CN1162608A - Photoimageable, dielectric, crosslinkable copolyesters - Google Patents
Photoimageable, dielectric, crosslinkable copolyesters Download PDFInfo
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Abstract
Disclosed is a photosensitive, dielectric-insulating and cross linkable polyester film which can be used as a photoresist film for dielectric material and microelectronic circuit, and is suitable for making MCM-L package. In all embodiments of the invention, a compound is provided, which is used for coating the surface of the microelectronic basal piece to form the photosensitive, dielectric-insulating and cross linkable polyester film. The invention can be used for preparing cross-linkable, copolyester and photosensitive oligomer and for preparing MCM-L products by cross-linkable copolyester.
Description
The present invention relates to photoimageable, crosslinked copolyesters dielectric medium, this dielectric medium can be used as the on-chip photoresist film of microelectronic chip and is used as the substrate of production microelectronics Packaging body such as multicore sheet combination layer casting die.
In the common manufacture method of microelectronic chip, there are many steps, comprise, for example, coating adhesion promotor and baking on chip surface, apply dielectric insulation layer and baking on it, coating one deck photoresist film and prebake conditions on it are with photoresist film exposure and development, etching pattern is removed photoresist material and is solidified figuratum circuit card.Except the more reliable chip of needs manufacturing, also wish manufacturing step as much as possible to be saved or merge.
People such as R.Rubner are at " light science and engineering (Photo.Sci.﹠amp; Eng.) " suggestion is incorporated into photosensitive group and makes it can be used as insulating material in the polyimide among 23 (5) 303-309 (1979).Yet, pointed as people such as R.Rubher, this light-sensitive polyimide system has many outstanding shortcomings, includes but not limited to low photosensitivity, about 60% high volumetric shrinkage, the higher cost of polyimide, specific inductivity is higher, and high solidification value needs vacuum to extract volatile matter, poor adhesion, and high-hydroscopicity.So, wish obtaining to form the polymkeric substance of photosensitive film, it has been got rid of one or more shortcomings of the photosensitization polyimide that people such as R.Rubher point out and has been saved a plurality of manufacturing steps in the microelectronic chip manufacturing processed.
In addition, the development need of multicore sheet combination layer casting die (MCM-L) is carried out big improvement to product aspect second-order transition temperature, specific inductivity, resistance, moistureproofness, thermal conductivity and thermal expansivity.Obviously, Resins, epoxy/glass or polyimide/glass system all can not satisfy the needs of MCM-L future development.So, also needing to be suitable for other system that MCM-L uses, it satisfies these needs.
According to the present invention, provide a kind of photosensitive, dielectric insulation, the crosslinkable copolyesters film that are used as dielectric medium and are used as the photoresist film of microelectronic circuit, but it also is suitable for producing MCM-L package and flexibility configuration system.In each embodiment of the present invention, provide to be used for being coated in lip-deep a kind of mixture photosensitive, dielectric insulation, crosslinkable copolyesters film that forms of microelectronic substrates, be used for producing the photosensitive oligopolymer of this crosslinkable copolyesters and the MCM-L product made from this crosslinked copolyesters.Especially advantageously these crosslinked copolyesters produce the ability of bonds well effect by heating and another crosslinked coating down solid-state.
In order to make photosensitive of the present invention, dielectric insulation, crosslinkable copolyesters, two kinds of oligopolymers are provided, a kind of oligopolymer has carboxylic end group and another kind of oligopolymer, and to have acyloxy (preferred acetoxyl group) end group and wherein at least a oligopolymer be branching and wherein a kind ofly in two kinds of oligopolymers to have a group responsive to photolithography (photoetching) in the oligopolymer structure, preferably as end group, thereby form the crosslinkable mixture of these two kinds of oligopolymers.
Term used in the present invention " oligopolymer " should refer to have the low-molecular weight polymer of about 3-25 monomeric unit.Though the molecular weight of oligopolymer changes in can be on a large scale, preferably molecular weight is lower than about 850 and preferably in about 700-850 scope.
Though any crosslinkable oligopolymer has the group responsive to photolithography (photoetching) that is present in the oligopolymer, preferably the responsive group of photolithography (photoetching) is present in the oligopolymer that contains carboxylic end group.
A kind of oligopolymer has carboxylic end group and another kind has the acyloxy end group.Though crosslinkable mixture can comprise two kinds of oligopolymers, should be realized that crosslinkable mixture can comprise two or more oligopolymers and have one or more oligopolymers that carboxylic end group is arranged has the oligopolymer of acyloxy end group with one or more.The acyloxy end group should make that after selecting any free acid that forms is volatile and can discharges from mixture in crosslinked and transesterification process.Example as this class acyloxy can be enumerated CH
3CO
2-, C
2H
5CO
2-, C
6H
5CO
2-, CH
3OCO
2-and similar group.Yet the acyloxy end group is the acetoxyl group end group preferably, i.e. CH
3CO
2-, thereby the volatile acid that discharges is an acetate.The use of using among the present invention " carboxylic end group " should be included in employed curing or crosslinking temperature decomposes the end group that produces carboxylic end group down.
A kind of oligopolymer must be a branching.That is, a kind of oligopolymer has plural end functional groups, promptly plural carboxylic acid or plural acyloxy end group.The oligopolymer that any oligopolymer that contains carboxylic end group can contain three or more carboxylic end group or contain the acyloxy end group can contain three or more acyloxy end group.
Oligopolymer can be a homopolymer.In addition, oligopolymer can be a multipolymer, branching for example, and grafted, linear, random, the multipolymer of alternative or block.Also have, if oligopolymer has stereocenter, this stereocenter has same absolute configuration, random configuration, alternately configuration or any other version.The monomer that is used for preparing above-mentioned oligopolymer includes, but not limited to the 4-hydroxy-benzoic acid, 2-hydroxyl-6-naphthoic acid, quinhydrones, m-phthalic acid, terephthalic acid, 4,4 '-bis-phenol, 1,3, the 5-benzenetricarboxylic acid, 1,2, the 4-benzenetricarboxylic acid, hexanodioic acid, ethylene glycol, oxalic acid quinhydrones ester, the 4-acetoxy-benzoic acid, 2-acetoxyl group-6-naphthoic acid and 4,4 '-the diacetoxy bis-phenol.
A kind of oligopolymer also can have the group responsive to photolithography (photoetching) in its structure, be that used photoresist film is used in photolithography so that resulting crosslinkable film is a photosensitive with film-formable mixture being suitable for producing.This oligopolymer can be introduced any suitable photosensitive group in its structure, thereby makes them have susceptibility to UV, X ray and electron beam photolithography (photoetching) etc.Can enumerate allyl group, especially acrylic acid series or metha crylic group, diazonium groups such as diazo naphthoquinones sulfonate and diazonium-Meldrum acid, oxonium salt group etc. as the example that can be incorporated into the photosensitive group in the oligopolymer structure.Yet preferably, photosensitive group is the allyl group that contains methacryloyl, especially derives and next group from 2-hydroxyethyl methacrylate
Photosensitive group is incorporated into can be by implementing with any synthetic method that the concrete photosensitive group that will introduce adapts with concrete oligopolymer in the oligopolymer.Most preferably, by allowing oligopolymer and the 2-hydroxyethyl methacrylate reaction that contains carboxylic end group, with group
Be incorporated in the oligopolymer that contains carboxylic end group as end group.Should be appreciated that, can change the consumption of 2-hydroxyethyl methacrylate and the some or all of carboxylic end group reactions in the oligopolymer.Obviously, the light reaction group can decompose at elevated temperatures to recover carboxylic end group, and this end group is mainly used to the oligopolymer that contains the acyloxy end group crosslinked.
It should be understood that, according to the present invention, produce photosensitive, dielectric insulation, a kind of in the required two kinds of oligopolymers of crosslinkable copolyesters film is used for first kind of oligopolymer with second kind of oligopolymer reaction, wherein this first kind of oligopolymer is included in the oligopolymer that exists in the oligopolymer the responsive group of photolithography (photoetching), and when this second kind of oligopolymer has the acyloxy end group this first kind of oligopolymer have carboxylic end group and when second kind of oligopolymer has carboxylic end group this first kind of oligopolymer have the acyloxy end group, its condition is, if this second kind of oligopolymer is not branching, then this first kind of oligopolymer is branching.
Can stablize the several months if photosensitivity oligopolymer of the present invention is stored in room temperature and dark, and in polar solvent such as tetrahydrofuran (THF), dimethyl formamide, N-Methyl pyrrolidone etc., be high stability.
In case made necessary oligopolymer, can prepare a kind of mixture that can form photosensitivity, dielectric insulation, crosslinkable copolyesters film, this mixture comprises and is dissolved in following (a) and (b) in the film forming solvent of two class oligopolymers:
(a) at least a oligopolymer with carboxylic end group and
(b) at least a have an oligopolymer of acyloxy end group and wherein, and it is branching that at least a oligopolymer has group and a kind of oligopolymer to the photolithography sensitivity that are present in the oligopolymer.
It should be understood that the film forming mixture can have other non-interfering additive, as photosensitizers, as Michler's keton or analogue.
The present invention also is included in and prepares method photosensitivity, copolyesters film dielectric insulation, crosslinkable on the microelectronic chip with substrate surface, may further comprise the steps:
(a) in film forming solvent, allow at least a oligopolymer mix with at least a oligopolymer with acyloxy end group with carboxylic end group, it is branching that wherein a kind of oligopolymer has group and a kind of oligopolymer to photolithography (photoetching) sensitivity that are present in the oligopolymer, thereby has formed a kind of mixture that forms photosensitivity, crosslinkable film;
(b),, photosensitivity, crosslinkable film on this substrate surface, have been formed on the substrate surface thereby be coated in for example by spin coated or dip-coating with this mixture;
(c) make this film become pattern and the pattern of the gained that develops with photolithography (photoetching) method; With
(d) by this patterned film being heated to the temperature of the photochemical crosslinking structure that is enough to rupture, solidify this acyloxy/carboxylic end group subsequently or simultaneously, on substrate surface, make this patterned film crosslinked.Typically, along with the volatilization at ethene and acrylate part or their degradation production, the structure of photochemical crosslinking ruptures.
Select to solidify employed time and temperature by skilled person in the art by using routine techniques.The composition that will depend on mixture for the accurate set time and the temperature of concrete oligomer mixture.For example, the mixture that comprises the oligopolymer that makes from aromatic monomer will need the higher solidification value of mixture than the oligopolymer that makes from partially aromatic monomer and part aliphatic monomers.Similarly, the mixture that comprises aliphatic oligopolymer will need than mixture of being made up of whole aromatics oligopolymers or the lower solidification value of mixture be made up of aromatics and aliphatic oligopolymer.In general, in solidification process, different oligopolymers further is polymerized to more high molecular weight polymers, takes place crosslinked then.Partly solidified process can be thought the interchain transesterification.After the curing, mixture is the crosslinked copolyesters of solid state.Solidify generally at about 180 ℃-Yue 325 ℃, proceed to many about 2 hours times under the temperature in preferred about 180 ℃-Yue 280 ℃ of scopes.Under certain conditions, under the situation that discharges the volatility structure fragment, solidify, cause crosslinked copolyesters for good and all to become blister.
Another embodiment of the present invention relates to this photosensitivity, dielectric insulation, crosslinkable copolyesters is in the purposes of producing multicore sheet combination layer casting die, production method is: in a manner described, on the liquid crystal polyester substrate, make for example power distribution circuit of several microelectronic circuits, grounding circuit and redistribution circuit etc., use photosensitivity oligopolymer film forming mixture, then two or this laminate of multi-disc are stacked mutually and the laminate that stacks together is applied enough heat and pressure, cause that this laminate bonds together mutually and form multicore sheet laminate by means of shifting in the intermolecular ester group exchange at the interface of copolymerzation with cross-linking ester film of the present invention and liquid crystal polyester substrate.Equally, it is evident that for skilled person in the art that copolyesters photosensitivity of the present invention, crosslinkable can be used for configuration flexible substrate system.
Photosensitivity produced according to the invention, dielectric insulation, crosslinked copolyesters film is characterised in that: the specific inductivity under 25 ℃ and 1MHz is below 4.75 to 2.5 or 2.5, has good dimensional stability, use temperature up to 350-400 ℃, have about 0.4% low-hygroscopicity and high chemical resistant properties, for producing MCM-L, crosslinked foams can be stablized to about 400 ℃, has good photosensitivity, produce good resolving power, with have excellent mechanical intensity and comprise insignificant contraction, for the thick pattern of 3 μ m, generally be lower than 0.1 μ m.And the monomer of producing these products generally is a starting raw material cheaply, about $6/ pound or more cheap.
Can recognize the step that the present invention can save the step of etching polyester and save coating and removed isolating photoresist film from thin dielectric film in the chip production process by reading the following examples.
With exemplary in nature the present invention is described by following embodiment, and nonrestrictive.
Embodiment
Embodiment 1: photoimageable, crosslinkable aromatics oligopolymer
In the flask of reflux exchanger is housed, at N
2Under the situation that air-blowing is swept, in the presence of the 29.11g pyridine, allow 16.8g 1,3,5-benzenetricarboxylic acid (TMA), 21.6g acetoxy-benzoic acid (ABA) and 7.76g oxalic acid quinhydrones ester (HQDA) react and be warming up to 230 ℃ and heated 15 minutes, preparation aromatics oligopolymer.Temperature is increased to 260 ℃ and after 30 minutes, adds additional 12.15g pyridine, and is transparent until solution becomes.Collect 34.65g acetate and pyridine overhead product (T=130 ℃) approximately and after 1 hour temperature is increased to 280 ℃.Stop heating and logical nitrogen after 3 hours, vacuumize then.Collect the 62.31g extractum, comprise about 12g acetate and 50.31g pyridine.By under agitation allowing reaction product mix with 10% acetate and distilled water, filter then, with water rinse twice, filtration and dry in 50 ℃ vacuum drying oven once more, thus reaction product is purified.Obtain about 26.3g buff powder product, isotropy oligopolymer, m.p.:142 ℃.
About 6g oligopolymer is dissolved in the 120ml tetrahydrofuran (THF) (THF),, under 90 ℃, allows reaction mixture refluxed 12 hours then with 15ml thionyl chloride reaction.Vacuum-evaporation thionyl chloride then and THF, obtain the oligopolymer with acid chloride end groups of powder type, then it is dissolved in the 120ml tetrahydrofuran (THF), the 15ml 2-hydroxyethyl methacrylate is added with 15ml triethylamine catalyzer, at room temperature reacted about 8 hours.Afterwards, reaction soln is joined in 50 to 60 times of water under the room temperature, allow oligopolymer precipitate.The solution suction filtration is obtained the light yellow photosensitivity oligopolymer of 3.6g powder (component A), and it has the photosensitivity group that is present in the oligopolymer simultaneously
Carboxylic end group with less concentration.
Has following general formula
Be suitable for subsequently aromatics oligopolymer (B component) with the crosslinking reaction of component A be by in the flask of reflux exchanger is housed under nitrogen atmosphere, allow 22.4g TMA, reacted in 10 minutes and to prepare 19.2g ABA, 72.4gHQDA and 17.72g m-phthalic acid (IPA) are warming up to 230 ℃ of heating.After 30 minutes, acetate begins to run out of with 150 ℃ of overhead product forms.After 2 hours, stopped reaction is collected 38ml acetate.Reaction product is filtration treatment then, with 50-60 times of water rinse, and filtration and dry in 150 ℃ of drying ovens once more, the oligopolymer B of acquisition 89.3g, m.p.:165 ℃.
In the saturated atmosphere of air (50-60% humidity) and solvent vapo(u)r, with Headway ModelEC101 photoresist material spin coated device, the solution rotating that through 20 seconds 2g photosensitivity oligopolymer component A and 0.6g oligopolymer B component is dissolved among the 10mlTHF with the speed of rotation of 2000rpm is coated on the silicon chip, obtains the thickness (measuring with DEKTAK 3030 Auto SurfaceProfilometer) of about 8 μ m on silicon chip.This film prebake conditions 15 minutes in 90 ℃ vacuum drying oven.Then in about 25 ℃, relative humidity are about 48% air-conditioning room and sending under the yellow light sources of light of wavelength＞500nm, with Karl S ü ss MJB3 Mask AligneF photogrammetric case on the photosensitivity film.The intensity of exposed is 15.5nW/cm under the 365nm wavelength
2About 270 seconds.The film of exposure developed for 20 seconds with acetone.
In second test, the Michler's keton photosensitizers of 2.7wt% is joined in the solution of aromatics oligopolymer in THF that concentration is 20wt%.Similarly this solution rotating is coated in and uses on the pretreated silicon chip of hexamethyldisilazane (HMDS).In the saturated atmosphere of air (50-60% humidity) and solvent vapo(u)r, be rotated coating with the speed of rotation of 2000rpm through 20 seconds, obtain the thickness of about 6 μ m.This film prebake conditions 15 minutes in vacuum drying oven.Then in about 25 ℃, relative humidity are about 48% air-conditioning room and sending under the yellow light sources of light of wavelength＞500nm, with Karl S ü ss MJB3Mask Aligner photogrammetric case on the photosensitivity film.The intensity of exposed is 15.5nW/cm under the 365nm wavelength
2About 240 seconds.The film of exposure developed for 20 seconds with acetone.
In two tests, Thinfilm pattern characterizes with Zeiss DSM960 scanning electronic microscope.In two tests, obtain the excellent resolution of 18 μ m, because obtained the excellent pattern line of about 50 μ m width.
Embodiment 2: photoimageable, crosslinkable aromatic-aliphatic oligopolymer
Be equipped with in the reaction flask of reflux exchanger one, 12.2g p-phthaloyl chloride and 3.6g (3.54ml) butanediol in 60mlTHF and 100 ℃ of following reflux 6 hours, are cooled to about 50 ℃ afterwards.In this reaction product, add the 5.2ml 2-hydroxyethyl methacrylate and reacted about 10 hours.After adding 50-60 water doubly, this mixture carries out the photosensitivity that has that suction filtration obtains the 7g white powder
The photosensitivity oligopolymer (component C) of group (carrying out esterification) with the carboxylic end group that is present in the oligopolymer.
Be suitable for subsequently can preparing in accordance with the following methods with copolymerizable, the crosslinkable resin (component D) of the crosslinking reaction of photosensitivity component C.The GP 2037 RESIN-FLAKE novolac resins (available from Georgia-Pacific Corp.) of 1mol by in 50ml 15%NaOH solution under room temperature with the in addition modification of about 2 hours of 3mol acetic anhydride, make component D, the modification varnish resin of following general formula:
Preparation 7g photosensitivity component C and the 2g mixture of 2g component D in 10mlTHF, according to method described in the embodiment 1, with the speed of 2000rpm through 20 seconds with the spin coated of 2g mixture on the silicon nitride disk that HMDS handled, on disk, form the thick film of about 26 μ m.After about 15 minutes, described in embodiment 1, allow this film under 365nm, implement pattern exposure 240 seconds, and develop 90 ℃ of following prebake conditions at this film with acetone.When joining 0.02g Michler's keton sensitizing agent in the film-forming soln, the time shutter was reduced to about 60 seconds.In two tests, Thinfilm pattern characterizes with Zeiss DSM960 scanning electronic microscope.In two tests, obtain the excellent resolution of 16 μ m, because obtained the excellent pattern line of 6 μ m width.
Embodiment 3: photoimageable, crosslinkable aromatic-aliphatic oligopolymer
In the reaction flask of reflux exchanger was housed, with 10.62g 1,3,5-benzene three carbonyl chlorides and 2.7g butanediol were in 80mlTHF, about 8 hours of 90 ℃ of following reflux.In this reaction product, add the solution of 5.2g 2-hydroxyethyl methacrylate in 80mlTHF, and be heated to 50 ℃ about 8 hours.Reaction product is handled in cold water, isolates the white powder photosensitivity oligomerization product (component E) of 8g, and this product has the photosensitivity that is present in the oligopolymer simultaneously
And carboxylic end group.
According to being similar to the method described in 1 and 2 of implementing, this photosensitivity oligopolymer component E can with any suitable crosslinkable copolymerization oligopolymer, as B component, use together and on silicon chip, obtain the photosensitivity film.
Embodiment 4: photoimageable, crosslinkable aromatic-aliphatic oligopolymer
In the reaction flask of reflux exchanger is housed, by with 2.65g 1,3,5-benzene three carbonyl chlorides, 2.7g butyleneglycol and 6.1g p-phthaloyl chloride are dissolved among the 80mlTHF and with this solution and prepared another kind of suitable photosensitivity oligopolymer (component F) in about 8 hours 80 ℃ of following reflux.In the reaction mixture product, add the solution of 2.6g methacrylic acid 2-hydroxyethyl ester in 40ml THF, and heated about 6 hours down at 50 ℃.Product is handled in cold water, isolates 6g white powder photosensitivity oligomerization product (component F), and this product has the photosensitivity that is present in the oligopolymer simultaneously
And carboxylic end group.
According to being similar to the method described in 1 and 2 of implementing, this photosensitivity oligopolymer component F can use with suitable crosslinkable copolymerization oligopolymer (as B component), obtains crosslinkable photosensitivity film on silicon chip.
Embodiment 5: photoimageable, crosslinkable aliphatic oligopolymer
N is being housed
2In the 100ml flask of gas ingress pipe, still head and thermometer, 6.8g tetramethylolmethane and 29.2g hexanodioic acid are warming up to about 1.5 hours of 180 ℃ of heating, cooling makes the 25g reaction product then.In the reaction flask of reflux exchanger is housed, 25g reaction product and 15ml thionyl chloride refluxed about 8 hours down at 80 ℃, subsequently 40 ℃ of following vacuum-evaporation, obtain 25g white cohesive powders powder reaction product, add the solution of 6g methacrylic acid 2-hydroxyethyl ester in 80ml THF to it, and under 50 ℃, heated about 6 hours, handle with postcooling with in 50-60 times of water, suction filtration obtain 17g photoimageable, crosslinkable product (component G), this product has the photosensitivity that is present in the oligopolymer
End group.
According to being similar to the method described in 1 and 2 of implementing, this photosensitivity oligopolymer component G can use with the varnish resin (component D) of acetic ester modification, obtains crosslinkable photosensitivity film on silicon chip.
After photolithographic process, as previously described in the embodiment, the crosslinkable band patterned films of two kinds of crosslinkable oligopolymers on the silicon chip surface of each embodiment is heated the regeneration carboxylic end group, by under nitrogen atmosphere, film being heated about 1 hour down at about 200 ℃-300 ℃, make the foaming of oligopolymer film and make oligopolymer be solidified into crosslinked copolyesters then.Heating can cause the structural degradation of crosslinked photogrammetric case and form carboxylic acid, subsequently, makes crosslinked this film that solidifies of two kinds of oligopolymers in film by forming crosslinked ester bond, discharges acetate simultaneously, causes that cured film bubbles.By the heating and the curing of control film, can control the decline of density of film, thus the control specific inductivity.The product of the Degradation of the structure of photogrammetric case also produces volatile matter, will help foaming at low temperatures.For example, when the patterned film of embodiment 1 solidified about 1 hour down at 280 ℃, it is about 30% that film foams and their density reduce, and promptly is reduced to about 70% density of initial density.Simultaneously, under 25 ℃ and 1MHz the specific inductivity of this film never the specific inductivity 4.75 of cured film be reduced to about 2.3.
In addition, solidified or crosslinked copolyesters film have kept their original size satisfactorily, and promptly those films of the pattern of photo-imaging are only vertically oppositely having thickness loss within reason.Patterned, crosslinked laminated polyester film keeps good in the suprabasil adhesivity of silicon chip.Cured film has passed through so-called adhesion tape test, wherein adheres to a sealing tape on film, then it is stripped down.Can downcut solidifying film layer by enough razors, not cause the crack at edge of rete, and do not reach with hard pencil trial of cut on rete.
And crosslinked, patterned photosensitivity laminated polyester film can be stablized several hrs under 400 ℃ in nitrogen, even the short period of time is exposed to 450 ℃ of influences that also can not cause relief design.
Copolyesters film crosslinked, photosensitivity, dielectric insulation of the present invention can be arranged on the various liquid crystal polyester chip substrates, make power distribution circuit, ground connection tandem circuit and redistribution circuit etc., various laminates stack into the multilayer package mutually, and by heating and pressurization, for example 275 ℃ and 13.7 * 10
6Pa bonds together, in the good cohesive action of intermolecular generation at the interface of crosslinked copolyesters film and liquid crystal polyester substrate.As the example of the liquid crystal polyester of substrate, can enumerate available from the Xydar liquid crystal polyester of Amoco Chemical Corp. with available from the Vectra liquid crystal polyester of Hoechst-Celanese.Yet other liquid crystal polyester that is suitable as substrate is clearly for skilled person in the art.Liquid crystal polyester is especially ideally as substrate.The some of them advantage is the thermal expansivity of control, thermostability, chemical resistant properties, moistureproofness and excellent intrinsic rigidity.All these improved performances the reliability of MCM-L.In the dimensional stability and thermostability that keep patterned film, obtained good cohesive action.Therefore, these crosslinkable films are particularly suitable for MCM-L and use and other package application, and especially for high speed and high-density multicore sheet combination layer casting die package, it improves the signal transmission speed greatly and minimizing is being got lines crossed.
For the narration of front, should be appreciated that for skilled person in the art, can do some improvement to the present invention without departing from the present invention.So, should not think that scope of the present invention is limited to illustrated and described specific embodiment.
Claims (23)
1, can form a kind of mixture of photosensitivity, dielectric insulation, crosslinkable copolyesters film, this mixture comprises and is dissolved in following (a) and (b) in the film forming solvent of two class oligopolymers:
(a) at least a oligopolymer with carboxylic end group and
(b) at least a have an oligopolymer of acyloxy end group and wherein, and it is branching that at least a oligopolymer has group and a kind of oligopolymer to the photolithography sensitivity that are present in the oligopolymer.
2, according to a kind of mixture of formed photosensitivity, copolyesters film dielectric insulation, crosslinkable of claim 1, wherein the acyloxy end group is CH
3CO
2-end group and the group to the photolithography sensitivity that is present in the oligopolymer are
End group.
3, according to a kind of mixture of formed photosensitivity, copolyesters film dielectric insulation, crosslinkable of claim 2, the monomer that wherein is used for preparing oligopolymer is to be selected from the 4-hydroxy-benzoic acid, 2-hydroxyl-6-naphthoic acid, quinhydrones, m-phthalic acid, terephthalic acid, 4,4 '-bis-phenol, 1,3,5-benzenetricarboxylic acid, 1,2, the 4-benzenetricarboxylic acid, hexanodioic acid, ethylene glycol, oxalic acid quinhydrones ester, the 4-acetoxy-benzoic acid, 2-acetoxyl group-6-naphthoic acid and 4,4 '-diacetoxy bis-phenol and methacrylic acid 2-hydroxyethyl ester.
4, according to a kind of mixture of formed photosensitivity, copolyesters film dielectric insulation, crosslinkable of claim 3, the monomer that wherein is used for preparing oligopolymer is to be selected from 1,3, the 5-benzenetricarboxylic acid, oxalic acid quinhydrones ester, 4-acetoxy-benzoic acid, m-phthalic acid and methacrylic acid 2-hydroxyethyl ester.
5, according to a kind of mixture of formed photosensitivity, copolyesters film dielectric insulation, crosslinkable of claim 4, wherein the molecular weight of oligopolymer is in about 850 scopes of about 700-.
6, according to a kind of mixture of formed photosensitivity, copolyesters film dielectric insulation, crosslinkable of claim 1, the oligopolymer that wherein has the acyloxy end group comprises part or all of acetylizad resol.
7, be used to prepare the oligopolymer of photosensitivity, dielectric insulation, crosslinked copolyesters film, this oligopolymer and second kind of oligopolymer reaction in preparation, wherein, described oligopolymer is included in the oligopolymer that exists in the oligopolymer the responsive group of photolithography (photoetching), and when this second kind of oligopolymer has the acyloxy end group described oligopolymer have carboxylic end group and when second kind of oligopolymer has carboxylic end group described oligopolymer have the acyloxy end group, its condition is, if this second kind of oligopolymer is not branching, described oligopolymer is a branching.
8, according to the oligopolymer of claim 7, wherein the acyloxy end group is CH
3CO
2-end group and the group to the photolithography sensitivity that is present in the oligopolymer are
End group.
9, oligopolymer according to Claim 8, wherein oligopolymer has carboxylic end group.
10, according to the oligopolymer of claim 7, the monomer that wherein is used for preparing oligopolymer is to be selected from the 4-hydroxy-benzoic acid, 2-hydroxyl-6-naphthoic acid, quinhydrones, m-phthalic acid, terephthalic acid, 4,4 '-bis-phenol, 1,3, the 5-benzenetricarboxylic acid, 1,2, the 4-benzenetricarboxylic acid, hexanodioic acid, ethylene glycol, oxalic acid quinhydrones ester, the 4-acetoxy-benzoic acid, 2-acetoxyl group-6-naphthoic acid and 4,4 '-diacetoxy bis-phenol and methacrylic acid 2-hydroxyethyl ester.
11, according to the oligopolymer of claim 9, the monomer that wherein is used for preparing oligopolymer is to be selected from 1,3,5-benzenetricarboxylic acid, oxalic acid quinhydrones ester, 4-acetoxy-benzoic acid, m-phthalic acid and methacrylic acid 2-hydroxyethyl ester.
12, according to the oligopolymer of claim 11, wherein the molecular weight of oligopolymer is in about 700-850 scope.
13, preparation is photosensitivity, the method for copolyesters film dielectric insulation, crosslinkable having on the microelectronic chip of substrate surface, may further comprise the steps:
(a) in film forming solvent, allow at least a oligopolymer mix with at least a oligopolymer with acyloxy end group with carboxylic end group, it is branching that wherein a kind of oligopolymer has group and a kind of oligopolymer to photolithography (photoetching) sensitivity that are present in the oligopolymer, thereby has formed a kind of mixture that forms photosensitivity, crosslinkable film;
(b),, photosensitivity, crosslinkable film on this substrate surface, have been formed on the substrate surface thereby be coated in for example by spin coated or dip-coating with this mixture;
(c) make this film become pattern and the pattern of the gained that develops with photolithography (photoetching) method; With
(d) by this patterned film being heated to the temperature of the photochemical crosslinking structure that is enough to rupture, solidify this acyloxy/carboxylic end group subsequently or simultaneously, on substrate surface, make this patterned film crosslinked.
14, according to the method for claim 13, wherein to obtain under 25 ℃ and 1MHz specific inductivity be 4.75 or lower copolymerzation with cross-linking ester for oligopolymer crosslinked.
15, according to the method for claim 13, wherein the acyloxy end group is CH
3CO
2-end group and be to be present in the oligopolymer that contains carboxylic end group to the group of photolithography sensitivity
End group.
16, according to the method for claim 15, the monomer that wherein is used for preparing oligopolymer is to be selected from the 4-hydroxy-benzoic acid, 2-hydroxyl-6-naphthoic acid, quinhydrones, m-phthalic acid, terephthalic acid, 4,4 '-bis-phenol, 1,3, the 5-benzenetricarboxylic acid, 1,2, the 4-benzenetricarboxylic acid, hexanodioic acid, ethylene glycol, oxalic acid quinhydrones ester, the 4-acetoxy-benzoic acid, 2-acetoxyl group-6-naphthoic acid and 4,4 '-diacetoxy bis-phenol and methacrylic acid 2-hydroxyethyl ester.
17, according to the method for claim 16, it is about 700-about 850 that the oligopolymer that wherein has a photosensitivity group has molecular weight.
18, according to any one the prepared microelectronic chip of method among the claim 13-17.
19, prepare the method for multicore sheet combination layer casting die, comprising:
(a) method according to claim 13 prepares a plurality of microelectronic layer casting dies, and each chip has patterned photosensitivity, dielectric insulation, the crosslinked copolyesters film on the liquid crystal polyester substrate surface,
(b) with two or this laminate of multi-disc stacks mutually and
(c) laminate that stacks together is applied enough heat and pressure, cause that by means of shifting this laminate bonds together formation multicore sheet laminate mutually in the intermolecular ester group exchange at the interface of crosslinked copolyesters film and liquid crystal polyester substrate.
20, prepare the method for multicore sheet combination layer casting die, comprising:
(a) method according to claim 15 prepares a plurality of microelectronic layer casting dies, and each chip has patterned photosensitivity, dielectric insulation, the crosslinked copolyesters film on the liquid crystal polyester substrate surface,
(b) with two or this laminate of multi-disc stacks mutually and
(c) laminate that stacks together is applied enough heat and pressure, cause that by means of shifting this laminate bonds together formation multicore sheet laminate mutually in the intermolecular ester group exchange at the interface of crosslinked copolyesters film and liquid crystal polyester substrate.
21,, be that specific inductivity is 4.75 or lower copolyesters film under 25 ℃ and 1MHz wherein at copolyesters film patterned photosensitivity, dielectric insulation, crosslinked on the liquid crystal polyester substrate surface according to the method for claim 19.
22,, be that specific inductivity is 4.75 or lower copolyesters film under 25 ℃ and 1MHz wherein at copolyesters film patterned photosensitivity, dielectric insulation, crosslinked on the liquid crystal polyester substrate surface according to the method for claim 20.
23, the multicore sheet laminate for preparing by the method for any one among the claim 19-22.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104860 CN1162608A (en) | 1996-03-01 | 1997-02-27 | Photoimageable, dielectric, crosslinkable copolyesters |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US609,465/08 | 1996-03-01 | ||
| CN 97104860 CN1162608A (en) | 1996-03-01 | 1997-02-27 | Photoimageable, dielectric, crosslinkable copolyesters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1162608A true CN1162608A (en) | 1997-10-22 |
Family
ID=5167537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97104860 Pending CN1162608A (en) | 1996-03-01 | 1997-02-27 | Photoimageable, dielectric, crosslinkable copolyesters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162608A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10654969B2 (en) | 2017-02-23 | 2020-05-19 | Industrial Technology Research Institute | Thin film and method for manufacturing the same and copper clad laminate |
-
1997
- 1997-02-27 CN CN 97104860 patent/CN1162608A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10654969B2 (en) | 2017-02-23 | 2020-05-19 | Industrial Technology Research Institute | Thin film and method for manufacturing the same and copper clad laminate |
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