Copper metallization of through silicon via

1. A method for metallizing a through silicon via feature in a semiconductor integrated circuit device substrate, wherein the semiconductor integrated circuit device substrate comprises a front surface, a back surface, and the via feature and wherein the via feature comprises an opening in the front surface of the substrate, a sidewall extending from the front surface of the substrate, and a bottom, the method comprising:

immersing the semiconductor integrated circuit device substrate into an electrolytic copper deposition composition, wherein the through silicon via feature has an entry dimension between 5 microns and 300 microns, a depth dimension between 50 microns and 250 microns, and an aspect ratio greater than about 0.3:1, the deposition composition comprising:

(a) a source of copper ions;

(b) an acid selected from among an inorganic acid, organic sulfonic acid, and mixtures thereof;

(c) one or more organic compounds selected from among polarizers and/or depolarizers, which one or more organic compounds promotes faster copper deposition at the via bottom than at the via opening; and

(d) chloride ions; and

supplying electrical current to the electrolytic deposition composition to deposit copper metal onto the bottom and sidewall for bottom-up filling to thereby yield a copper filled via feature.

2. The method of claim 1 wherein the via feature has an entry dimension between about 10 and about 100 microns.

3. The method of claim 1 wherein the source of copper ions is an organic copper sulfonate and the acid is the sulfonic acid.

4. The method of claim 1 wherein the one or more organic compounds consists of a polarizer.

5. The method of claim 1 wherein the polarizer is a vinyl pyridine based compound.

6. The method of claim 5 wherein the vinyl pyridine based compound is a substituted pyridyl polymer compound having a molecular weight of less than about 160,000 g/mol.

7. The method of claim 5 wherein the vinyl pyridine based compound is a substituted pyridyl polymer compound having a molecular weight of between about 500 g/mol and about 150,000 g/mol.

8. The method of claim 5 wherein the vinyl pyridine based compound is methyl quaternized poly(vinyl-4-pyridine).

9. The method of claim 5 wherein the polarizer further comprises poly(propylene glycol)bis(2-aminopropyl ether).

10. The method of claim 5 wherein the polarizer further comprises a random ethylene oxide/propylene oxide copolymer.

11. The method of claim 1 wherein the one or more polarization compounds consists of a polarizer and a depolarizer.

12. The method of claim 11 wherein the polarizer is methyl quaternized poly(vinyl-4-pyridine).

13. The method of claim 11 wherein the depolarizer is an organic sulfur compound having the following general structure (1):

wherein

X is O, S, or S═O;

n is 1 to 6;

M is hydrogen, alkali metal, or ammonium as needed to satisfy the valence;

R 1 is an alkylene or cyclic alkylene group of 1 to 8 carbon atoms, an aromatic hydrocarbon or an aliphatic aromatic hydrocarbon of 6 to 12 carbon atoms; and

R 2 is hydrogen, hydroxyalkyl having from 1 to 8 carbon atoms, or MO 3 SR 1 wherein M and R 1 are as defined above.

14. The method of claim 11 wherein the depolarizer is 3,3′-dithiobis(1-propanesulfonic acid).

15. The method of claim 11 wherein the polarizer is methyl quaternized poly(vinyl-4-pyridine) and the depolarizer is 3,3′-dithiobis(1-propanesulfonic acid).

16. The method of claim 1 wherein the one or more polarization compounds yields a copper deposition potential at the via bottom which is at least about 50 millivolts less negative than a copper deposition potential at the via opening.

17. The method of claim 1 wherein the via feature has an entry dimension between about 5 and about 100 microns.

18. The method of claim 1 wherein the via feature has an aspect ratio between about 0.3:1 and about 5:1.

19. The method of claim 1 wherein the via feature has an aspect ratio between about 1.75:1 and about 5:1.

20. A method for metallizing a via feature in a semiconductor integrated circuit device substrate, wherein the semiconductor integrated circuit device substrate comprises a front surface, a back surface, and the via feature and wherein the via feature comprises an opening in the front surface of the substrate, a sidewall extending from the front surface of the substrate, and a bottom, the method comprising:

immersing the semiconductor integrated circuit device substrate into an electrolytic copper deposition composition, wherein the via feature has a depth between about 50 and about 250 microns, and a via feature entry dimension between about 5 and about 100 microns, the deposition composition consisting essentially of:

(a) copper methane sulfonate as a source of between about 50 and about 110 g/L copper ions;

(b) methane sulfonic acid in a concentration between about 1 and about 25 g/L;

(c) one or more organic compounds selected from among polarizers at a concentration between about 1 and about 200 ppm and depolarizers at a concentration between about 3 micromolar and about 100 micromolar, which one or more organic compounds promotes a faster copper deposition at the via bottom than at the via opening; and

(d) chloride ions in a concentration between about 10 and about 90 mg/L; and

supplying electrical current at an average current density between about 0.3 A/dm 2 and about 5 A/dm 2 to the electrolytic deposition composition to deposit copper metal onto the bottom and sidewall for bottom-up filling to thereby yield a copper filled via feature.

21. The method of claim 20 wherein the one or more organic compounds are a polarizer which is methyl quaternized poly(vinyl-4-pyridine) in a concentration between about 1 and about 40 ppm and a depolarizer which is 3,3′-dithiobis(1-propanesulfonic acid) in a concentration between about 1 PPM and about 50 PPM.