US3779807A

US3779807A - Process for applying multiple microelectronic layers to substrate

Info

Publication number: US3779807A
Application number: US00188475A
Authority: US
Inventors: L Taylor; J Grier
Original assignee: Owens Illinois Inc
Current assignee: Techneglas LLC
Priority date: 1971-10-12
Filing date: 1971-10-12
Publication date: 1973-12-18
Anticipated expiration: 1990-12-18

Abstract

There is disclosed a process for applying multiple microelectronic layers to a substrate which comprises applying at least two different fugitive vehicle systems to a substrate, each system comprising at least one microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the binder, each solvent being capable of removal from the substrate at a temperature below the pyrolyzing temperatures of the polymer in its respective system and the polymer in each previously applied system. The polymeric binder of each applied system is insoluble in the polymeric binder and solvent of the subsequently applied system. Each solvent is appropriately vaporized from the substrate so as to form at least two layers of microelectronic material dispersed in a film of binder.

Description

United States Patent 9 Taylor et al.

[ Dec. 18, 1973 PROCESS FOR APPLYING MULTIPLE MICROELECTRONIC LAYERS TO SUBSTRATE [75] lhventors: Lynn J. Taylor, Haslett; John D.

Grier, Temperance, both of Mich.

[73] Assignee: Owens-Illinois, lnc., Toledo, Ohio [22] Filed: Oct. 12, 1971 [21] Appl. No.: 188,475,

[52] U.S. Cl. 117/215, 117/46 CA, 117/69, 117/217, 117/218 [51] Int. Cl B44d 1/14 [58] Field of Search 117/217, 218, 215, 117/46 R, 46 CA, 69

[56] References Cited UNITED STATES PATENTS 2,105,552 1/1938 Ruben 117/217 2,880,181 3/1959 Williams 117/217 3,565,694 2/1971 Chireau 117/216 3,580,738 5/1971 Ranby 117/218 3,722,045 3/1973 Beuscher 117/217 Primary ExaminerCameron K. Weiffenbach Attbrney-Donald Keith Wedding et al.

57 ABSTRACT There is disclosed a process for applying multiple microelectronic layers to a substrate which comprises applying at least two different fugitive vehicle systems to a substrate, each system comprising at least one microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the binder, each solvent being capable of removal from the substrate at a temperature below the pyrolyzing temperatures of the polymer in its respective system and the polymer in each previously applied system. The polymeric binder of each applied system is insoluble in the polymeric binder and solvent of the subsequently applied system. Each solvent is appropriately vaporized from the substrate so as to form at least two layers of microelectronic material dispersed in a film of binder.

22 Claims, No Drawings PROCESS FOR APPLYING MULTIPLE MICROELECTRONIC LAYERS TO SUBSTRATE BACKGROUND OF THE DISCLOSURE a layer of each microelectronic material dispersed in a film of its respective binder.

More particularly, there is provided a process for applying multiple layers of materials to a substrate which This invention relates to the application of multi- 5 comprises the steps of:

microelectronic layers to a substrate.

Fugitive vehicle systems are generally well known in the prior art, as evidenced for example by U. S. Pat. No. 2,312,229 issued to Anderson which discloses a process for coating vitreous surfaces withfluorescent materials by suspending fluorescent powder in a binder comprising a solution of polystyrene in a solvent. Similar systems are disclosed by U. S. Pat. No. 2,328,101 issued to Rosenblatt and U. S. Pat. No. 3,475,161 issued to Ramirez.

Fugitive vehicle systems have been especially useful in the coating art. Thus particulate coating materials are commonly applied to substrates by a wet process, that is, while dispersed in a system consisting of a binder and a solvent. Such a process typically requires mixing of the binder, the solvent, and the inorganic material to form a paste or slurry which is applied to the surface to be coated.

The wet coating technique is commonly used to seal glass or ceramic parts, as in the formation of cathode ray tubes wherein the face plate is attached to the funnel. In such technique, a paste having solder glass dis tributed throughout a binder-solvent system is applied to the edges of one part in the form of a ribbon. The remaining part is then placed in contact with the paste and the assemblage is heated to evaporate the solvent, burn out the binder, and fuse the solder glass. While this technique is extensively used, quality control is difficult and expensive because of carbonaceous or like residue which may not be removed by evaporation or burning during the heating step. Likewise, during the evaporation of the solvent,there may be changes in the viscosity and/or thixotropic character of' the system which may result in sutih deleterious effects as orange peel formation, fish eye formation, etc., especially on flat surfaces. V

In an effort to overcome the difficulties inherent in applying a coating or sealant to substrates via a binder solvent system, the prior art has used-dry coating compositions containing polymeric binders and having the particulate coating material uniformly distributed therethrough. These compositions are formed into films which are applied to the substrate to be coated and then heated to burn out the binder and form a coating of the inorganic material usually in fused or sintered form. However, the presence of a carbonaceous residue may still present a problem in such a system.

In accordance with this invention, there is provided a process for applying multiple microelectronic layers to a substrate which comprises applying at least two different, fugitive vehicle systems to a substrate, each system comprising at least one microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the binder, each solvent being capable of removal from the substrate at a temperature below the pyrolyzing temperatures of the polymer in its respective system and the polymer in each previously applied system; the polymeric binder of each applied system being insoluble in the polymeric binder and solvent of the subsequently applied system; and then vaporizing each solvent from the substrate so as to form applying to the substrate a first fugitive vehicle system containing microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the polymeric binder, the solvent being capable of removal from the substrate by vaporization at a temperature below the pyrolyzing temperature of the binder;

vaporizing the solvent from the substrate so as to form a first layer of microelectronic material dispersed in a film of binder;

' applying to the first layer a second fugitive system containing microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the polymeric binder, the solvent being capable of removal from the second fugitive system by vaporization at a temperature below the pyrolyzing temperature of each binder in each system,

the polymeric binder of the first system being insoluble in the polymeric binder and solvent of the second system;

and vaporizing the solvent from the second fugitive system so as to form a second layer of microelectronic material dispersed in a film of binder.

If it is desired to apply further layers, the process is continued, e.g. by applying a third system, vaporizing the solvent therefrom, etc.

As used herein, pyrolyzing is defined as the decomposition of the polymeric material to gaseous products without passing through a broad liquid range and without leaving a noticeable carbonaceous or other like residue which would interfere with the intended function of the system.

The polymeric material is one which will pyrolyze, as distinguished from vaporization, when appropriate energy is applied thereto at some predetermined energy level above the level of energy required to remove the solvent.

Energy level, as used herein, is intended to include any reasonably measurable molecular energy .state which is related to the pyrolyz ing of the polymer and/or removal of the solvent. The most obvious energy level is temperature, which has been defined as the average molecular kinetic energy. Hereinafter, temperature level will be used as a synonym for energy level. However, the invention is not limited to temperature level alone, but is intended to include any molecular energy level or state which can be obtained by any appropriate energy from any source or means, such as chemical,

contemplated if the conditions of handling so warrant.

The use of a solid polymeric material is advantageous in' that the material behaves as a binder during the interval between the evaporation of the solvent and the pyrolytic removal of the polymeric material. This may be especially important when the fugitive vehicle system is being loaded with other materials, e.g. for'coating a substrate.

The polymeric material is typically selected from one or more pyrolyzable solid polymers or copolymers which tend to pyrolyze cleanly in an inert environment, such as polyethers including poly(tetrahydrofuran), poly(l,3-dioxolane), and poly(alkylene oxides), especially poly(ethylene oxide) or poly(propylene oxide);

poly(alkyl methaerylates) including those where the alkyl contains one to six carbons, especially poly(- methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate); methacrylate copolymers including methyl methaerylate/n-butyl methacrylate copolymers, methyl methacrylate/alpha methyl styrene copolymers, n-butyl methaerylate/alpha methyl styrene copolymers, methyl methacrylate/styrene copolymers, and methyl methacrylate/dimethyl itaconate copolymers; and other selected polymers and copolymers including polyisobutylene; poly(trimethylene carbonate); poly(beta-propiolactone); poly(deltavalerolactone); poly(ethylene carbonate); poly(propylene carbonate); poly(ethylene oxalate); vinyl toluene/alphamethylstyrene copolymers; styrene/alphamethylstyrene copolymers; and olefin-sulfur dioxide copolymers.

In one specific embodiment hereof, there is used a polymeric material having oxygen atoms selectively incorporated in its molecular chain, as, for example, peroxy linkages in the chain. Such a pyrolyzable polymer is disclosed in copending U.S. Pat. application Ser. No. 653,020, filed July 13, 1967 by Dr. Don N. Gray and assigned to the same assignee as that of the instant patent application. Typically there is used a copolymer, terpolymer, or quadpolymer of oxygen and at least one monomer of alkyl methacrylate with the alkyl containing one to six carbon atoms, e.g. methyl to hexyl, preferably butyl. Copolymers of oxygen with other vinyl monomers may also be utilized.

The common characteristic of the selected polymeric material is that it must be solid at ambient temperature and pyrolyzable at an elevated temperature, e.g. about 250C. to about 450C.

This pyrolysis mechanism of removal of the composition of the invention is of great advantage in nonoxygen containing atmospheres, but the compositions may also be used in an oxygen-containing atmosphere. This characteristic permits the use of a continuum of atmospheric pressures downward from somewhat less than 14.7 lbs. per sq. in. absolute to vacua approaching the micron range. Likewise, inert environments such as nitrogen, argon, etc. may be used.

In addition there may be utilized polymers which tend to pyrolyze more cleanly in the presence of an oxidizing environment such as air relative to an inert environment.

Typical polymers include cellulose derivations such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and methyl hydroxypropyl cellulose; poly(vinyl alcohol); polycaprolac tone; and poly(vinyl acetate).

The organic solvent component of the vehicle system preferably comprises one or more organic solvents having a boiling temperature below the pyrolysis temperature of the polymer, e.g. within a range of about 100C. to about 400C., preferably about 200C. to about 350C. The use of high boiling solvents makes the fugitive system effectively non-drying at room temperature.

Examples of suitable solvents include polychlorinated polyphenyls (Arochlor 122] or 1232, manufactured by Monsanto Chemical Co.,); dialkyl phthalates, such as dimethyl, diethyl, or di-n-butyl phthalate; di-n-butyl succinate; dimethyl sebacate; di-benzyl ether; butyl benzoate; acetyl triethyl citrate; glyceryl triacetate; beta-ethoxy ethyl benzoate; isoamyl benzoate; benzyl benzoate; isobutyl salicylate; isoamyl salicylate; benzyl salicylate; ethyl laurate; butyl oleate; ethyl myristate; butyl benzyl phthalate; dimethyl suberate; diethyl sebacate; diethyl azelate; di-n-butyl adipate; diisobutyl adipate; dibutyl sebacate; dibutyl tartrate; glyceryl tributyrate; diethyl isophthalate; butyl palmitate; dodecylbenzene; tetradeeylbenzene; pentaethylbenzene; diphenylmethane; l,1-diphenylethane; l-chloronaphthalene; l-bromonaphthalene; dimethylnaphthalene (various isomers, and mixtures thereof); l-methoxy naphthalene; n-alkanes containing 14 to 20 carbon atoms and mixtures thereof; diphenyl ether; bis(alpha-methylbenzyl) ether; tetraethylene glycol dimethyl ether; 2-benzyloxyethanol; phenyl n-hexyl carbinol; triethylene glycol; 1,5-pentanediol; hexanophenone; l-naphthyl methyl ketone; p-n-pentylphenol; N-cyclohexyl-2-pyrrolidone; glutaronitrile; and pmethoxyphenylacetonitrile. The selected solvent may also be thermally degradable to volatile products, e.g. within the boiling range temperatures indicated above.

It is also contemplated using volatile solvents having a relatively low boiling temperature. Typical solvents include water; volatile alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ketones such as acetones, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, amyl acetate; ethers such as dibutyl ether, ethylene glycol monoethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic and alicyclic hydrocarbons such as nheptane, isooctane, methyl cyclohexane, cyclohexane; chlorinated aliphatic and aromatic hydrocarbons such as chlorobenzene, chloroform, l,l,l-trichloroethane; amides such as N,N-dimethyl formamide; and nitriles such as acetonitrile, benzonitrile.

Among the organic solvents, it is also possible to se lect some which act as plasticizers for the polymer, thereby obtaining a beneficial solvating effect.

The relative proportions of solvent (or plasticizer) and polymeric material will depend upon the respective types of materials. However, the weight ratio of solvent to polymeric material will generally be within a range of about :1 to about 1:100, preferably about 10:1 to about 1:10.

The fugitive vehicle compositions of this invention have numerous advantages and utility depending upon what microelectronic materials are incorporated therein. Such microelectronic materials include electrically conductive, resistive, insulating, and/or semiconductive ceramics, metals, metalloids, glasses, oxides, etc, including mixtures thereof.

In addition, the compositions may contain other suitable ingredients such as pigments, fillers, resins, etc.

This invention is especially advantageous in the formation of thick-film systems designed for processing in non-oxidizing atmospheres, e.g. as in the preparation of microelectronic circuits, devices, and components thereof. Another particular use comprises a glazing process wherein a powdered glass is applied to a subpolymeric binder and a solvent for the binder, each solvent being capable of removal from the substrate at a temperature below the pyrolyzing temperatures of the polymer in its respective system and the polymer in each previously applied system; the polymeric binder of each applied system being insoluble in the polymeric binder and solvent of the subsequently and adjacently applied system; and vaporizing each solvent from said fugitive vehicle systems by the application of heat so as to form at least two layers, each layer comprising microelectronic material dispersed in a polymeric binder, and

. removing each binder from each layer by pyrolysis and fusing or sintering the microelectronic material of each layer at temperatures between about 250C and about 450C so as to form a continuous multilayered microelectronic structure.

2. The invention of claim 1 wherein each solvent is vaporized from its respectivesystem prior to the applying of the subsequent and adjacent system.

3. The invention of claim 1 wherein the solvent of a previously applied system is simultaneously vaporized with the solvent of a subsequently applied system.

4. The invention of claim 1 wherein each polymeric binder is a solid at a temperature of about 40F to about 120F.

5. The invention of claim 1 wherein each solvent has a boiling or decomposition temperature of about 100C to about 400C.

6. The invention of claim 1 wherein the weight ratio of solvent to polymeric material within each system ranges from about 100:1 to about 1:100.

7. The invention of claim 1 wherein at least three fugitivevehicle systems are applied so as to form at least three layers of microelectronic material dispersed in a polymeric binder, the binder or solvent of the first applied system. being the same as that of the third applied system. i v y 8. The invention of claim 1 wherein the polymeric binder of each system is .a pyrolyzable soluble polymer selected from polyisobutylene, poly(trimethylene carbonate poly(beta-propiolactone poly(deltavalerolactone), poly(ethylene carbonate), poly(propylene carbonate), poly(ethylene oxalate), methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, poly(vinyl alcohol), polycaprolactone, and poly(vinyl acetate).

9. The invention of claim 1 wherein the polymeric binder of each system is a pyrolyzable copolymer selected from a methyl methacrylate/n-butyl methacrylate copolymer, a methyl methacrylate/alpha methyl styrene copolymer, a methyl methacrylate/styrene copolymer, a methyl methacrylate/dimethyl itaconate copolymer, a vinyl toluene/alpha-methylstyrene copoly mer, and a styrene/alpha-methylstyrene copolymer.

10. The invention of claim 1 wherein the solvent of each system is selected from dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-butyl succinate, dimethyl sebacate, di-benzyl ether, butyl benzoate, acetyl triethyl citrate, glyceryl triacetate, beta-ethoxy ethyl benzoate, isoamyl benzoate, benzyl benzoate, isobutyl salicylate, isoamyl salicylate, benzyl salicylate, ethyl laurate, butyl oleate, ethyl myristate, butyl benzyl phthalate, dimethyl suberate, diethyl sebacate, diethyl azelate, di-n-butyl adipate, diisobutyl adipate, dibutyl 'sebacate, dibutyl tartrate, glyceryl tributyrate, diethyl iosphthalate, butyl palmitate, dodecylbenzene, tetradecylbenzene, pentaethylbenzene, diphenylmethane, 1,1- diphenylethane, l-chloronaphthalene, lbromonaphthalene, dimethyl-naphthalene, l-methoxy naphthalene, diphenyl ether, bis(alpha-methylbenzyl) ether, tetraethylene glycol dimethyl ether, 2 benzyloxyethanol, phenyl n-hexyl carbinol, triethylene glycol, 1,5 pentanediol, hexanophenone, l-naphthyl methyl ketone, pn-pentylphenol, N-cyclohexyl-2- pyrrolidone, glutaronitrile, prnethoxyphenylacetonitrile, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, amyl acetate, dibutyl ether, ethylene glycol monoethyl ether, benzene, toluene, xylene, n-heptane, isooctane, methyl cyclohexane, cyclohexane, chlorobenzene, chloroform, 1,1,1-trichloroethane, N,N-dimethyl formamide, acetonitrile, and benzonitrile.

11. The invention of claim 1 wherein at least one polymeric binder is a poly (alkyl methacrylate) with the alkyl containing one to six atoms.

12. The invention of claim 1 1 wherein the poly (alkyl methacrylate) has oxygen atoms selectively incorporated in its molecular chain.

13. The invention of claim 1 wherein the polymeric binder of each system is a pyrolyzable solid polymer selected from polyethers and poly (alkyl methacrylates).

14. The invention of claim 13 wherein the polymeric binder of each system is a pyrolyzable solid polymer selected from poly(tetrahydrofuran), poly(1,3- dioxolane), poly(ethylene oxide), poly(propylene oxide), poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate).

15. A process for forming a microelectronic structure comprising a. applying multiple layers of materials to a substrate by the steps of:

applying to the substrate a first fugitive vehicle system containing microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the polymeric binder, the solvent being capable of removal from the substrate by vaporization at a temperature below the pyrolyzing temperature of the binder;

vaporizing the solvent from saidfirst fugitive vehicle system so as to form a first layer of microelectronic material dispersed in a film of binder;

applying to the first layer a second fugitive system containing microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the polymeric binder, the solvent being capable of removal from the second fugitive system by vaporization at a temperature below the pyrolyzing temperature of each binder in each system, the polymeric binder of the first system being insoluble in the polymeric binder and solvent of the second system; and vaporizing the solvent from the second fugitive system so as to form a second layer of microelectronic material dispersed in a film of binder, and

b. removing each binder from each layer by pyrolysis and fusing or sintering the microelectronic material of each layer at temperatures between about 250C and about 450C so as to form a continuous multilayered microelectronic structure.

16. The invention of claim wherein each solvent has a boiling or decomposition temperature within the range of about 100C to about 400C.

17. The invention of claim 15 wherein the weight ratio of solvent to polymeric material within each system ranges from about lOOzl to about 1:100.

18. The invention of claim 15 wherein the polymeric binder of each system is a pyrolyzable soluble polymer selected from polyisobutylene, poly(trimethylene carbonate), poly(beta-propiolactone), poly(deltavalerolactone), poly(ethylene carbonate), poly(propylene carbonate), poly(ethylene oxalate), methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, poly(vinyl alcohol), polycaprolactone, and poly(vinyl acetate).

19. The invention of claim 15 wherein the polymeric binder of each system is a pyrolyzable copolymer selected from a methyl methacrylate/n-butyl methacrylate copolymer, a methyl methacrylate/alpha methyl styrene copolymer, a methyl methacrylate styrene copolymer, a methyl methacrylate/dimethyl itaconate copolymer, a vinyl toluene/alphamethylstyrene copolymer, and a styrene/alpha-methylstyrene copolymer.

20. The invention of claim 15 wherein the solvent of each system is selected from dimethyl phthalate, di-

methyl ketone, p-n-pentylphenol, N-cyclohexyl-Z- pyrrolidone, glutaronitrile, pmethoxyphenylacetonitrile, water, methyl alcohol,

ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, amyl acetate,dibutyl ether, ethylene glycol monoethyl ether, benzene, toluene, xylene, n-heptane, isooctane, methyl cyclohexane, cyclohexane, chlorobenzene, chloroform, 1,1,1-trichloroethane, N,N-dimethyl formamide, acetonitrile, and benzonitrile.

21. The invention of claim 15 wherein the polymeric binder of each system is a pyrolyzable solid polymer selected from polyethers and poly(alkyl methacrylates).

22. The invention of claim 21 wherein the polymeric binder of each system is a py rolyzable solid polymer selected from poly(tetrahydrofuran poly( 1,3- dioxolane), poly(ethylene oxide), poly(propylene oxide), poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate).

Claims

2. The invention of claim 1 wherein each solvent is vaporized from its respective system prior to the applying of the subsequent and adjacent system.
3. The invention of claim 1 wherein the solvent of a previously applied system is simultaneously vaporized with the solvent of a subsequently applied system.
4. The invention of claim 1 wherein each polymeric binder is a solid at a temperature of about 40*F to about 120*F.
5. The invention of claim 1 wherein each solvent has a boiling or decomposition temperature of about 100*C to about 400*C.
6. The invention of claim 1 wherein the weight ratio of solvent to polymeric material within each system ranges from about 100:1 to about 1:100.
7. The invention of claim 1 wherein at least three fugitive vehicle systems are applied so as to form at least three layers of microelectronic material dispersed in a polymeric binder, the binder or solvent of the first applied system being the same as that of the third applied system.
8. The invention of claim 1 wherein the polymeric binder of each system is a pyrolyzable soluble polymer selected from polyisobutylene, poly(trimethylene carbonate), poly(beta-propiolactone), poly(delta-valerolactone), poly(ethylene carbonate), poly(propylene carbonate), poly(ethylene oxalate), methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, poly(vinyl alcohol), polycaprolactone, and poly(vinyl acetate).
9. The invention of claim 1 wherein the polymeric binder of each system is a pyrolyzable copolymer selected from a methyl methacrylate/n-butyl methacrylate copolymer, a methyl methacrylate/alpha methyl styrene copolymer, a methyl methacrylate/styrene copolymer, a methyl methacrylate/dimethyl itaconate copolymer, a vinyl toluene/alpha-methylstyrene copolymer, and a styrene/alpha-methylstyrene copolymer.
10. The invention of claim 1 wherein the solvent of each system is selected from dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-butyl succinate, dimethyl sebacate, di-benzyl ether, butyl benzoate, acetyl triethyl citrate, glyceryl triacetate, beta-ethoxy ethyl benzoate, isoamyl benzoate, benzyl benzoate, isobutyl salicylate, isoamyl salicylate, benzyl salicylate, ethyl laurate, butyl oleate, ethyl myristate, butyl benzyl phthalate, dimethyl suberate, diethyl sebacate, diethyl azelate, di-n-butyl adipate, diisobutyl adipate, dibutyl sebacate, dibutyl tartrate, glyceryl tributyrate, diethyl iosphthalate, butyl palmitate, dodecylbenzene, tetradecylbenzene, pentaethylbenzene, diphenylmethane, 1,1-diphenylethane, 1-chloronaphthalene, 1-bromonaphthalene, dimethyl-naphthalene, 1-methoxy naphthalene, diphenyl ether, bis(alpha-methylbenzyl) ether, tetraethylene glycol dimethyl ether, 2-benzyloxyethanol, phenyl n-hexyl carbinol, triethylene glycol, 1,5 pentanediol, hexanophenone, 1-naphthyl methyl ketone, p-n-pentylphenol, N-cyclohexyl-2-pyrrolidone, glutaronitrile, p-methoxyphenylacetonitrile, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, amyl acetate, dibutyl ether, ethylene glycol monoethyl ether, benzene, toluene, xylene, n-heptane, isooctane, methyl cyclohexane, cyclohexane, chlorobenzene, chloroform, 1,1,1-trichloroethane, N,N-dimethyl formamide, acetonitrile, and benzonitrile.
11. The invention of claim 1 wherein at least one polymeric binder is a poly (alkyl methacrylate) with the alKyl containing one to six atoms.
12. The invention of claim 11 wherein the poly (alkyl methacrylate) has oxygen atoms selectively incorporated in its molecular chain.
13. The invention of claim 1 wherein the polymeric binder of each system is a pyrolyzable solid polymer selected from polyethers and poly (alkyl methacrylates).
14. The invention of claim 13 wherein the polymeric binder of each system is a pyrolyzable solid polymer selected from poly(tetrahydrofuran), poly(1,3-dioxolane), poly(ethylene oxide), poly(propylene oxide), poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate).
15. A process for forming a microelectronic structure comprising a. applying multiple layers of materials to a substrate by the steps of: applying to the substrate a first fugitive vehicle system containing microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the polymeric binder, the solvent being capable of removal from the substrate by vaporization at a temperature below the pyrolyzing temperature of the binder; vaporizing the solvent from said first fugitive vehicle system so as to form a first layer of microelectronic material dispersed in a film of binder; applying to the first layer a second fugitive system containing microelectronic material dispersed in a film-forming, pyrolyzable, polymeric binder and a solvent for the polymeric binder, the solvent being capable of removal from the second fugitive system by vaporization at a temperature below the pyrolyzing temperature of each binder in each system, the polymeric binder of the first system being insoluble in the polymeric binder and solvent of the second system; and vaporizing the solvent from the second fugitive system so as to form a second layer of microelectronic material dispersed in a film of binder, and b. removing each binder from each layer by pyrolysis and fusing or sintering the microelectronic material of each layer at temperatures between about 250*C and about 450*C so as to form a continuous multi-layered microelectronic structure.
16. The invention of claim 15 wherein each solvent has a boiling or decomposition temperature within the range of about 100*C to about 400*C.
17. The invention of claim 15 wherein the weight ratio of solvent to polymeric material within each system ranges from about 100:1 to about 1:100.
18. The invention of claim 15 wherein the polymeric binder of each system is a pyrolyzable soluble polymer selected from polyisobutylene, poly(trimethylene carbonate), poly(beta-propiolactone), poly(delta-valerolactone), poly(ethylene carbonate), poly(propylene carbonate), poly(ethylene oxalate), methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, poly(vinyl alcohol), polycaprolactone, and poly(vinyl acetate).
19. The invention of claim 15 wherein the polymeric binder of each system is a pyrolyzable copolymer selected from a methyl methacrylate/n-butyl methacrylate copolymer, a methyl methacrylate/alpha methyl styrene copolymer, a methyl methacrylate styrene copolymer, a methyl methacrylate/dimethyl itaconate copolymer, a vinyl toluene/alphamethylstyrene copolymer, and a styrene/alpha-methylstyrene copolymer.
20. The invention of claim 15 wherein the solvent of each system is selected from dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-butyl succinate, dimethyl sebacate, di-benzyl ether, butyl benzoate, acetyl triethyl citrate, glyceryl triacetate, beta-ethoxy ethyl benzoate, isoamyl benzoate, benzyl benzoate, isobutyl salicylate, isoamyl salicylate, benzyl salicylate, ethyl laurate, butyl oleate, ethyl myristate, butyl benzyl phthalate, dimethyl suberate, diethyl sebacate, diethyl azelate, di-n-butyl adipate, diisobutyl adipate, dibutyl sebacate, dibutyl tartrate, glyceryl tributyrate, diethyl isophthalAte, butyl palmitate, dodecylbenzene, tetradecylbenzene, pentaethylbenzene, diphenylmethane, 1,1-diphenylethane, 1-chloronaphthalene, 1-bromonaphthalene, dimethyl-naphthalene, 1-methoxy naphthalene, diphenyl ether, bis(alpha-methylbenzyl) ether, tetraethylene glycol dimethyl ether, 2-benzyloxyethanol, phenyl-n-hexyl carbinol, triethylene glycol, 1,5 pentanediol, hexano-phenone, 1-naphthyl methyl ketone, p-n-pentylphenol, N-cyclohexyl-2-pyrrolidone, glutaronitrile, p-methoxyphenylacetonitrile, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, amyl acetate,dibutyl ether, ethylene glycol monoethyl ether, benzene, toluene, xylene, n-heptane, isooctane, methyl cyclohexane, cyclohexane, chlorobenzene, chloroform, 1,1,1-trichloroethane, N,N-dimethyl formamide, acetonitrile, and benzonitrile.
21. The invention of claim 15 wherein the polymeric binder of each system is a pyrolyzable solid polymer selected from polyethers and poly(alkyl methacrylates).
22. The invention of claim 21 wherein the polymeric binder of each system is a pyrolyzable solid polymer selected from poly(tetrahydrofuran), poly(1,3-dioxolane), poly(ethylene oxide), poly(propylene oxide), poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate).