Molecular Organometallic Resists for EUV

• US 20150079393A1
• Filed: 09/13/2013
• Published: 03/19/2015
• Est. Priority Date: 09/13/2013
• Status: Active Grant

• Current Assignee: The Research Foundation for The State University of New York (State University of New York)
• Original Assignee: The Research Foundation for The State University of New York (State University of New York)
• Inventors: CARDINEAU, Brian, FREEDMAN, Daniel, MARNELL, Miles, BRAINARD, Robert
• Granted Patent: US 9,372,402 B2
• Time in Patent Office: Days
• US Class Current: 428/402
• 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 7/0043 Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof G03F7/0044 takes precedence
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

Described herein are organometallic or inorganic complexes with high extreme ultraviolet (EUV) optical density (OD) and high mass density for use in thin films. These thin films are used as high resolution, low line edge roughness (LER) EUV photoresists. The complexes may also be included in nanoparticle form for use in photoresists.

Claims

1. A photoresist comprising at least one complex (BD₂)_zM(L^a)_n (L^b)_o(L^c)_p(L^d)_q or (A)_yM(L^e)_n(L^f)_o(L^g)_p(L^h)_q, wherein:

M is a metal having a coordination number of Q;

Q is an integer selected from 2, 3, 4, 5, 6, 7, or 8;

BD₂ is oxalate or carbonate;

L^a, L^b, L^c and L^d are ligands, each having a denticity of, respectively, w^a, w^b, w^c and w^d;

z is 1, 2 or 3;

n, o, p, and q are independently zero, one or two;

the sum of (n·

w^a) plus (o·

w^b) plus (p·

w^c) plus (q·

w^d) is equal to (Q minus 2z);

A is selected in each instance from azide and (—

NO₂);

L^e, L^f, L^g and L^h are ligands, each having a denticity of, respectively, w^e, w^f, w^g and w^h;

y is any integer up to and including Q; and

the sum of (n·

w^e) plus (o·

w^f) plus (p·

w^g) plus (q·

w^h) is equal to (Q minus y);

wherein said complex is balanced by a counter ion, if necessary.

2. The photoresist according to claim 1, wherein BD₂ is oxalate.

3. The photoresist according to claim 1, wherein M is selected from zirconium, manganese, aluminum, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, thulium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, and bismuth.

4. The photoresist according to claim 3, wherein M is selected from manganese, nickel, palladium, platinum, iron, antimony, tellurium, tin, cobalt, bismuth, chromium, and copper.

5. The photoresist according to claim 3, wherein M is selected from chromium, copper, iron, tin, cobalt, and bismuth.

6. The photoresist according to claim 1, wherein Q is selected from 4 or 6.

7. The photoresist according to claim 1, wherein L^a, L^b, L^c, L^d, L^e, L^f, L^g and L^h, when present, are selected independently in each instance from:

carbonyl;

cyano;

nitrite;

thiocyanate;

nitrile;

aqua;

hydroxy;

oxo;

alkoxy;

phenoxy;

thiol;

sulfide;

halogen;

phenanthroline;

polymine;

bis(diphenylphosphino)ethane;

bis(diphenylphosphino)methane;

imine;

ethylenediaminetetraacetate;

cyclopentadienyl;

R^aNC;

R^aCN;

NR^a;

P(R^a)₃;

a heterocyclic compound;

8. The photoresist according to claim 7, wherein L^a, L^b, L^c, L^d, L^e, L^f, L^g and L^h, when present, are selected independently from ethylenediammine, phenanthroline,

9. The photoresist according to claim 1, wherein BD₂ is oxalate;

and z is 2 or 3.

10. The photoresist according to claim 9, wherein z is 2;

Q is 6;

(L^a) is 2-2′

-bipyridine optionally substituted with (C_1-6)alkyl; and

o, p, and q are each zero.

11. The photoresist according to claim 9, wherein M is cobalt, iron, or chromium.

12. The photoresist according to claim 11, wherein z is 2;

Q is 6;

(L^a) is 2-2′

-bipyridine optionally substituted with ((C_1-6)alkyl; and

o, p, and q are each zero.

13. The photoresist according to claim 1, wherein y is 2.

14. The photoresist according to claim 1, wherein y is 2;

(L^e) and (L^f) are each 2-2′

-bipyridine optionally substituted with (C_1-6)alkyl; and

p and q are each zero.

15. The photoresist according to claim 1, wherein the minimum solubility of said complex is 0.5% by weight.

16. The photoresist according to claim 1, wherein said complex is in the form of a nanoparticle.

17. The photoresist according to claim 1, wherein said counter ion is selected from P(R)₄⁺, N(R)₄⁺, S(R)₃⁺, and I(R)₂⁺, wherein R is independently selected in each instance from (C₁-C₈)alkyl, aryl, and aryl(C_1-8)alkyl.

18. The photoresist according to claim 1, wherein at least two of said complexes are present, forming a multi-nuclear structure.

19. A nanoparticle comprising at least one complex (BD₂)_zM(L^a)_n(L^b)_o(L^c)_p(L^d)_q or (A)_yM(L^e)_n(L^f)_o(L^g)_p(L^h)_q, wherein:

M is a metal having a coordination number of Q;

Q is an integer selected from 2, 3, 4, 5, 6, 7, or 8;

BD₂ is oxalate or carbonate;

L^a, L^b, L^C and L^d are ligands, each having a denticity of, respectively, w^a, w^b, w^c and w^d;

z is 1, 2 or 3;

n, o, p, and q are independently zero, one or two;

the sum of (n·

w^a) plus (o·

w^b) plus (p·

w^c) plus (q·

w^d) is equal to (Q minus 2z);

A is selected in each instance from azide and (—

NO₂);

L^e, L^f, L^g and L^h are ligands, each having a denticity of respectively, w^e, w^f, w^g and w^h;

y is any integer up to and including Q; and

the sum of (n·

w^e) plus (o·

w^f) plus (p·

w^g) plus (q·

w^h) is equal to (Q minus y);

wherein said complex is balanced by a counter ion, if necessary; and

wherein one of the ligands L^a, L^b, L^c, L^d, L^e, L^f, L^g, or L^h, when present, optionally may be native to the nanoparticle.

20. A photoresist comprising a nanoparticle;

wherein said nanoparticle comprises a ligand selected from oxalate, carbonate, azide, and —

NO₂;

wherein said ligand is bound to a metal atom of said nanoparticle; and

wherein said nanoparticle has a diameter between 0.5 nm and 20 nm.