Source: https://patents.google.com/patent/US6066889?oq=flatulence
Timestamp: 2018-03-22 12:20:54
Document Index: 142037463

Matched Legal Cases: ['application No. 07', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 09', 'application No. 09', 'application No. 09']

US6066889A - Methods of selectively filling apertures - Google Patents
Methods of selectively filling apertures Download PDF
US6066889A
US6066889A US09158811 US15881198A US6066889A US 6066889 A US6066889 A US 6066889A US 09158811 US09158811 US 09158811 US 15881198 A US15881198 A US 15881198A US 6066889 A US6066889 A US 6066889A
US09158811
Preferably, the diglycidyl ether of the bisphenol A has an epoxide value of from about 0.1 to about 5, more preferably from about 1 to about 3, most preferably about 1.5 equivalents per kilogram, a weight per epoxide of from about 200 to about 1000, more preferably from about 500 to about 750, most preferably about 675 and a melting point of from about 70° C. to about 150° C., more preferably from about 80° C. to about 110° C., most preferably about 97° C.
The hole fill film is thermally stable, particularly at lamination temperatures preferably up to at least 125° C. for 1 hour. The hole fill film in the preferred embodiment is thermally stable particularly at electroless bath temperatures. Typically, copper electroless plating baths have a pH of at least 11, and a temperature of at least about 70° C. A typical bath contains a caustic agent typically, sodium hydroxide, formaldehyde and a copper source such as copper sulfate. Typically gold electroless plating baths have a pH of about 14, and a temperature of about 70° C. The gold bath typically contains dimethyl amino borane and caustic agents.
The hole fill film of the preferred embodiment withstands gold electroless plating bath conditions at pH 14, at least 60° C. for 45 minutes and withstands copper electroless plating bath conditions at pH 11, at least 73° C. for 10 hours.
The film is prepared by coating a liquid or paste onto a support, preferably a polymeric support, such as polyester. Suitable polyester support for the film, includes, for example, polyethylene terephthalate available under the trade name MYLAR®, from DuPont, and MELINEX from ICI. The film is applied to the polymeric support in liquid form or paste form, using conventional application methods such as, for example, curtain coating, screen coating, roller coating or spray coating. Good results have been obtained using about a 1 to 4 mil thick film.
After the film is applied to the substrate, the backing, if present, is removed; optionally the solvent is driven off from the film to provide a solvent content preferably less than about 5%, more preferably less than about 3%. Good results have been obtained by drying at about 100° C. for about 1 hour. The backing is preferably reapplied before lamination.
The apertures, such as through holes, are filled with hole fill film by reflowing the hole fill film. Preferably a lamination press, more preferably vacuum lamination press, is used to impart pressure and temperature to the hole fill film to cause the film to flow into the apertures. Good results have been obtained using a vacuum lamination press at about 500 psi and about 125° C., for about 1 hour. If the hole fill film is applied to only one side there is often shrinkage on the opposite side which results in an indentation in the cured hole fill film. Accordingly, the hole film is preferably also applied to the backside of the substrate, preferably the second layer of hole film is applied using a vacuum laminator. The polymeric support is then peeled and preferably, solvent is removed from the hole fill film; good results have been obtained by drying in conventional oven at 125° C. for about one hour.
The hole fill film present in the apertures is then photo-imaged using conventional techniques. Preferably, the hole fill film is exposed to ultraviolet light through desired artwork which is preferably in contact with the hole fill film, to expose the filled apertures. The hole fill film is then baked; good results have been obtained at 125° C. for about one hour. The hole fill film is then developed, preferably using propylene carbonate or butyrolactone to remove the hole fill film which was not exposed to the actinic radiation. Thus, the hole fill film remains in those apertures which were exposed to actinic radiation, along with hole fill film surrounding the perimeter of the exposed apertures. The hole fill film in the apertures is then finally cured, preferably in a two step process. First the hole fill film is exposed to ultraviolet light, preferably in the range of 250 to 400 nm, and preferably at a dosage of 4 Joules; secondly the hole fill film is thermally cured. Good thermal cures have been obtained in a convection oven at from about 150° C. to about 180° C. for about 30 to about 90 minutes.
A photoimageable composition was prepared having a solids content of from about 86.5% to about 89%, such solids comprising: about 27.44% PKHC a phenoxy resin; 41.16% of Epirez 5183 a tetrabromobisphenol A; 22.88% of Epirez SU-8, an octafunctional epoxy bisphenol A formaldehyde novolac resin, 4.85% UVE 1014 photoinitiator; 0.07% ethyl violet dye; 0.03% FC 430 a fluorinated polyether nonionic surfactant from 3M Company; 3.85% Aerosil 380, an amorphous silicon dioxide from Degussa. The solvent content is typically greater than about 20%. The solvent was a mixture of methyl ethyl ketone and propylene glycol monomethyl ether acetate. The photoimageable composition was coated onto a 1.42 mil thick polyethylene terephthalate designated "MYLAR®, D" a polyester carrier from Dupont. The photoimageable composition was allowed to dry to provide a 2.8 mil thick photoimageable hole fill film on the polyethylene terephthalate carrier, to provide a solvent content of from about 11 to about 13.5% of the total weight of the hole fill film.
The core was placed in a vacuum laminator so that the hole fill film was adjacent to a release sheet and next to a first surface of the core, then the core was laminated at about 60° C. for about 15 seconds. The core was then placed in a vacuum press at 125° C., 500 psi for 60 minutes. The core was then removed from the press, the MYLAR® polymeric support was removed, and the core was baked at 125° C. for about 1 hour to drive off solvent. Then the core was photoimaged by exposing it to 2000 mj/cm2 ultraviolet light through a film mask. The core was then partially cured by baking at 125° C. for 1 hour and then developed with propylene carbonate. Next, the hole fill film was uv bumped, that is, blanket exposed to 4 Joules/cm2 and then baked at 180° C. for 1 hour. Nubs were removed by mechanical sanding. The resulting structure had completely filled through holes.
Next, circuitry was formed by conventional processes; and prepared for gold plating using conventional processes. The core was placed in a conventional gold electroless plating bath containing dimethyl amino borane, at 60° C., pH 14 for about 45 minutes, rinsed, and then dried. The cured hole fill film was examined after the immersion in the plating bath; the cured hole fill film was intact. Microscopic examination at 30X revealed no bubbling, and no lifting of the cured hole fill film. The electroless plating bath was not contaminated.
A planar copper core was prepared as in Example 1, except prior to placing the core in the lamination press, the core was baked at 125° C. for 60 minutes to substantially remove the solvent from the dry film.
apertures disposed in said circuitized substrate;
cured hole fill film disposed in said apertures;
wherein the hole fill film comprises solids which comprise an epoxy resin system comprising:
i. from about 10 to about 80% of phenoxy polyol resin which is the condensation product of epichlorohydrin and bisphenol A, having a molecular weight of from about 40,000 to about 130,000;
ii. from about 20% to about 90% of an epoxidized multifunctional bisphenol A formaldehyde novolac resin having a molecular weight of from about 4,000 to about 10,000;
iii. from 0 to 50% of a diglycidyl ether of bisphenol A having a molecular weight of from about 600 to about 2,500;
from 0 to about 20% of a thixotrope.
2. The circuitized structure of claim 1, wherein there is:
from about 20% to about 40% of phenoxy polyol resin having a molecular weight of from about 60,000 to about 90,000;
from about 25 to about 30% of an epoxidized multifunctional bisphenol A formaldehyde novolac resin having a molecular weight of from about 5,000 to about 7,000;
from about 35 to about 50%, of a brominated diglycidyl ether of bisphenol A having a molecular weight of from about 1,000 to about 1,700.
3. The circuitized structure of claim 2, wherein there is:
about 45% diglycidyl ether a tetrabromobisphenol A having an epoxide value of about 1.5 equivalents per kilogram, a weight per epoxide of about 675 and a melting point of about 97° C.; and
4. The circuitized structure of claim 2, wherein the circuitized structure is a circuit board, card, carrier, organic or inorganic single chip module, organic or inorganic multi-chip module, ceramic carrier, laminate chip carrier or interposer card.
6. A circuitized structure comprising:
apertures disposed in said substrate filled with cured hole fill film;
from 0 to about 20% of a thixotrope;
an electrolessly plated structure, disposed on and in contact with the substrate;
solder mask disposed on, and in contact with the substrate; electronic components, soldered or wire bonded to the electrolessly plated structure.
7. The circuitized structure of claim 6, wherein there is:
8. The circuitized structure of claim 7, wherein there is:
9. The circuitized structure of claim 6, wherein the circuitized structure is a circuit board, card, carrier, organic or inorganic single chip module, organic or inorganic multi-chip module, ceramic carrier, laminate chip carrier or interposer card.
US09158811 1998-09-22 1998-09-22 Methods of selectively filling apertures Expired - Fee Related US6066889A (en)
US09158811 US6066889A (en) 1998-09-22 1998-09-22 Methods of selectively filling apertures
US09484671 US6376158B1 (en) 1998-09-22 2000-01-18 Methods for selectively filling apertures
US09484671 Division US6376158B1 (en) 1998-09-22 2000-01-18 Methods for selectively filling apertures
US6066889A true US6066889A (en) 2000-05-23
ID=22569808
US09158811 Expired - Fee Related US6066889A (en) 1998-09-22 1998-09-22 Methods of selectively filling apertures
US09484671 Expired - Fee Related US6376158B1 (en) 1998-09-22 2000-01-18 Methods for selectively filling apertures
US (2) US6066889A (en)
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:JONES, GERALD W.;MARCELLO, HEIKE;PAPATHOMAS, KOSTAS;REEL/FRAME:009477/0550;SIGNING DATES FROM 19980918 TO 19980921