Stable metal compounds as hardmasks and filling materials, their compositions and methods of use

1. A soluble, multi-ligand-substituted metal compound of structure (I):

wherein M is a metal and n is 1 to 20, and wherein at least one of R 1 , R 2 , R 3 , and R 4 is i) and at least one of R 1 , R 2 , R 3 , and R 4 is ii), where i) is a silicon bearing organic moiety having at least 2 carbons, and ii) is

an organic moiety (II),

wherein R 8 is selected from a group consisting of C 2 -C 10 alkylene, C 3 -C 12 branched alkylene, C 5 -C 12 cycloalkylene, C 2 -C 10 alkylene containing a C═C double bond, C 3 -C 12 branched alkylene containing a C═C double bond, and a C 5 -C 12 cycloalkylene containing a C═C double bond, and R 9 is the alkyloxycarbonyl moiety (III), where R 10 is a C 1 -C 9 alkyl group,

provided that the silicon bearing moiety bearing an organic moiety having at least 2 carbons i) ranges from about 10 mole % to about 80 mole %, and ii) ranges from about 20 mole % to about 90 mole % of the total groups R 1 , R 2 , R 3 , and R 4 .

2. The compound of claim 1 , wherein the silicon bearing moiety bearing an organic moiety having at least 2 carbons i) ranges from 30 mole % to 60 mole %, and that the organic moiety ii) ranges from 30 mole % to 60 mole % of the total of groups R 1 , R 2 , R 3 , and R 4 .

3. The compound of claim 1 , wherein in structure (I) at least one of R 1 , R 2 , R 3 , and R 4 further comprises C 1 -C 8 alkyl moiety ranging up to 50 mole % of the total of groups R 1 , R 2 , R 3 , and R 4 .

4. The compound of claim 1 , wherein in structure (I) at least one of R 1 , R 2 , R 3 , and R 4 further comprises C 1 -C 5 alkyl moiety ranging up to 35 mole % of the total of groups R 1 , R 2 , R 3 , and R 4 .

5. The compound of claim 1 , wherein the metal is selected from a group consisting of titanium, zirconium, tantalum, lead, antimony, thallium, indium, ytterbium, gallium, hafnium, aluminum, magnesium, molybdenum, germanium, tin, iron, cobalt, nickel, copper, zinc, gold, silver, cadmium, tungsten, and platinum.

6. The compound of claim 1 , wherein the metal is more than one metal when n is 2 to 20.

7. The compound of claim 1 wherein the silicon bearing organic moiety having at least 2 carbon i) is selected from a group consisting of a trisubstitutedsilyl moiety (IV) and a siloxane moiety (V)

wherein R 5 , and R 6 , are independently selected from a group consisting of C 1 -C 8 alkyl, C 3 -C 12 branched alkyl, and aryl, R 7 is independently selected from a group consisting of C 1 -C 8 alkyl, aryl and hydroxyl, and R 8′ is selected from group consisting of hydrogen, a C 1 -C 8 alkyl, a C 1 -C 8 alkyl substituted with a hydroxyl group, a carboxylic acid group (CO 2 H), and an aryl, and further where p represents the number of repeat units in the siloxane moiety (v).

8. The compound of claim 1 , where the silicon bearing organic moiety having at least 2 carbon I) is a trisubstitutedsilyl moiety (IV).

9. The compound of claim 1 , where the silicon bearing organic moiety having at least 2 carbon I) is a siloxane moiety (V).

10. The compound of claim 1 where M is Ti, and the organic moiety i) is selected from the group consisting of

and further wherein n=4-16.

11. The compound of claim 1 where M is Ti and the silicon bearing organic moiety at least 2 carbon ii) is selected from the group consisting of

and further wherein n=4-16.

12. A composition comprising:

a. a soluble, multi-ligand-substituted metal compound of the following structure (I)

wherein M is a metal and n is 1 to 20, and wherein at least one of R 1 , R 2 , R 3 , and R 4 is i) and at least at least one of R 1 , R 2 , R 3 , and R 4 is ii), where i) is a silicon bearing organic moiety having at least 2 carbons, and ii) is

an organic moiety (II),

wherein R 8 is selected from a group consisting of C 2 -C 10 alkylene, C 3 -C 12 branched alkylene, C 5 -C 12 cycloalkylene, C 2 -C 10 alkylene containing a C═C double bond, C 3 -C 12 branched alkylene containing a C═C double bond, and a C 5 -C 12 cycloalkylene containing a C═C double bond, and R 9 or the alkyloxycarbonyl moiety (III), where R 10 is a C 1 -C 8 alkyl group,

provided that the silicon bearing moiety bearing an organic moiety having at least 2 carbons i) ranges from about 10 mole % to about 80 mole %, and ii) ranges from about 20 mole % to about 90 mole % of the total groups R 1 , R 2 , R 3 , and R 4 , and

(b) a solvent.

13. The composition of claim 12 where the composition further comprises a surfactant.

14. The composition of claim 12 , further comprising at least one selected from a group consisting of a thermal acid generator, a thermal base generator, and a thermally activated peroxide.

15. The composition of claim 12 , wherein n is 2 to 20.

16. The composition of claim 12 , wherein n is 1.

17. The composition of claim 12 , further comprising a crosslinking additive.

18. A method of manufacturing an electronic device on a substrate comprised of a patterned photoresist comprising, vias, trenches, holes or other hollow topographical features where the method comprises:

a. applying a composition from claim 12 onto the substrate;

b. baking the film;

c. removing the composition overlaying the top of the patterned photoresist; and

d. removing the resist with an oxygen plasma, thereby forming a negative tone image of the original patterned resist.

19. The method of claim 18 , further comprising removing the residual composition with a stripper composition.