Etch chemistries for metallization in electronic devices
View Patent ↗In various embodiments, etchants featuring (i) mixtures of hydrochloric acid, methanesulfonic acid, and nitric acid, or (ii) mixtures of phosphoric acid, methanesulfonic acid, and nitric acid, are utilized to etch metallic bilayers while minimizing resulting etch discontinuities between the layers of the bilayer.
1. A method of forming an electrode of a thin-film transistor, the method comprising:
providing a base layer comprising at least one of silicon or glass;
depositing over the base layer a barrier layer comprising one or more refractory metals or an alloy of one or more refractory metals with one or more additional metallic components;
depositing over the barrier layer a conductor layer comprising at least one of Cu, Ag, Au, or Al;
forming a mask layer over the barrier layer;
patterning the mask layer to reveal a portion of the conductor layer, a remaining portion of the mask layer at least partially defining a shape of the electrode;
thereafter, applying an etchant to remove portions of the conductor layer and the barrier layer not masked by the patterned mask layer, thereby forming a sidewall of the electrode comprising (a) an exposed portion of the barrier layer, (b) an exposed portion of the conductor layer, and (c) an interface between the exposed portion of the barrier layer and the exposed portion of the conductor layer,
wherein the etchant comprises (i) a mixture of, by weight, 5%-15% hydrochloric acid, 20%-40% methanesulfonic acid, 7%-10% nitric acid, and the balance water, or (ii) a mixture of, by weight, 40%-75% phosphoric acid, 5%-30% methanesulfonic acid, 2%-5% nitric acid, and the balance water.
2. The method of claim 1 , wherein the sidewall of the electrode is substantially free of discontinuities notwithstanding the interface between the exposed portion of the barrier layer and the exposed portion of the conductor layer.
3. The method of claim 1 , wherein, proximate the interface between the exposed portion of the barrier layer and the exposed portion of the conductor layer, the exposed portion of the barrier layer protrudes from the exposed portion of the conductor layer by 6 μm or less.
4. The method of claim 3 , wherein the exposed portion of the barrier layer protrudes by between 1 μm and 5 μm.
5. The method of claim 3 , wherein the exposed portion of the barrier layer protrudes by between 1 μm and 3 μm.
6. The method of claim 1 , wherein, after the etchant is applied, the electrode is substantially free of etch residue at (i) the interface between the exposed portion of the barrier layer and the exposed portion of the conductor layer and (ii) an interface between the exposed portion of the barrier layer and the base layer.
7. The method of claim 1 , wherein the etchant contains at least 49% water by weight.
8. The method of claim 1 , wherein the etchant contains at least 51% water by weight.
9. The method of claim 1 , wherein the etchant comprises citric acid.
10. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 7% nitric acid, 9% hydrochloric acid, 33% methanesulfonic acid, and 51% water.
11. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 7% nitric acid, 12% hydrochloric acid, 30% methanesulfonic acid, and 51% water.
12. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 7% nitric acid, 12% hydrochloric acid, 25% methanesulfonic acid, and 56% water.
13. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 7% nitric acid, 5% hydrochloric acid, 37% methanesulfonic acid, and 51% water.
14. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 7% nitric acid, 12% hydrochloric acid, 30% methanesulfonic acid, 5% citric acid, and 46% water.
15. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 9% nitric acid, 12% hydrochloric acid, 30% methanesulfonic acid, and 49% water.
16. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 3.5% nitric acid, 60% phosphoric acid, 15% methanesulfonic acid, and 21.5% water.
17. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 3.5% nitric acid, 50% phosphoric acid, 20% methanesulfonic acid, and 26.5% water.
18. The method of claim 1 , wherein the etchant comprises a mixture consisting of, by weight, 3.5% nitric acid, 68.6% phosphoric acid, 10% methanesulfonic acid, and 17.9% water.
19. The method of claim 1 , wherein the barrier layer comprises Mo, W, or an alloy of Mo and W.
20. The method of claim 1 , wherein the barrier layer comprises an alloy of Mo and/or W with one or more additional metallic components.
21. The method of claim 1 , wherein the conductor layer comprises Cu.
22. The method of claim 1 , wherein the barrier layer comprises Mo and the conductor layer comprises Cu.
23. The method of claim 1 , wherein the mask layer comprises photoresist.
24. The method of claim 1 , further comprising removing the remaining portion of the patterned mask layer.
25. The method of claim 1 , wherein the base layer comprises glass.
26. The method of claim 1 , wherein the base layer comprises silicon.
27. The method of claim 26 , wherein the base layer comprises amorphous silicon.