Ionization radiation imageable photopolymer compositions

• US 6,916,598 B2
• Filed: 03/21/2003
• Issued: 07/12/2005
• Est. Priority Date: 10/05/1998
• Status: Expired due to Fees

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Wang, Ying
• Primary Examiner(s): Huff, Mark F.
• Assistant Examiner(s): Lee, Sin J.
• Application Number:
  US10/394,060
• Publication Number:
  US 20030180665A1
• Time in Patent Office: 844 Days
• Field of Search: 430/281.1, 430/280.1, 430/283.1, 430/284.1, 430/285.1, 430/905, 430/906, 430/907, 430/909, 430/910, 430/966, 430/967, 430/942, 430/953, 430/325, 430/313, 430/311, 430/330, 430/331, 430/314, 430/945, 264/401
• US Class Current: 430/325
• CPC Class Codes: B33Y 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: Y10S 430/106 Binder containing
• CPC Class Codes: Y10S 430/107 Polyamide or polyurethane
• CPC Class Codes: Y10S 430/108 Polyolefin or halogen containing
• CPC Class Codes: Y10S 430/11 Vinyl alcohol polymer or derivative
• CPC Class Codes: Y10S 430/111 Polymer of unsaturated acid or ester
• CPC Class Codes: Y10S 430/143 Electron beam
• CPC Class Codes: Y10S 430/146 Laser beam
• CPC Class Codes: Y10S 430/154 Neutron beam
• CPC Class Codes: Y10S 430/167 X-ray
• CPC Class Codes: Y10S 430/168 X-ray exposure process

Abstract

This invention discloses compositions that can be polymerized/crosslinked imagewise upon exposure to ionization radiation such as x-ray, electron beam, ion beam, and gamma-ray. This invention also discloses methods of use for these compositions for microfabrication of ceramics, for stereolithography, and for x-ray, e-beam, and ion-beam lithography which can be used for photoresists.

Claims

1. A method of microfabricating ceramic or metal patterns on a solid substrate using ionization radiation comprising the steps of:

mixing together a light stable composition consisting essentially of a reactive monomer, a multi-functional cross-linking agent and ceramic or metal filler;

said mixing process optionally carried out either by heating the composition until melted or by dissolving components in a common solvent;

optionally, in the presence of binder; and

optionally, in the presence of a radiation sensitizer;

casting the composition on a solid substrate to form a film of desired thickness;

irradiating the film with ionization radiation through a mask to form a polymerized/cross-linked image;

developing the polymerized/cross-linked image by rinsing the irradiated film in a solvent to remove unirradiated composition; and

sintering the polymerized/cross-linked image in microfabricated ceramics or metal patterns.

2. The method of claim 1 wherein the composition is selected from the group consisting of (I) a composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetamide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of;

hydrogen;

alliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃; and

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(b) carboxylic acid, —

COOH;

(C) epoxides,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors;

(D) 5 to 90 weight percent of a polymer binder; and

(E) 5 to 90 weight percent of metallic particle or ceramic oxide fillers, said metallic filler is selected from group consisting of Al, Ti, V, Cu, Mn, Fe, Go, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb;

said oxide filler is selected from the group consisting of Al, Ti, V, Cu, Mn, Fe, Go, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W, and Si; and

(II) a composition, that can be polymenzed/cross-linked imagewise by ionizing radiation, consisting essentially of;

(A) from 10 to 90 weight percent of a reactive monomer having at least one arnide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetamide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of;

hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃; and

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(C) 5 to 90 weight percent of a polymer binder; and

(D) 5 to 90 weight percent of metallic or oxide fillers, said metallic filler is selected from group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb;

said oxide filler is selected from the group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W, and Si.

3. The method of claim 1 wherein the source of ionizing radiation is selected from the group consisting of x-ray, electron beam and gamma ray.

4. The method of claim 1 wherein the solid substrate is glass.

5. A method of performing lithography on a semiconductor surface using ionization radiation, comprising the steps of:

mixing together a composition consisting essentially of a reactive monomer and a multi-functional cross-linking agent, optionally by heating the composition until melted or by dissolving in a common solvent;

optionally, in the presence of a polymer binder; and

optionally, in the presence of a radiation sensitizer;

casting the composition on the surface of the solid semiconductor substrate to form a film of desired thickness;

irradiating the film with ionization radiation through a mask to form a polymerized/cross-linked image; and

developing the polymerized/cross-linked image by rinsing the irradiated film in a solvent to remove unirradiated composition.

6. The method of claim 5 further comprising subjecting the semiconductor surface to etching and doping while the portion of the semiconductor surface covered by the polymerized/cross-linked region of the film is protected from etching and doping.

7. The method of claim 5 wherein the composition is selected from the group consisting of (I) a composition that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (m=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetamide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃; and

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors;

(II) a composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of;

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH_2n+1 (n=1 to

     20);

unsaturated aliphatic groups C_nH_2n+1 (n=1 to

     20);

aliphatic groups with amide or acrylainide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of;

hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+1 and C_nH_2n+1 (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃; and

 

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

 

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH_2n+1 (n=1 to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

 

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH_2n+1 (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, HB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors; and

(D) 5 to 90 weight percent of a polymer binder; and

(III) a composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of;

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH_2n+1 (n=1 to

     20);

aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetamide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of;

hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃; and

 

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

 

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

 

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(C) 5-90 weight percent of a polymer binder.

8. The method of claim 5 wherein the ionization radiation is selected from the group constisting of x-ray, electron beam, gamma ray, and ion beam.

9. The method of claim 5 wherein the solid substrate is glass.

10. A method of forming a three-dimensional solid object of polymers, ceramics, or metals using ionization radiation, comprising the steps of:

mixing together a light stable composition consisting essentially of a reactive monomer, a multi-functional cross-linking agent, and a polymer binder, said mixing process optionally done by dissolving in a common solvent or by pouring the composition into a container with a target substrate immersed in it;

optionally, in the presence of a radiation sensitizer; and

optionally, in the presence of a metallic or oxide filler;

irradiating the composition with ionization radiation through a mask or a focused source of ionization radiation to deposit a layer of material on the targeted substrate;

stepping back the substrate and irradiating the substrate;

repeating the step of stepping back the substrate and irradiating the substrate until a desired three-dimensional solid object is formed; and

optionally, treating the solid object post-irradiation to burn out polymer binders.

11. The method of claim 10 wherein the post-irradiation treatment is sintering.

12. The Method of claim 10 wherein the composition is selected from the group consisting of

(II) a composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of:

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH_2n+1 (n=1 to

     20);

aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH_2n+1 (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetamide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁and R₂ are selected from the group consisting of;

hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=l to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyariurate, C₃N₃O₃; and

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=l to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, IIIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors; and

(D) 5 to 90 weight percent of a polymer binder,

(III) a composition, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of;

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH_2n+1 (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetamide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁and R₂ are selected from the group consisting of;

hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃; and

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(C) from 0.1 to 80 weight percent of an inorganic radiation sensitizer having a particle size in the range of 1 nanometer to 1000 nanometers, said radiation sensitizer is selected from the group consisting of VB-VIB semiconductors, VB-VIIB semiconductors, IIB-VIB semiconductors, IIB-VB semiconductors, IIIB-VB semiconductors, ITIB-VIB semiconductors, IB-VIB semiconductors, and IVB-VIIB semiconductors;

(D) 5 to 90 weight percent of a polymer binder; and

(E) ₅ to 90 weight percent of metallic particle or ceramic oxide fillers, said metallic filler is selected from group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb;

said oxide filler is selected from the group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W, and Si;

(IV) a compositon, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of;

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, said monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

aliphatic groups with amide or acrylamide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetamide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH_2n−

(n=1 to

     20); and

amino-substituted aliphatic groups C_nH_2n+1 and C_nH_2n−

(n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone is selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)n—

, n=1-1000, where R represents an ailiphatic group, C_nH_2n+1 and C_nH_2n−

(n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-1000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃; and

wherein the functional groups are selected from the group consisting of;

(a) acrylates,

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH_2n−

(n=1 to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH_2n−

(n=1 to

     20); and

(C) 5-90 weight percent of a polymer binder;

(V) a compositon, that can be polymerized/cross-linked imagewise by ionizing radiation, consisting essentially of;

(A) from 10 to 90 weight percent of a reactive monomer having at least one amide functional group, saed monomer selected from the group consisting of;

where R₁, R₂, R₃, R₄, and R₅ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

aliphatic groups with amide or acrylarnide substituent, and aliphatic groups with R′

O—

substituent where R′

represents aliphatic group, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

acetarnide;

where R₁ and R₂ are selected from the group consisting of hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20); and

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20);

where R₁ and R₂ are selected from the group consisting of;

hydrogen;

aliphatic groups C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

unsaturated aliphatic groups C_nH<sub>2n−

1</sub> (n=1 to

     20); and

amino-substituted aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(B) from 10 to 90 weight percent of a multifunctional cross-linking agent, said cross-linking agent consists of a backbone having at least 2 functional groups, said backbone selected from the group consisting of;

(1) linear or branched aliphatic chains, —

(CRH)_n—

, n=1-1000, where R represents an aliphatic group, C_nH_2n+and C_nH_2n+1 (n=1 to

     20);

(2) ethylene glycol chains, —

(CH₂CH₂O)_n—

where n=1-1000;

(3) propylene glycol chains, —

(CH(CH₃)CH₂O)_n—

where n=1-l000;

(4) cyclohexyl; and

(5) isocyanurate, C₃N₃O₃and wherein the functional groups are selected from the group consisting of;

(a) acrylates,

where R₁, R₂, and R₃ are selected from the group consisting of hydrogen and aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=1 to

     20);

(b) carboxylic acid, —

COOH;

(c) epoxides,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH_2n+1 (n1 to

     20); and

(d) vinyls,

where R₁, R₂, and R₃ are selected from;

hydrogen or aliphatic groups, C_nH_2n+1 and C_nH<sub>2n−

1</sub> (n=l to

     20);

(C) 5 to 90 weight percent of a polymer binder; and

(D) 5 to 90 weight percent of metallic or oxide fillers, said metallic filler is selected from group consisting of Al, Ti, V, Cu, Mn, Fe, Ca, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb;

said oxide filler is selected from the group consisting of Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W, and Si.

13. The method of claim 12 wherein ionization radiation source is selected from the group consisting of x-ray and electron beam.