Highly plasma etch-resistant photoresist composition containing a photosensitive polymeric titania precursor

• US 6,303,270 B1
• Filed: 03/01/1999
• Issued: 10/16/2001
• Est. Priority Date: 03/01/1999
• Status: Expired due to Term

• Current Assignee: Brewer Science Inc., Curators of the University of Missouri (University of Missouri)
• Original Assignee: Brewer Science Inc., Curators of the University of Missouri (University of Missouri)
• Inventors: Guerrero, Douglas J., Petrovsky, Vladimir, Fowler, Michelle R., James, William J., Flaim, Tony D., Anderson, Harlan U.
• Primary Examiner(s): Hamilton, Cynthia
• Application Number:
  US09/259,229
• Time in Patent Office: 960 Days
• Field of Search: 430/287.1, 430/285.1, 430/284.1, 430/311, 525/389, 528/220, 528/395
• US Class Current: 430/284.1
• CPC Class Codes: C08G 79/00 Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
• CPC Class Codes: G03F 7/0042 with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists G03F7/075 takes precedence
• CPC Class Codes: G03F 7/0388 with ethylenic or acetylenic bands in the side chains of the photopolymer

Abstract

A composition is derived from an addition polymerizable organotitanium polymer which upon exposure to an oxygen plasma or baking in air, is converted to titanium dioxide (titania) or is converted to a mixed, titanium-containing metal oxide. The metal oxide formed in situ imparts etch-resistant action to a patterned photoresist layer. The composition may also be directly deposited and patterned into permanent metal oxide device features by a photolithographic process.

Claims

1. A plasma etch-resistant photoresist composition comprised of:

(a) an organotitanium polymer or organotitanium copolymer produced by reacting;

a poly(alkyltitanate) or a poly(alkyltitanate-co-alkylmetallate) or mixtures thereof wherein the alkyl groups of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate) are bonded to respective oxygen atoms which are bonded to the titanium atom of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate), with

addition polymerizable beta-diketones, beta-ketoesters, alpha-hydroxy carboxylic acid salts, alpha-hydroxy carboxylic acid esters or mixtures thereof; and

(b) a solvent vehicle suitable for obtaining high quality thin films on device substrates by spin casting.

2. The plasma etch-resistant photoresist composition of claim 1 is further comprised of an addition polymerizable co-monomer having at least one ethylenically unsaturated double bond.

3. The plasma etch-resistant photoresist composition of claims 1 or 2 wherein the composition is further comprised of a soluble metallic compound which is stable in the photoresist composition.

4. The plasma etch-resistant photoresist composition of claim 3 wherein the soluble metallic compound is selected from the group consisting of soluble metal carboxylates, metal alkoxides, metal hydroxides, metal organo chelates, metal chlorides, and metal nitrates.

5. The plasma etch-resistant photoresist composition of claim 2 wherein the co-monomer is selected from the group of mono- and polyfunctional (meth)acrylate esters consisting of 2-hydroxyethyl (meth)acrylate;

ethylene glycol dimethacrylate, pentaerythritol triacrylate and tetraacrylate;

dipentaerythritol pentaacrylate and hexaacrylate;

polyester (meth)acrylates obtained by reacting (meth)acrylate acid with polyester prepolymers;

urethane (meth)acrylates;

epoxy (meth)acrylates prepared by reacting (meth)acrylic acid with epoxy resins such as bisphenol-A epoxy resins, bisphenol-F epoxy resins, and novolak epoxy resins; and

tris(2-acryloyloxyethyl) isocyanurate.

6. The plasma etch-resistant photoresist composition of claim 2 wherein the co-monomers are selected from acrylic-functional metal complexes prepared by transesterifying titanium or zirconium alkoxides with 2-hydroxyethyl acrylate or a chelating organic moiety having at least one ethylenically unsaturated double bond.

7. The plasma etch-resistant photoresist composition of claim 1 wherein the copolymerized alkylmetallate is selected from the group consisting of —

(RO)Al—

O—

, —

(RO)₂Zr—

O—

, —

(R′

)₂Si—

O—

, and —

(RO)₂Si—

O—

, wherein R and R′

are monovalent organic radicals.

8. The plasma etch-resistant photoresist composition of claim 1 wherein the organotitanium polymer is produced by reacting poly(n-butyltitanate) and 2-acetoacetoxyethyl (meth)acrylate, said polymer or copolymer having the formula;

wherein R_c equals —

CH₂—

CH₂—

O—

CO—

C(CH₃)═

CH₂, Bu equals —

CH₂—

CH₂—

CH₂—

CH₃, x+y=2, x equals 0.1 to 2.0, and n>

2.

9. The plasma etch-resistant photoresist composition of claim 1 wherein the organotitanium polymer is the reaction product of a poly(alkyltitanate) and a titanium chelant which has been functionalized to enable addition polymerization.

10. The plasma etch-resistant photoresist composition of claim 1 wherein the organotitanium polymer is produced by reacting poly(n-butyltitanate) and an alpha-hydroxy carboxylic acid salt, said polymer or copolymer having the formula:

where B⁺ equals —

(H₃C)₂NH⁺—

R—

COCA═

CH₂, R equals —

CH₂—

CH₂—

CH₂—

NH—

or —

CH₂—

CH₂—

O—

, Bu equals —

CH₂CH₂CH₂CH₃, x+y=2, x is between 0.1 to 2.0, A equals —

H or —

CH₃, and n>

2.

11. The plasma etch-resistant photoresist composition of claim 1 wherein the organotitanium polymer is the reaction product of a titanate orthoester having at least one ethylenically unsaturated double bond and a limited amount of water to form a soluble polymeric condensation product.

12. The plasma etch-resistant photoresist composition of claim 1 wherein the organotitanium polymer is produced by reacting copolymers of alkytitanates and alkylsilicates and other alkylmetallates having metals selected from the group consisting of aluminum, zirconium, cerium, niobium, and tantalum.

13. The plasma etch-resistant photoresist composition of claim 1 wherein the photoresist composition is further comprised of materials to enhance color, with the material being selected from the group consisting of solvent-soluble dyes and pigments.

14. The plasma etch-resistant photoresist composition of claim 1 wherein the solvent is selected from the group consisting of:

alcohols, esters, glymes, ethers, glycol ethers, ketones, and combinations thereof.

15. The plasma etch-resistant photoresist composition of claim 1 wherein exposure to a high energy source will crosslink the organotitanium polymer or copolymer by inducing addition polymerization.

16. The plasma etch-resistant photoresist composition of claim 15 wherein the high energy source is selected from the group consisting of an electron beam, an x-ray source, and combinations thereof.

17. The plasma etch-resistant composition of claim 1 wherein the composition further comprises a free radical-generating photopolymerization initiator or initiator system.

18. The plasma etch-resistant photoresist composition of claim 17 wherein the free radical initiator or initiator system operates effective 200-500 nm exposure wavelenghts.

19. An organotitanium polymer capable of addition polymerization, wherein the organotitanium polymer is selected from the group consisting of:

(a)

where R_c equals —

CH₂CH₂OCOC(CH₃)═

CH₂, Bu equals —

CH₂CH₂CH₂CH₃, x+y=2, x is between 0.1 and 2.0, and n>

2; and

where B⁺ equals —

(H₃C)₂NH⁺—

R—

COCA═

CH₂, R equals —

CH₂—

CH₂—

CH₂—

NH—

or —

CH₂—

CH₂—

O—

, Bu equals —

CH₂CH₂CH₂CH₃, x+y=2, x is between 0.1 and 2.0, A equals —

H or —

CH₃, and n>

2.

20. A method for forming an organotitanium polymer capable of addition polymerization, wherein the method is comprised of:

reacting a titanium polymer or copolymer selected from the group consisting of poly(alkyltitanates) and poly(alkyltitanates-co-alkylmetallates) with a compound selected from the group consisting of addition polymerizable beta-diketones, beta-ketoesters, alpha-hydroxy carboxylic acid salts, and alpha-hydroxy carboxylic acid esters, wherein the alkyl groups of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate) are bonded to respective oxygen atoms which are bonded to the titanium atom of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate).

21. An organotitanium polymer capable of addition polymerization, wherein the organotitanium polymer is the reaction product of:

(a) a titanium polymer or copolymer selected from the group consisting of poly(alkyltitanates) and poly(alkyltitanates-co-alkylmetallates), wherein the alkyl groups of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate) are bonded to respective oxygen atoms which are bonded to the titanium atom of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate; and

(b) a compound selected from the group consisting of addition polymerizable beta-diketones, beta-ketoesters, alpha-hydroxy carboxylic acid salts, and alpha-hydroxy carboxylic acid esters.

22. A dried photoresist composition on a substrate, wherein the photoresist composition is comprised of:

(a) an addition polymerizable organotitanium polymer added in an amount equal to between about 15% by weight and about 90% by weight of the photoresist composition, said polymer being produced by reacting;

a poly(alkyltitanate) or a poly(alkyltitanate-co-alkylmetallate) or mixtures thereof wherein the alkyl groups of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate) are bonded to respective oxygen atoms which are bonded to the titanium atom of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate), with

addition polymerizable beta-diketones, beta-ketoesters, alpha-hydroxy carboxylic acid salts, alpha-hydroxy carboxylic acid, esters or mixtures thereof; and

(b) a photopolymerization initiator that operates at 200-500 nm added in an amount equal to between about 1% and about 20% by weight of the photoresist composition.

23. The photoresist composition of claim 22 wherein the addition polymerizable organotitanium polymer is added in an amount equal to between about 40% and about 80% by weight of the photoresist composition.

24. The photoresist composition of claim 22 wherein the photopolymerization initiator is added in an amount equal to between about 10% and about 15% by weight of the photoresist composition.

25. The photoresist composition of claim 22 wherein the addition polymerizable organotitanium polymer is selected from the group consisting of:

where R_c equals —

CH₂CH₂OCOC(CH₃)═

CH₂, Bu equals —

CH₂CH₂CH₂CH₃, x+y=2, x is between 0.1 and 2.0, and n>

2; and

,

(b)

where B⁺ equals —

(H₃C)₂NH⁺CH₂CH₂OCOCA═

CH₂, Bu equals —

CH₂CH₂CH₂CH₃, x+y=2, x is between 0.1 and 2.0, A equals —

H or —

CH₃, and n>

2.

26. The photoresist composition of claim 22 wherein the photopolymerization initiator is selected from the group consisting of:

trihalomethyl-substituted triazines, trihalomethyl-substituted oxadiazoles, imidazoles, hexaaryl biimidazoles, benzoin alkyl ethers, anthraquinones, benzanthrones, benzophenones, acetophenones, thioxanthones, benzoic acid esters, acridines, phenazines, titanium compounds, and mixtures thereof.

27. The photoresist composition of claim 22 wherein the photoresist composition includes a co-monomer added in an amount equal to between about 0 and about 80% by weight of the photoresist composition, with the co-monomer selected from the group consisting of:

mono- and polyfunctional (meth)acrylate esters, ethylene glycol dimethacrylate, pentaerythritol triacrylate, tetraacrylate, dipentaerythritol pentaacrylate and hexaacrylate;

polyester (meth)acrylates obtained by reacting (meth)acrylate acid with polyester prepolymers, urethane (meth)acrylates, epoxy (meth)acrylates prepared by reacting (meth)acrylic acid with epoxy resins such as bisphenol-A epoxy resins, bisphenol-F epoxy resins, and novolak epoxy resins, and tris(2-acryloyloxyethyl) isocyanurate.

28. The photoresist composition of claim 27 wherein the co-monomer is added in an amount equal to between about 0 and about 50% by weight of the photoresist composition.

29. The photoresist composition of claim 22 wherein the photoresist composition includes a non-photopolymerizable metallic compound added in an amount equal to between about 0 and about 60% by weight of the photoresist composition, with the metallic compound selected from the group consisting of:

metal carboxylates, metal alkoxides, metal hydroxides, metal organo chelates, and metal salts.

30. The photoresist composition of claim 29 wherein the non-photopolymerizable metallic compound is added in an amount equal to between about 0 and about 40% by weight of the photoresist composition.

31. A method for preparing a photoresist composition, wherein the method is comprised of:

(a) stirring in a solvent solution an addition polymerizable organotitanium polymer and a photopolymerization initiator, said polymer being produced by reacting;

a poly(alkyltitanate) or a poly(alkyltitanate-co-alkylmetallate) or mixtures thereof wherein the alkyl groups of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate) are bonded to respective oxygen atoms which are bonded to the titanium atom of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate), with

addition polymerizable beta-diketones, beta-ketoesters, alpha-hydroxy carboxylic acid salts, alpha-hydroxy carboxylic acid, esters or mixtures thereof; and

(b) diluting the composition of step (a) with additional solvent to achieve a total solids level of about 30% by weight, thereby forming the photoresist composition.

32. The method of claim 31 wherein the solution is selected from the group consisting of:

alcohols esters, glymes, ethers, glycol ethers, ketones, and combinations thereof.

33. The method of claim 31 wherein a co-monomer is added to the photoresist composition.

34. The method of claim 31 wherein a non-addition polymerizable metallic composition is added to the photoresist composition.

35. A microelectronic device structure comprising a plasma etch resistant, titanium-containing photoresist layer coated on a substrate wherein the photoresist layer has a film thickness ranging between about 0.05 microns and about 1.00 microns, with the microelectronic device structure comprised of:

(a) the substrate selected from the group consisting of ceramic, metal, polymer, and semiconductor substrates; and

(b) the photoresist layer, with the photoresist layer comprised of an addition polymerizable organotitanium polymer added in an amount equal to between about 15% by weight and about 90% by weight of the photoresist composition and a photopolymerization initiator that operates at 200-500 nm added in an amount equal to between about 1% and about 20% by weight of the photoresist composition, said polymer being produced by reacting;

a poly(alkyltitanate) or a poly(alkyltitanate-co-alkylmetallate) or mixtures thereof wherein the alkyl groups of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate) are bonded to respective oxygen atoms which are bonded to the titanium atom of the poly(alkyltitanate) or poly(alkyltitanate-co-alkylmetallate), with

addition polymerizable beta-diketones, beta-ketoesters, alpha-hydroxy carboxylic acid salts, alpha-hydroxy carboxylic acid esters or mixtures thereof.

36. A method for forming a microelectronic device structure having a titanium containing metal oxide layer, comprised of:

(a) selecting a substrate material selected from the group consisting of ceramic, metal, polymer, and semiconductor substrates;

(b) applying a photoresist composition comprised of a photopolymerizable organotitanium polymer to the substrate by spin coating the photoresist composition onto the substrate at a speed ranging between 500 and 5000 rpm for a time equal to between about 30 seconds and 90 seconds, so that the photoresist is present on the substrate at a thickness equal to between about 0.05 microns and about 1.00 microns, thereby forming a photoresist coated substrate;

(c) exposing the photoresist coated substrate to ultraviolet radiation passing through a mask, wherein the ultraviolet radiation is equal to between about 10 mJ/cm² and about 1000 mJ/cm² to form an exposed photoresist coated substrate;

(d) developing the exposed photoresist coated substrate in a solution selected from the group consisting of an aqueous alkali solution and an aqueous chelant solution to form a patterned photoresist; and

,

(e) converting the patterned photoresist to an etch resistant metal oxide layer on the substrate by heating, thereby forming the microelectronic device structure.

37. The method of claim 36 wherein step (e) is achieved by baking the patterned photoresist in air at a temperature ranging between about 150°

C. and about 300°

C. for a time period ranging between about 15 minutes and about 60 minutes so as to decompose organic components and leave an inorganic layer that is etch resistant.

38. A plasma etch-resistant photoresist composition comprised of:

(a) an organotitanium polymer or copolymer produced by reacting;

a poly(alkyltitanate) or a poly(alkyltitanate-co-alkylmetallate) or mixtures thereof, with

addition polymerizable alcohols, carboxylic acids, beta-diketones, beta-ketoesters, or alpha-hydroxy carboxylic acids, alpha-hydroxy carboxylic acid salts, alpha-hydroxy carboxylic esters, or mixtures thereof, said polymer comprising an addition polymerizable co-monomer having at least one ethylenically unsaturated double bond;

(b) a free radical-generating photopolymerization initiator or initiator system; and

,

(c) a solvent vehicle suitable for obtaining high quality thin films on device substrates by spin casting.

39. The plasma etch-resistant photoresist composition of claim 38 wherein the composition is further comprised of a soluble metallic compound which is stable in the photoresist composition.

40. The plasma etch-resistant photoresist composition of claim 38 wherein the comonomer is selected from the group consisting of mono- and polyfunctional (meth)acrylate esters consisting of 2-hydroxyethyl (meth)acrylate;

ethylene glycol dimethacrylate, pentaerythritol triacrylate and tetraacrylate;

dipentaerythritol pentaacrylate and hexaacrylate;

polyester (meth)acrylates obtained by reacting (meth)acrylate acid with polyester prepolymers;

urethane (meth)acrylates;

epoxy (meth)acrylates prepared by reacting (meth)acrylic acid with epoxy resins such as bisphenol-A epoxy resins, bisphenol-F epoxy resins, and novolak epoxy resins; and

tris(2-acryloyloxyethyl) isocyanurate.

41. The plasma etch-resistant photoresist composition of claim 38 wherein the comonomers are selected from the group consisting of acrylic-functional metal complexes prepared by transesterifying titanium or zirconium alkoxides with 2-hydroxyethyl acrylate or a chelating organic moiety having at least one ethylenically unsaturated double bond.

42. The plasma etch-resistant photoresist composition of claim 41 wherein the soluble metallic compound is selected from the group consisting of soluble metal carboxylates, metal alkoxides, metal hydroxides, metal organo chelates, metal chlorides, and metal nitrates.

43. A plasma etch-resistant photoresist composition comprised of:

(a) an organotitanium polymer or copolymer produced by reacting alkyltitanates and alkylsilicates and other alkylmetallates having metal selected from the group consisting of aluminum, zirconium, cerium, niobium, and tantalium;

(b) a free radical-generating photopolymerizable initiator or initiator system; and

(c) a solvent vehicle suitable for obtaining high quality thin films on device substrates by spin-casting.

44. A plasma etch-resistant photoresist composition comprised of:

(a) an organotitanium polymer or copolymer produced by reacting poly(n-butyltitanate) and 2-acetoacetoxyethyl (meth)acrylate, said polymer or copolymer having the formula;

wherein R_c equals —

CH₂—

CH₂—

O—

CO—

C (CH₃)═

CH₂, Bu equals —

CH₂—

CH₂—

CH₂—

CH₃, x+y=2, x equals 0.1 to 2.0, and n>

2.

45. A plasma etch-resistant photoresist composition comprised of:

(a) an organotitanium polymer or copolymer produced by reacting a poly(alkyltitanate) and titanium chelant which has been functionalized to enable addition polymerization;

(b) a free radical-generating photopolymerizable initiator or initiator system; and

(c) a solvent vehicle suitable for obtaining high quality thin films on device substrates by spin-casting.

46. A plasma etch-resistant photoresist composition comprised of:

(a) an organotitanium polymer or copolymer produced reacting poly(n-butyltitanate) and an alpha-hydroxycarboxylic acid salt, said polymer or copolymer having the formula;

where B⁺ equals (H₃C)₂NH⁺—

R—

COCA═

CH₂, R equals —

CH₂—

CH₂—

CH₂—

NH—

or —

CH₂—

CH₂—

O—

, Bu equals —

CH₂CH₂CH₂CH₃, x+y=2, x is between 0.1 to 2.0, A equals —

H or —

CH₃, and n>

2;

(b) a free radical-generating photopolymerizable initiator or initiator system; and

(c) a solvent vehicle suitable for obtaining high quality thin films on device substrates by spin-casting.

47. A method for preparing a photoresist composition, wherein the method is comprised of:

(a) stirring in a solvent solution an addition polymerizable organotitanium polymer, a photopolymerization initiator, and a co-monomer; and

(b) diluting the composition of step (a) with additional solvent to achieve a total solids level of about 30% by weight, thereby forming the photoresist composition.

48. A method for preparing a photoresist composition, wherein the method is comprised of:

(a) stirring in a solvent solution an addition polymerizable organotitanium polymer, a photopolymerization initiator, and a non-addition polymerizable metallic composition; and

(b) diluting the composition of step (a) with additional solvent to achieve a total solids level of about 30% by weight, thereby forming the photoresist composition.