketones, esters, etc. An example of a solvent that can be used in the practice of is dimethylformamide (DM F), hexamethylphosphoramide (HMPA), N-methylacetamide (NMAc), N,N-dimethylacetamide (DMAc), dimethylsulfo Sid (DMSO), N-methylpyrrolidone (NMP), benzene, toluene , xylene, ethylbenzene, cumene, dichloromethane, chloroform, tetrachloride Carbon, chlorobenzene, tetrachloroethane, tetrachloroethylene, trichloro loethane, gamma-butyrolactone, methyl ethyl ketone, diethyl ketone, Xanone, heptanone, octanone, methyl acetate, ethyl acetate, butyl acetate, vinegar 2-methoxyethyl acid, methoxyethanol, ethoxyethanol, diglyme, Includes triglyme and the like. The fJ medium is non-reactive with both the substrate and the photosensitive oligomer. and the resin should be dissolved at least about 10 weight-volume percent. Should be able to provide solutions. The solvent is typically is removed, so a solvent with the lowest possible boiling point is used consistent with the above considerations. It is also preferable.

Although the oligomer can be directly photopolymerized, a photosensitizer or photoinitiator may be used and may be useful to reduce irradiation time. photosensitization If an agent or photoinitiator is used, it is added along with the oligomer during the coating step. from about 0.001 to about 5.0 weight percent relative to the oligomer. The light intensifier that can be used continuously in the practice of the present invention will increase at 0. Examples of sensitizers or photoinitiators are benzophenone, 4,4'-bis(dimethylamino ) benzophenone, 4,4'-dimethoxybenzophenone, xanthone, acetate Phenone, 4-trifluoromethyl-acetophenone, triphenylene, thioxy Santhone, anthraquinone, 4-phenylbenzophenone, naphthalene, 2-a Setonaphthalene, 1-acetonaphthalene, chrysene, anthracene, 9.10- Dichloroanthracene, pyrene, triphenylene, 1-fluoronaphthalene, 1 -chloronaphthalene, 1-bromonaphthalene, 1-iodonaphthalene, 1.3- Dicyanobenzene, dimethyl isophthalate, diethyl isophthalate, 3-cyano Methyl benzoate, ethyl 3-cyanobenzoate, phenyl 3-cyanobenzoate, 2 ゜2-dimethoxyacetophenone, 2,2-dimethoxyacetophenone, 2,2 '-dimethoxy-2-phenylacetophenone, 2,2'-jethoxy-2-phenyl Phenylacetophenone, benzoin methyl ether and 1-phenyl-1,2 -bropanedione-2-0-benzoyloxime. The preferred sensitizer is Benzophenone, 4.4'-bis(dimethylamino)benzophenone, 1.3- Dicyanobenzene, dimethyl isophthalate, diethyl isophthalate, 3-cyano Includes methyl benzoate, and phenyl 3-cyanobenzoate.

When the photosensitive oligomer is applied as a solution to the substrate, the solvent used is not irradiated or Therefore, before irradiation, if present, coated substrate for a period sufficient to remove essentially all solvent present. It is customary to heat the This is a known stage. It is for this reason that the use of low boiling point solvents is preferred. It is.

Oligomers can begin to harden at temperatures as low as about 110°C. , it is acceptable to use sufficient heat to provide a semi-cured coating. soft bake The process is carried out in vacuum under an inert atmosphere (e.g. nitrogen, helium, argon, etc.). Or it can be done in air.

A mask containing the desired pattern or image is placed in contact with the coated substrate or placed in close proximity and the oligomer coating is then exposed to X-rays, electron beams, ion beams, Irradiation through the mask by ultraviolet or visible light. for economic reasons and in the range of about 200 to about 800 nanometers for reasons of ease of manufacture. It is preferable to use radiation, as lower wavelength radiation provides better resolution. Radiation in the 200-500 nm range is preferred as it tends to The irradiated portions of the coating are then crosslinked, resulting in photocrosslinked oligos. mer remains quite soluble in the same solvent in which the original photosensitive oligomer remains completely soluble. Insoluble.

Irradiation can be carried out either in the presence or absence of oxygen. can. For suitable photocrosslinking to provide the desired differential solubility properties The required exposure time depends on the wavelength of the light used, its intensity, and the presence of a photosensitizer or photoinitiator. It varies from 2.3 seconds to several minutes depending on the presence or absence of the device. manufacturing purpose Therefore, shorter exposure times are highly preferred. One of the photosensitive oligomers of the present invention Two desirable properties are that they are photochemically cross-linked throughout the entire thickness of the film. It is to match. Therefore, the pattern is completely undercut during development. Shows little or no sign.

A selective pattern appears upon development with a solvent. As mentioned above, for irradiation The more photosensitive oligomer resins are extensively cross-linked, the more the oligomers are cross-linked. i.e., the irradiated portion and the oligomer are not cross-linked, i.e., the irradiated portion is It continues to have a large difference in solubility between the parts that are not present. For development Solvents used in generally create solutions of oligomers for coating purposes. This is the same solvent used for. Therefore, the class of solvents is solvents, aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, glymes, Includes calpitol, mixed solvent systems, etc.

The raised area after development corresponds to photochemically cross-linked oligomers. A selective pattern emerges. These relief structures are then hardened by heat. , highly resistant to high temperatures, chemical degradation and ionic migration and effective Highly cross-linked, infusible glass that serves as a protective layer and dielectric insulator Provides a solid. Curing is accompanied by cross-linking of the Zunyl groups and thermally, chemically Curing can be carried out manually or photochemically, with thermal curing being preferred. Thermal curing is Generally carried out over a temperature range of about 00°C to about 300°C and often multiple It is carried out at the stage of Therefore, for example, curing is performed at approximately 150°C for 0.5 to 5 hours. Curing is carried out at a temperature of approximately 200°C, followed by curing at approximately 180°C for approximately 0.5 to 24 hours. Performed at ~300°C. Curing is also possible with azo-bis-isobutyrolitrile, peroxide It is also carried out using free radical initiators such as benzoyl, monobutyl peroxide, etc. It can be done.

The oligomers of the invention are coated as a solution where they have a high solids concentration. since less solvent can be used and thus has to be evaporated, Particularly useful in photodefinable applications It was discovered that Also, since no volatile by-products are generated during curing, the film There is almost no contraction.

Turf I treatment Substrates (i.e., ceramic, alumina, silicon, printed wiring boards, etc.) can be prepared by those skilled in the art. Using conventional cleaning methods as known in the art, using conventional cleaning solvents (e.g. For example, methylene chloride, chloroform, Genesolv@, tri Chloroethylene, ethanol, methanol, sodium bisulfite, sodium sulfite potassium sulfite, etc.). Furthermore, the base May contain circuits already welded onto it, 1&body should be used after cleaning process. Adhesion between a substrate and a metal and/or polymeric dielectric layer may be used or It may be surface treated to increase its properties.

If used, the adhesion promoting side between the substrate and the dielectric layer will react with the polymer of the invention. may be selected from a range of surface silylating agents containing reactive groups that can Wear. Examples of surface silylating agents that can be used are vinylmethyldimethoxysilane, vinyl rutrimethoxysilane, vinylmethyljethoxysilane, vinyltriethoxysilane Ran, Jetoxymethylvinylphenethylsilane, Dimethoxymethylvinylphenethylsilane Netylsilane, triethoxyvinylphenethylsilane, trimethoxyvinylphene Such as netylsilane. Preferred silylating agents are vinylmethyldimethoxysilane, Vinylmethyljethoxysilane, jetoxymethylvinylphenethylsilane and The surface silylating agent is alcohol and dimethoxymethylvinylphenethylsilane. - Applied onto a substrate by dipping, spin coating or other techniques from an aqueous solution. For example, a 1-10% by weight solution of the silylating agent can be prepared in an alcohol (e.g. methanol). , ethanol, isopropanol, etc.) and 1 to 13 parts by weight of water. Dissolved in the amount%. The substrate is immersed in this solution for 15 seconds to 5 minutes, and then for 1 minute to 5 minutes. air dried for 5 hours and then placed in a convection oven, vacuum oven or hot plate Soft baking is performed at 60° C. to 100° C. for 1 minute to 5 hours.

The cleaned and/or surface treated substrate is covered with a metal pattern, 500 to 1000 of e.g. chromium, which is then covered with a dielectric layer of the invention. layer, 8000~20000 layer of copper and 500~1ooo layer of chromium A zero-order metal layer may be sputtered onto the surface and coated with a commercially available photoresist. and spin coating, soft baking, imaging, development and hardening. Processed according to a recommended treatment plan that utilizes a baking cycle. child This exposes the portion of the metal layer that is to be etched away to create the pattern. are doing. The metal is etched using standard wet techniques; e.g. The ROM layer is etched in a 1-30% hydrochloric acid solution activated with aluminum for 10 seconds to 5 minutes. the copper layer was etched with sodium persulfate solution for 10 seconds to 10 minutes; The bottom chrome layer was treated with aluminum activated 1-30% hydrochloric acid for 10 seconds to 5 minutes. etched and finally the etched substrate is deionized for 10-60 seconds. 9. Next, the remaining photoresist is washed with water, recommended for photoresist The metal pattern is stripped from the metal pattern according to a processing technique used. Finally clean up The treated substrate is dried before the next processing step.

A dielectric layer is coated on the substrate and its metal pattern and processed as follows. prepolymer (e.g. 1 0-80 wt%) on the substrate at a speed of 500-250 Orpm (7) for 30-90 seconds. Nispin-coated, prepolymer-coated substrates are treated with nitrogen bleed ( bleed) or without nitrogen bleed in a vacuum oven for 15 to 24 minutes. Soft baked at a temperature of 25-60℃ for an hour, then soft baked The coating is done using a mask of the desired design for the bias (vtas) etc. Images were formed using an ultraviolet light source (220-320 nm range) for 5 seconds to 30 minutes. , then the photocured polymer is cured using ultrasound for 5-120 seconds or using ultrasound. in a suitable solvent system (e.g. toluene, toluene/hexane, toluene/ethanol, cyclohexane, acetic acid butyl, butyl acetate, diglyme, etc.) and then the developed substrate is Solvents that are miscible with imaging solvents but are poor solvents for polymeric systems. Stop bath or based on system (e.g. hexane, pentane, ethanol etc.) Can be exposed to a rinse bath or solvent spray (optional step), then via Vias are cleaned using plasma etching or wet etching. The cured and finally dried substrate was heated from 25°C to 300°C for 30 minutes to 10 hours. Heat at a ramp of 300°C for 5 hours and then 300°C for 30 minutes to 10 hours. Using a preferred curing cycle that includes cooling with a ramp from 25°C to 25°C, Hard-baked in vacuum or in an inert atmosphere (i.e., argon, etc.) It will be done.

The processing is performed to form electronic interconnect structures of desired electrical and dielectric level. be repeated as necessary.

50.0. Bisphenol-A-formaldehyde (BPA-F) (Mn-3 94, Mw = 680.1. Is the dispersity of 7 mechanical? Stirrer, thermometer, heat monitor (There-0-Watch), addition funnel and 220 Jd of acetone in a 1000d three neck round bottom flask with nitrogen purge dissolved in 66 milliliters (0,4644 moles) of vinylbenzyl chloride (60/40 rose/metam) was added to the reaction mixture and stirred for 30 minutes. Heat the reaction mixture to 65°C and then add 143 ml of methanol. 41.80 g (0°745 mol) of potassium hydroxide in The reaction mixture was heated to reflux for 1 hour. Stirring The reaction mixture was cooled to ambient temperature and stirred for an additional 18 hours. The material was collected, dried over magnesium sulfate, filtered and concentrated under vacuum to give Mn- A red resinous product with a dispersity of 501, Mw-778, 1,6 was obtained.

5TBPA-F 70VBz OPr Use bisphenol-A-formaldehyde (BPA-F) as follows: : 456.58g (2,00mol) of bisphenol-A, paraformalde 90.00 g of hydride (100 moles of formaldehyde functionality) and 500 m A little ethanol is prepared using a mechanical stirrer, a thermometer, and a heat monitor (Ther-0J). latch), condenser, addition funnel and nitrogen purge. The reaction mixture, placed in a three-necked flask, was heated to 80 °C and 2 ．． 0 reaction in which OO ml of concentrated sulfuric acid was added dropwise over 30 min intervals. It was maintained at 80°C for 1 day.

Distilling the solvent from the reaction mixture using a reactor equipped with a Dean-Stark trap Then, resin is further injected into aluminum to obtain Mn=740, Mw-8800. , 50 g 7 g of resin with a dispersity of , 12,0 were produced.

Mechanical stirrer, addition funnel, condenser, thermometer, nitrogen purge and thermal monitoring 2000d three-necked round bottom frass with a container (There-0-11atch) The above BPA is added to 700 ml of N-methylpyrrolidinone (NMP) in a -228.31 grams of F were dissolved. To this reaction mixture, 21167 g (1, 400 mol) of vinylbenzyl chloride (60/40 para/meta isomer ratio) and and 0.10 g of 2,6-di-tert-butyl-P-cresol (BIT). The reaction mixture was heated to 60°C and dissolved in 325 ml of methanol. of potassium hydroxide over a period of 1.5 hours. and added dropwise. Maintain the reaction at 60 °C for 19 h with stirring under a nitrogen purge. Ta. 99.63 g (0,810 mol) of n-propyl bromide was added to the reaction mixture. was added and then the reaction mixture was diluted with 1501d in methanol over a 2 hour interval. 45.45 g (0,810 mol) of potassium hydroxide was added and the reaction was continued at 6 p.m. The temperature was maintained at 60°C. After cooling to room temperature, transfer the reaction mixture to another funnel and add 2 liters. of toluene and then washed four times with 2 liters of water and poured onto magnesium sulfate. dried, filtered and stripped under vacuum to give Mn-1100, Mw-1 636.6 g of resin with a dispersity of 8000.17.0 was produced.

IR shows no residual hydroxyl moieties present.

”-1 Styrene Bis Enol-A-Formal-Human 5TBPA-F 70V Bz　30Pr bisphenol-A-formaldehyde (BPA-F) as follows Built as a cage: mechanical stirrer, temperature needle, heat monitor (There-0-1 1 patch), 2000 mm with condenser, addition funnel and nitrogen purge 456.6 g (:L00 mol) of bisphenol in a three-necked flask -A, 45.04 g (1,50 mol formaldehyde functionality) of paraforma The reaction mixture charged with aldehyde and 350 milliliters of ethanol was ℃ and dropwise addition of 4.00 milliliters/torr of concentrated sulfuric acid over 5 minute intervals. The zero reaction was added and maintained at 80°C for 1 day.

The solvent was removed from the reaction mixture using a reactor equipped with a DC Stark trap. 1II and then the resin was further injected with aluminum to form Mn-230, Mw 447.6 g of resin with a dispersity of -1400.5.8 was produced.

Mechanical stirrer, addition funnel, condenser, temperature needle, nitrogen purge and thermal monitoring 2000ml three-neck round bottom with a watch (Tber So-0-Watch) 22 in 700 milliliters of N-methylpyrrolidinone (NMP) in a flask. 8.29 grams of the above BPA-F was dissolved. To this reaction mixture, 21167 g (1,400 mol) of vinylbenzyl chloride (60/40 para/meta isomer ratio ) and 0.10 g of 2°6-tart-butyl-p-cresol (BH Heat the reaction mixture to 60°C and add 430ml of methanol. 98.19 g (1,750 moles) of potassium hydroxide in I added it dropwise. Maintain reaction at 60 °C for 19 h with stirring under nitrogen purge. did. 99.63 g (0,810 mol) of n-propyl bromide was added to the reaction mixture. , then this reaction mixture was added with 230 milliliters of potassium hydroxide in methanol. 45.45 g (0,810 mol) was added over a 1.25 hour interval and the reaction was maintained at 60°C for 18 hours. After treatment, analysis of a small fraction of the reaction mixture 9.96 g of n-propyl bromide (0 , 081 mol) and then potassium hydroxide in 30 ml of methanol. 4.54 g (0,081 mol) of um were added to the reaction mixture and heated at 60 °C. Allowed time to react. After cooling to room temperature, transfer the reaction mixture to another funnel and add 1.5 liters. of toluene and then washed four times with 1 liter of water and poured onto magnesium sulfate. dried, filtered and stripped under vacuum to give Mn-730, Mw-18 334.73g of resin with a dispersity of 00,2,5 was produced. IR remains and droxy does not indicate the existence of the file part.

Example – soil Styrene bisphenol-A-formal-hyperdihydroxybenzophene /70) Gold 1 (STBPA-F-BP 70VBz 30Pr)) Bisphenol Ru-A-formaldehyde-dihydroxybenzophenone (BPA-F-BP) was constructed with the following: mechanical stirrer, thermometer, heat monitor (there -0-Watch), condenser, addition funnel and nitrogen purge 433.75 g of bisphenol A (1 , 90 mol), 21.42 g of 4,4'-dihydroxybenzophenone (0,1 0 mol), 69.07 g of paraformaldehyde (2.30 mol of formaldehyde), 0 reaction mixture charged with 500 ml of ethanol) and 500 ml of ethanol. Heat to 80℃ and add 4.00ml of concentrated sulfuric acid dropwise at 3 minute intervals. added. The reaction was maintained at 80°C for 1 day. Equipped with a DC Stark trap A reactor is used to distill the solvent from the reaction mixture and then the resin is poured into aluminum pellets. Inject the resin with a dispersity of Mn-300, Mw-2300, 7,9. 415.5g was obtained.

Mechanical stirrer, addition funnel, condenser, thermometer, nitrogen purge and thermal monitoring 2000ml three-necked bottle with a container (There-0-1+Iatch) in a 700 ml bottle of N-methylpyrrolidinone (NMP) in a round bottom flask. 228.29 grams of the above BPA-F-BP was dissolved. salt in this reaction mixture 213.67 g of vinylbenzyl chloride (60/40 rose/meta isomer ratio) ( 1,400 mol) was added. The reaction mixture was heated to 60°C and methanol 98.19 g (1,750 moles) of potassium hydroxide in 375 milliliters of was added dropwise over a 2.0 hour interval. 1 while stirring under nitrogen purge. The reaction was maintained at 60°C for 9 hours. 99 of n-propyl bromide in the reaction mixture. ．． 63 g (0,810 mol) and then to the reaction mixture 250 g (0,810 mol) of methanol. 45.45 g (0,810 mol) of potassium hydroxide in milliliter was heated for 2 hours. The reaction mixture was added over intervals and the reaction was maintained at 60°C for 18 hours. Amounts of fractions were removed, worked-up and subjected to IR Analysis shows residual hydroxyl moieties of 9.96% of n-propyl bromide in the reaction mixture. g (0,081 mol) and then in 20 ml of methanol Add 4.54 g (0,081 mol) of potassium hydroxide and mix the reaction The material was allowed to react for 18 hours. After cooling to room temperature, the reaction mixture was transferred to another funnel and 1.5 Add a liter of toluene and then wash three times with 1 liter of water and remove the sulfuric acid magnet. Mn=700, Mw 2LL8g of resin having a dispersity of -2400,3,4+71 was obtained. IR is residual hydroxyl Does not indicate the presence of sill parts.

Mechanical stirrer, addition funnel, condenser, thermometer, heat monitor (Ther-1) 〇-11atch), 3000mm cylinder equipped with drying tube and nitrogen purge Tetraphenolethane (TPE) (Mn-27 4, 353.0 g (0,500 mol) of Mwm711), 3.30 g of BHT (0,0150 mol) and 1670 ml of N-methylpyrrolidinone (NMP) Added Little. When dissolving TPA, Hinylhenzyl chloride (VBC) (7) 37:0 reaction mixture to which 19 g (2.45 mol) was added was heated to 60 °C. 160.25g of potassium hydroxide in 360ml of methanol ( 2,500 mol) was added dropwise over a period of 300 minutes. 3 more of the mixture ．． maintained at 60°C for 5 hours and then heated to 127.0 mm of 1-bromopropane. (1,400 moles) in 150 milliliters of zero order methanol. 68.68 g (1,070 mol) of potassium hydroxide was added over 300 minute intervals. was added dropwise and the temperature was maintained at 60°C for a further 1.5 hours.

The mixture was cooled and 2 liters of toluene were added. Mixture with 5 liters of water and three times with 5 liters of 1M sodium chloride solution. Sulfurize the organic phase dried over sodium chloride, filtered through Celite, filtered again and dried Concentrated in air to obtain a resinous material with Mn-576, Mw=915.1.59 dispersity. 84% product was obtained.

■Once Contains styrene-tophenolene (100' vinylbenzyl 5TTPE 　100VBz mechanical stirrer, addition funnel, condenser, thermometer, heat monitor (Therm-0-Watch), equipped with a drying tube and nitrogen purge. Tetraphenol ethane (Mn= 274, Mw-711) 200.0g (0,284 mol), BHT 1.8 8 g (0,00853 mol) and 95 of N-methylpyrrolidinone (NMP) Added 0 ml. , during the dissolution of TPH, vinyl chloride (VBC) 242.65 g (1,50 mol) of

The reaction mixture was heated to 60°C and hydroxyl acid in 230 ml of methanol was added. 101.95 g (1,590 mol) of potassium oxide was added dropwise over 300 minute intervals. I took it down and added it. The mixture was maintained at 60° C. for an additional 4675 hours.

15.17 g (0,0994 mol) of vinylbenzyl chloride was added. methanol 6.37 g (0,0994 mol) of potassium hydroxide in 15 milliliters of Add dropwise over 300 minute intervals and maintain temperature at 60°C for an additional 1.7 hours. I held it. 0 to which 15.17 g (0,0994 mol) of vinylbenzyl chloride was added. Next, 6.37 g of potassium hydroxide (0,0 994 mol) was added dropwise over 300 minute intervals and the temperature was increased for a further 1 hour. It was maintained at 60°C.

The mixture was cooled and 1.2 liters of toluene was added. 3 liters of mixture of water and twice with 3 liters of 1M sodium chloride solution. organic phase dried over sodium sulfate, filtered through Celite, and filtered again. and condensed under vacuum to obtain a dispersity of Mn=778, Mw=1079, l, and 39. 95% resinous product was produced.

Spot Yu Examples 1.2.3 and 4, each of a series of styrene-terminated bisphenol-A-phosphors. Lumaldehyde (STBPA-F) resin samples A, B, C1 and D were Curing cycle: 2 hours at 80°C, 16 hours at 100°C, 4 hours at 120°C, 16 It will cure after 16 hours at 0°C, 2 hours at 200°C and 1 hour at 225°C. and measured their properties. The results are summarized in the following table.

1-1 Tg ("C)"' 206 > 300 > 300 > 300 T s p ( 'C)"' 193±6118±5205±3153±3αwe　(ppm/ “C)”’ 55±1 52±4 49±3 80±8αthe (pps/ “C)”’77±1 66±4 75±4125±6ε””3.29 2.86 2.86 2.91t a n 6”’ 0.004 0.001 0.006 0.006ε’” ND 2.90 2.91 2.94ta nδ3'''' N D O, 00050, 0060, 017 water absorption%'' O, 1540, 3000, 264ND: Not measured (Glass transition temperature measured by differential scanning calorimeter.

伽）　Thermomechanical Analysis (Thers+o　Mechanical Analysis ) softening point (trace thermal transition).

(C) Coefficient of thermal expansion between 25°C and softening point.

(a) Coefficient of thermal expansion between 25°C and 260°C.

(e) Relative permittivity at 1M Hz and 0% relative temperature and humidity at 25°C.

(f) Loss tangent at IMHz and 0% relative temperature and humidity at 25°C ( loss tangent) * @ Relative permittivity at 50% relative humidity at IMHz and 25°C.

(c) Loss tangent at IMHz and 50% relative humidity at 25°C (loss tangent) * (i) 168 hours at 25°C and 50% relative humidity.

Group-1 A solution of 0.4936 g of 5TBPA-F from Example 1 dissolved in 4.4493 g of DMF. 0.5049 g of 5TBPA-F of Example 0 using Samples A to D from Solution 1 and and 0.0063 g of 4,4'-bis(dimethylamino)benzophenone in DMF. Samples E-H were prepared from Solution 2 dissolved in 4.6008 g of STB of Example 1. 0.415g of PA-F and 4,4'-bis(dimethylamino)benzopheno Sample I was prepared from solution 3 in which 0.0250 g of DMF was dissolved in 5.3100 g of DMF. -I made L.

Spin coat these solutions onto a silicon wafer at 1150 rpm for 10 seconds. The wafer was exposed to a 200 watt water vapor lamp at various time intervals. and then the solubility in DMF was investigated.

A30 Easily soluble: Slightly resistant to dissolution.

B60 Resistant to dissolution: Dissolves with long exposure to solvent (>0.5 hours).

Resistant to C120 dissolution: dissolves with long exposure to solvent (>0.5 hours).

D 300 Very resistant to dissolution.

E30 Slightly resistant to dissolution: Dissolves with long exposure to solvent (>0.5 hours).

F60 Resistant to dissolution: Dissolves with long exposure to solvent (>0.5 hours).

G120 Resistant to dissolution: Dissolves with long exposure to solvent (>0.5 hours).

Very resistant to H300 dissolution.

1.30 Resistant to dissolution: Dissolves with long exposure to solvent (>1.0 hours).

J60 Resistant to dissolution: Dissolves with long exposure to solvent (>1.0 hours).

K 120 Very resistant to dissolution.

L 300 Very resistant to dissolution.

±−yu A 40.60% by weight solution of 5TBPA-F Example 2) in toluene was heated at 11 Spin coating onto a silicon surface at 000 rpm. true coated desk After soft baking at 25℃ for 18 hours under air, they were filtered through a quartz/water filter. The zero order was exposed to UV radiation for 3 minutes using a 200 watt mercury vapor lamp. Expose the irradiated and uncured coatings to various solvents and remove the dissolved resin. The amount was measured. The results are shown in the table below.

l--Lord 5TBPA-F's 6 0 of 5TBPA-F ooooooo.

30 95.8B 96.93 54.71 25.95 6.51 -1.2 060 98.82 99.39 61.18 31.01 8.28 -2. 41120 98.24 99.39 65.29 36.0B 11.24 -3.01180 97.65 10Q, 00 66.47 3B, 61 13 ．． 02 -1.81300 98.24 100. OQ 68.82 42.4 1 15.98 - 1.20a) coated on silicon wafer and 18 o'clock 5TBPA-F soft baked at 25°C.

b) Weight % solution.

l-1↓ 7°″ of 5TBPA-F” 0- of 5TBPA-F 30 95.88 94.27 90.59 56.82 14.04 0.0 060 98.82 98.44 95.88 64.39 18.13 -1 ．． 21120 98.24 96.88 95.29 70.45 22.22 0.00180 97.65 97.92 96.47 74.24 26. 32 0.00300 98.24 98.44 97.06 78.03 3 0.41 1.21a) Coated on silicon wafer and 25° for 18 hours 5TBPA-F soft baked at C.

b) Weight % solution.

l-once °　　　6 of 5TBPA-F- 0 of 5TBPA-F 30 1.74 4.71 1.16 -0.61 -0.60 -0.586 0 1.16 3.53 1.74 -1.22 -1.80 -1.7312 0 1.74 4.12 0.58 -1.22 -2.40 -2.3118 0 1.74 4.71 0.00 -5.49 -1.80 -2.3130 0 2.91 -3.53 2.91 1.22 -1.80 -1.738) Coated on a silicon wafer and soft baked at 25℃ for 18 hours. Cured in a 200 watt mercury vapor lamp for 3 minutes using a quartz/water filter. 5TBPA-F.

b) Weight % solution.

table - once oo　o　o　o　o　.

30 1.74 0.60 -0.61 0.00 0.00 -0.5160 1.16 0.60 0.00 -1.17 -1.20 -2.02120 1.74 0.00 0.61 -1.75 -1.80 -2.53180 1.74 1.19 0.61 0.60 -0.60 -3.03300 2.91 1.79 1.83 1.75 -1.20 -3.03a) Siri coated onto a con wafer, soft-baked at 25°C for 18 hours, and then 200 watts of water using a water filter [5] cured in an air lamp for 3 minutes TBPA-F.

b) Weight % solution.

30 1.07 -1.05 -2.20 0.0060 2.67 1.05 0.00 -1.21120 4.2B 2.62 1.65' 0.001 80 6.42 4.19 3.30 0.00300 9.63 7.33 6.59 1.21a) Coated on silicon wafer and kept at 25°C for 18 hours 5TBPA-F soft baked.

b) Weight % solution.

table - once 5TBPA-F" r" Re? -5TBPA-F O o　o　oo　.

30 −2.67 −1.55 −2.58 ~ 0.5160 −2.14 − 1.55 -2.06 -2.02120 -2.67 -2.07 -2.5 8 -2.53180 -4.28 -4.15 -5.15 -3.0330 0 -3.21 -1.04 -2.06 -3.03a) Silicon wafer coated on top, soft baked at 25°C for 18 hours, and quartz/water filtered. 5TBPA cured for 3 minutes with a 200 watt mercury vapor lamp using a -F.

b) Weight % solution.

Friend - once 5TBPA-F"・ゝの" 5TBPA-F O oo　oo　oo.

30 98.25 93.78 -1.04 93.26 7.98 91.3 360 98.83 100.00 -0.52 100.00 12.77 100.00120 99.42 100.48 0.00 100.00 1 3.83 100.00180 100.00 98.09 -5.21 96 ．． 0? 12.23 94.22300 100.00 100.00 0.5 2 101.12 1B, 62 100.58a) Coated on silicon wafer 5TBPA-F and soft baked at 25° C. for 18 hours.

b) Nitromethane and ethyl acetate development system after each exposure to developing solvent An ethanol rinse was used for this purpose.

Ju 5TBPA-F Theory - Gourd's ゛　ka 5TBPA-F O oo　o　o　o　o　.

30 1.16 -0.53 0.00 -2.06 -2.01 4.866 0 2.33 0.53 -10.53 1.03 -6.03 -4.321 20 4.07 2.14 -1.58 6.70 -2.51 6.4918 0 5.81 2.67 -4.74 3.61 -6.53 0.00300 6.40 1.60 -2.63 7.73 -1.51 7.57a) coated onto a silicon wafer, soft baked at 25°C for 18 hours, and Cured for 3 minutes in a 200 watt mercury vapor lamp using a quartz/water filter. 5TBPA-F.

b) of nitromethane and methyl acetate development systems after each exposure to developing solvents. An ethanol rinse was used for this purpose.

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30 98.32 98.38 97.83 14.95 95.7960 1 00.00 100.00 100.00 19.59 98.95120 1 00.00 100.54 100.54 22.68 100.00180 94.97 96.76 97.28 23.20 96.84300 101 ．． 12 100.54 100.54 29.90 100.53a) Silico 5TB coated onto a wafer and soft baked at 25°C for 18 hours. PA-F.

b) An ethanol rinse was used after each exposure to developing solvent.

Table--1λ 5TBPA-F''・'　r''6 5TBPA-F O oo　o　o　o　.

30 2.76 2.16 5.26 -2,65 3.6860 5.52 5.95 5.79 -1.59 7.37120 5.52 7.57 3. 68 -2.65 8.95180 1.66 4.32 -0.53 -5. 82 5.79300 6.63 8.65 6.32 -1.59 7.89 8) Coated on silicon wafer and soft baked at 25°C for 18 hours. and a 200 watt mercury vapor lamp using a quartz/water filter. 5TBPA-F cured for 3 minutes.

b) An ethanol rinse was used after each exposure to developing solvent.

Mawari-1dan 5TBPA-F of Example 2 was dissolved in toluene to give 40.60% by weight of 5TBPA-F. and 59.40% by weight of toluene. 500~ for 60 seconds Apply this solution onto a silicon surface using a spin coating speed of 2000 rpm. The 9th layer was spin-coated and soft-baked for 18 hours at 25°C under vacuum. The sample was analyzed using a USAF test resolution pattern and a quartz/water filter. To the 0th order a) exposed for 60-180 seconds to UV radiation in a 200 Watt mercury lamp toluene with xane rinse or b) diglyme with ethanol rinse. The photocured polymer was developed at 25° C. for 45 seconds to 120 seconds. 2 Heat with a ramp from 25°C to 230°C for an hour, maintain at 230°C for 1 hour and then for 2 hours. Air dry the substrate using a curing cycle under vacuum with cooling to room temperature over a period of time. Hard baked.

The film thickness of the photocured polymer was 1° (Tyler Poplin Talysurf). Taylor-Hobson Talysurf 10) Measured using a profilometer determined.

1500180 Toluene 90 19.62 500 120 Jig IJ M1 20 16.53 800 120 Torxun 90 14.04 800 12 0 Jig rim 60 14.05 800 120 Jig IJ rim 120 14 ．． 76 800 60 Jig 90 12.27 1000 120 Jig Rim 45 12.88 1000 120 Jigrim 90 14.49 10 00 60 Digrim 120 12.110 1500 120 Digrim 45 9.611 1500 120 Jigrim 90 10.712 1500 60 Digrim 120 10.013 2000 120 Digrim 60 7 ．． 414 2000 60 Jigrim 60 8.315 2000 120 Diglyme 90 8.0 Example 2 (7) Dissolve STBPA-F in xylene to 5TB A solution with a composition of 42.16% by weight of PA-F (7) and 57.84% by weight of xylene. produced a liquid. Use a spin coating speed of 500-2000 rpm for 60 seconds. This solution was spin-coated onto a silicon surface using 0-order USAF test resolution patterns and quartz/water filters soft-baked for a while. Using a router, transfer the sample to UV irradiation with a 200 watt mercury lamp. After exposure for 20 seconds to 180 seconds, ethyl acetate (Et Ac) or diglyme for 45 to 120 seconds at 25°C. imaged. Heat ramp from 25°C to 230°C in 2 hours and maintain at 230°C for 1 hour using a curing cycle under vacuum, cooling to room temperature for 2 hours. , the air-dried substrate was hard-baked.

Tyler Poplin Talysurf 10 (Taylor-Bobson Ta1 ysurf 10) Analyze the thickness of the photocurable polymer film using a rough needle. Ta.

2 500 120 Digrim 90 20.53 500 180 EtAc 120 18.24 800 180 EtAc 120 9.35 800 120 Digrim 90 8.56 800 120 E t A c 90 9.77 1000 120 EtAc 90 B, 08 1000 120 Digrim 90 8.99 1000 120 Digrim 90 8.410 1500 120 EtAc 90 7.811 1500 120 EtA c 45 7.812 1500 120 Digrim 45 8.013 20 00 120 Digrim 45 8.714 2000 120 Digrim 4 5 7.515 2000 120 EtAc 45 10.0 Medical-Sat I A solution of 60.87% by weight 5TBPA-F-BP (Example 4) in toluene was Spin coating onto a silicon surface at 11000 rpm for seconds. coated de Zero-order quartz/water filter soft-baked at 25°C for 18 hours under vacuum Expose them for 3 minutes to UV radiation with a 200 watt mercury vapor lamp using The zero-order irradiated coatings and uncured coatings were exposed to various solvents and dissolved. The amount of resin released was measured. The results are shown in the table below.

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30 96.62 2.06 6.34 99.00 96.23 96.15 60 100.00 2.75 9.86 101.00 99.69 99. 04120 5.50 14.44 --- --- --- 180 5.15 19.72 --- --- --- 300 4.47 19.37 --- --- ---a) Coated on silicon wafer and heated at 25°C for 18 hours 5TBPA-F-BP soft-baked in

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30 7.43 1.01 1.03 6.29 6.18 6.6460 7 ．． 7? 2.02 3.09 7.34 8.73 9.59120 9.80 1.6B 3.09 7.34 11.64 9.23180 9.80 2 ．． 02 4.47 7.69 12.36 9.59300 9.46 2.6 9 3.09 B, 39 15.64 8.86a) Covered on silicon wafer Covered and soft baked at 25°C for 18 hours using a quartz/water filter. 5TBPA-F-BP was cured in a 200 watt mercury vapor lamp for 3 minutes.

L-uni 5TBPA-F-BP So・1'' 0 of 5TBPA-F-BP oooooooo.

30 95.86 98.65 4.53 97.63 98.95 100. 0060 100.69 100.34 7.32 100.00 98.95 100.72a) Coated on a silicon wafer and soaked at 25°C for 18 hours. 5TBPA-F-BP soft baked.

b) An ethanol rinse was used after each exposure to developing solvent.

Table 1” 5TBPA-F-BP-・b °　″ 6 5TBPA-F-BP-0 oooooooo.

30 15.32 16.61 2.10 13.71 4.75 6.786 0 13.25 17.29 2.80 19.40 8.14 7.1212 0 12.91 16.27 2.10 22.0? 13.56 7.461 80 11.92 17.29 1.40 22.74 16.61 7.46 300 14.24 15.93 2. IQ 23.41 20.00 6.4 4a) Coated on silicon wafer and soft baked at 25°C for 18 hours. And using a quartz/water filter, 200 watts of water i2! in the g-lamp 5TBPA-F-BP cured for 3 minutes.

b) An ethanol rinse was used after each exposure to developing solvent.

30 97.93 B1.91 21.0560 99.66 90.78 2 5.96120 100.00 93.52 29.12180 93.52 30.88 300 93.86 31.93 a) Coated on silicon wafer and soft baked at 25°C for 18 hours 5TBPA-F-BP.

b) An ethanol rinse was used after each exposure to developing solvent.

30 13.98 6.64 8.2560 13.26 6.99 3.30 120 12.90 8.39 2.97180 12.19 8.39 2. 31300 12.19 8.04 2.31a) Coating on silicon wafer and soft baked at 25°C for 18 hours and using a quartz/water filter. 5TBPA-F-BP was cured in a 200 wand mercury lamp for 3 minutes.

b) An ethanol rinse was used after each exposure to developing solvent.

■−Upper Yu Dissolve 5TBPA, -F-BP of Example 4 in toluene to obtain 4 of 5TBPA-F-BP. A solution with a composition of 6.17% by weight and 53.83% by weight of toluene was produced. 4 Apply this solution using a spin coating speed of 500-200 Orpm for 0 seconds. was spin-coated onto a silicon surface. USAF test resolution pattern and Using a quartz/water filter, the sample was exposed to a 200 watt mercury lamp. After exposure to UV radiation for 30-90 seconds, acetic acid blotch with ethanol rinse was used. Develop the photocured polymer for 15 seconds at 25°C using chill (BuAc) or diglyme. imaged. Heat ramp from 25°C to 230°C for 2 hours and maintain at 230°C for 1 hour. using a curing cycle under vacuum, cooling to room temperature for 2 hours. The air-dried substrate was then hard baked.

Tyler Poplin Surf 10 (Taylor-Hobson) surf 10) The thickness of the photocurable polymer film was analyzed using a profilometer. .

-Table 11 λ1- 1 500 90 BuAc 15 9.62 500 30 BuAc 15 8.23 500 90 Jigrim 15 8.24 800 90 Jigrim Mu 15 7.65 800 30 Jigrim 15 7.26 800 90 BuAc 15 7.27 1000 90 BuAc 15 6.38 1 000 45 BuAc 15 6.39 1000 90 Digrim 15 6.410 1500 90 Digrim 15 5.811 1500 90 BuAc 15 5.912 1500 90 BuAc 15 5.313 2000 90 BuAc 15 4.814 2000 30 BuAc 1 5 4.615 2000 90 Jigrim 15 4.8■-1 Sat Styrene-terminated bisphenol-A-formaldehyde (STBPA-F) of Example 2 and the styrene-terminated tetraphenolethane (STTPE) of Example 5 (see below). The mixture of samples A, B and C) was then cured for 2 hours at 80°C for the next curing cycle. 16 hours at 100℃, 4 hours at 120℃, 16 hours at 160℃, 200℃ C. for 2 hours and 225.degree. C. for 1 hour and their properties determined.

Table - Straight 5TBPA-F: 5TTPE A B C 3TBPA-F:5TTPE 90:10 75:25 so:s.

Tg ('C)"'>300>300>300Tsp('C)')1 30±5134±6218±7age (ppm/”C) Lc′ 51+3 66+2 39+2αgms(Ppm/”C)”’ 62±2 85±2 4 4±1ε"" 2.85 2.85 2.90tanδ"' 0.0003 0 ．． 002 0.003ε' (豐' 2.89 2.88 2.94t a n 6”’ 0.002 0.002 0.003 Water absorption% 1” 0.169 0.152 0.163 (a) Glass transition temperature measured by differential scanning calorimeter.

[Yes]) Softening point (trace thermal transition) by thermomechanical analysis.

(C) Coefficient of thermal expansion between 25°C and softening point.

(d) Coefficient of thermal expansion between 25°C and 260°C.

(e) Dielectric constant at IMHz and 0% relative humidity at 25°C.

(f) Loss tangent at 0% relative temperature and humidity at IMHz and 25°C (loss tangent).

(6) Dielectric constant at IMHz and 50% relative humidity at 25°C.

(b) Lostangen at IMHz and 50% relative humidity at 25°C loss tangent (i) 16a hours at 50% relative humidity at 25°C.

Medicine - Upper 1 50: 50 of 5TBPA-F (Example 2): 5TTPE (Example 5) of 39.8 A 9% resin solids coating solution was made in toluene solution. 110 for 60 seconds The solution was applied to the silicon surface via spin coating at 00 rpm. coated The desk was soft-baked at 25°C for 18 hours under vacuum, then fused to quartz/water. Using a filter, they were exposed to UV radiation from a 200 watt mercury vapor lamp for 3 hours. Exposure was made for a minute. The irradiated and uncured coatings are then exposed to various solvents and The amount of resin dissolved was measured. The results are shown in the table below.

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30 91.97 88.10 88.24 2.41 85.54 -6.9 860 100.00 98.8! 97.65 16.87 9B, 80 1 ．． 16120 97.81 97.62 97.65 20.48 98.80 3.49180 101.46 98.81 98.82 22.89 10 0.00 4.65300 101.46 98.81 97.65 25.3 0 100.00 4.65a) Coated on silicon wafer and for 18 hours So:so 5TBPA-F:5TTPE soft baked at 25°C.

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30 1.12 2.30 -1.12 -4.40 8.89 -1.096 0 17.98 12.64 14.61 4.40 20.00 B, 701 20 14.61 10.34 11.24 -2.20 15.56 1.0 9180 1? , 98 14.94 16.85 2.20 20.00 5. 43300 1? , 98 13.79 16.85 0.00 20.00 3 ．． 26a) Coated on silicon wafer and soft baked at 25°C for 18 hours 200 watts of water using filters and quartz/water filters! ! with a steam lamp 50:50 5TBPA-F:5TTPE cured for 3 minutes.

--1i so: so's 5TBPA-F: 5TTPE song and others' ゛　'ka? -5TBP A-F 5TTPE o　o　o　o　o　.

30 B3.53 85.15 86.81 86.78 B7.3660 9 4.12 94.06 93.41 96.67 95.40120 94.1 2 93.07 94.51 95.56 94.25180 92.94 9 4.06 93.41 95.56 95.40300 92.94 95.0 5 94.51 95.56 95.40a) Silicon wafer is coated with 50:50 5TBPA-F:5 soft-baked at 25°C for 18 hours TTPE.

b) Ethanol rinsing of samples after exposure to developing solvent.

稟--1dan 5TBPA-F with 50:50: 5TTPE”・5TBPA-F with 1 5TTPE O o　o　o　o　o　.

30 11.11 B, 70 21.65 18.1B 19.7860 23 ．． 33 21.74 24.74 21.59 20.88120 16.67 16.30 1B, 56 13.64 16.48180 20.00 20 ．． 65 23.71 18.18 18.68300 20.00 19.57 22.68 19.32 16.48a) coated on a silicon wafer, Soft-baked at 25°C for 18 hours and using a quartz/water filter, 50:50 5TBPA cured for 3 minutes in a 00 Watt mercury vapor lamp F: 5TTPE.

b) Ethanol rinsing of samples after exposure to developing solvent.

l engineering so: so's 5TBPA-F: 5TTPE''-''s 5TBPA-F 0 of 5TTPE 30 32.95 46.59 -3.3360 47.73 63.64 4 ．． 44120 50.00 68.18 3.33180 51, 14 69. 32 3.33300 54.55 70.45 3.33a) Silicon wafer 5 of so:so was coated with TBPA-F: 5TTPE.

b) Ethanol rinsing of samples after exposure to developing solvent.

30 7.61 10.64 7.3760 10.87 12.77 8.4 2120 7.61 12.77 8.42180 7.61 12.77 8 ．． 42300 7.61 12.77 6.32a) Covered on silicon wafer Covered, soft baked at 25°C for 18 hours and filtered using a quartz/water filter. 5TBP of so:so cured for 3 minutes in a 200 watt mercury vacuum lamp. A-F: 5TTPE.

b) Ethanol rinsing of the sample after exposure to developing solvent.

Group-1st 5TBPA-F from Example 2 and 5TTPE from Example 5 were dissolved in toluene to yield 23.39 wt% 5TBPA-F, 23.39wt% 5TTPE and 53.22wt. % toluene was produced. Speed at 500-2000 rpm for 60 seconds Spin coat this solution onto the silicon surface using a slow coating speed. Zero-order USAF test solution Using an image pattern and a quartz/water filter, the sample was Ethanol rinse after 60-180 seconds exposure to UV radiation in a mercury lamp The photocurable polymer was cured using butyl acetate (BuAc) or diglyme with Developed for 15 to 45 seconds at <RTIgt;C. Heat at a gradient of 25°C to 230°C for 2 hours, Harden under vacuum maintaining at 230 °C for an hour and then cooling to room temperature for 2 hours. The air-dried substrate was hard-baked using a drying cycle.

Tyler Poplin Surf 10 (↑aylor-Hobson Talys urf 10) The thickness of the photocurable polymer film was analyzed using a rough needle.

-Table-X 1 500 120 Digrim 45 16.22 500 180 Digrim 30 18.03 500 120 B u A c 30 16.04 8 00 120 B u A c 30 12.55 800 90 BuAc 30 12.86 800 90 Digrim 15 11.97 1000 9 0 Digrim 15 10.38 1000 90 BuAc 15 11.0 9 1000 60 B u A c 15 10.810 1500 90 BuAc 15 9.211 1500 60 BuAc 15 9.012 1500 90 Digrim 15 9.513 1800 90 Digrim 1 5 11.214 1800 90 BuAc 15 8.315 1800 60 BuAc 15 8.1 Translation submission form of amendment (Article 184-8 of the Patent Act) September 1993 λ71;

Claims (12)

[Claims] 1. (a) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, the repeating unit Q is the structure ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ have, and n is an integer from 1 to 10, s is 0 or 1, Each X is independently CH2, C(CH3)2, O, S, SO2, CO and OC selected from the group consisting of 6H4O, Each R1 and R2 is independently hydrogen, alkyl containing 1 to 10 carbon atoms. Kyl and alkoxy moieties, selected from the group consisting of phenyl and phenoxy, a and b are independently 0 or an integer from 1 to 4, Z is Cl or Br, E is a vinylbenzyl moiety, an alkyl moiety having 1 to 10 carbon atoms or a base; selected from the group consisting of dihydric phenol and formaldehyde, The substrate is coated with a prepolymer, which is an ether of an oligomeric condensation product with hydride. , (b) The coated prepolymer of (a) is irradiated by passing through the masking. (c) selectively crosslinking portions of the coating of (a); selectively dissolve the unirradiated areas, and (d) further crosslinking the crosslinked prepolymer coating and at 100°C to 300°C for a sufficient time to convert the polymer into an infusible glassy solid. Harden the cross-linked portion of the prepolymer coating by heating to a range of temperatures. to make A method for forming a polymer in a predetermined pattern on a substrate, characterized in that: 2. (a) Formula (1) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, the repeating unit Q is the structure ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ have, and n is an integer from 1 to 10, s is 0 or 1, Each X is independently CH2, C(CH3)2, O, S, SO2, CO and OC selected from the group consisting of 6H4O, Each R1 and R2 is hydrogen, alkyl containing 1 to 10 carbon atoms and an alkoxy moiety independently selected from the group consisting of phenyl and phenoxy; and b are independently 0 or an integer from 1 to 4, Z is Cl or Br, E is a vinylbenzyl moiety, an alkyl moiety containing 1 to 10 carbon atoms, or is selected from the group consisting of benzyl, provided that at least 50% of all E dihydric phenol and formamine, with the proviso that it is a rubenzyl moiety) Ether and (2) (i) 1 molar proportion of oligomeric condensation products with aldehyde of dialdehyde and (ii) about 3 to about 4 molar proportions of phenol. The ether of the synthesis product, and the dialdehyde is OHC(CH2)mC HO (where m is 0 or an integer of 1 to 6), cyclopentanedialdehyde, Phthalaldehyde, isophthalaldehyde, terephthalaldehyde, hexahyde Loftaldehyde, cycloheptane dialdehyde, hexahydroisophthala hexahydroterephthaldehyde and cyclooctanedialdehyde The phenol has the structure R3C6H4 (where R3 is hydrogen or an alkyl group containing from 1 to about 10 carbon atoms), and the preceding The phenolic residues of the oligomeric condensation products described above have a ratio of vinylbenzyl to other moieties. 1:1 to about 6:1, vinylbenzyl, alkyl containing 1 to 10 carbon atoms; a cycloalkyl moiety of 5 to 10 carbon atoms, and a benzyl moiety. etherified with one or more substituents randomly selected from the group. an ether of said oligomeric condensation product, providing an ether moiety; coating a substrate with a mixture of prepolymers consisting of (b) the coated prepolymer of (a); irradiate through the masking pattern to select the areas of the coating that are irradiated. (c) selectively cross-links the non-irradiated portions of the prepolymer coating of (a). selectively dissolve, and (d) further crosslinking said crosslinked coating and rendering said prepolymer infusible; at a temperature in the range of 100°C to 300°C for a sufficient time to convert to a glassy solid. curing the crosslinked portions of the prepolymer coating by heating with , A method for forming a polymer in a predetermined pattern on a substrate, characterized in that: 3. R1 and R2 are hydrogen or alkyl having 1 to 10 carbon atoms The method according to claim 1 or 2. 4. Claim 1 or 2, wherein R1 and R2 are methyl or t-butyl moieties. is the method in Section 2. 5. Claim 1, wherein Z is Br and a and b are 1 to 4, or Method of Section 2. 6. E is at least 70-100% vinylbenzyl moiety and the remaining Claim 1 or 2, wherein E is alkyl having 1 to 10 carbon atoms. Section method. 7. The dialdehyde is OHC(CH2)mCHO and m is 0 or an integer from 1 to 6 The method according to claim 2, wherein: 8. 3. The method of claim 2, wherein R3 is hydrogen or methyl. 9. The ether portion of condensation product (2) is approximately 70% vinylbenzyl and 30% 3. The method of claim 2, wherein the propyl is propyl. 10. Claim 2, wherein the condensation product (2) has a molecular weight of 400 to 6,000. Method. 11. Contains a cured polymer produced by the method according to claim 1 or 2. Electronic interconnect structure. 12. 12. The electrical device of claim 11, wherein said cured polymer is adhered to a chromium metal layer. Child interconnect structure.