Self-protective layer formed on high-k dielectric layers with different materials

1. A semiconductor device, comprising:

a first gate structure and a second gate structure on a substrate; wherein the first gate structure includes a first gate dielectric layer having a first material, and the second gate structure includes a second gate dielectric layer having a second material, the first material being different from the second material, wherein the first and the second gate structures further comprise:

a first and a second self-protective layers disposed on the first and the second gate dielectric layers respectively, wherein the first self-protective layer comprises metal phosphate and the second self-protective layer comprises boron comprising complex agents; and

a first work function tuning layer on the first self-protective layer in the first gate structure.

2. The semiconductor device of claim 1 , wherein the second gate structure further comprises:

a second work function tuning layer on the second self-protective layer in the second gate structure.

3. The semiconductor device of claim 2 , further comprising:

a gate electrode metal on the first or second work function tuning layer.

4. The semiconductor device of claim 1 , wherein a metal element from the metal phosphate is embedded in the first gate dielectric layer.

5. The semiconductor device of claim 1 , wherein the first gate dielectric layer and the first self-protective layer share a common metal element.

6. The semiconductor device of claim 5 , wherein the common metal element is at least one of Ta, Ti, Hf, Zr, or a combination thereof.

7. The semiconductor device of claim 1 , wherein the second gate dielectric layer and the second self-protective layer share common silicon elements.

8. The semiconductor device of claim 7 , wherein the silicon elements from the second gate dielectric layer and the second self-protective layer form the boron comprising complex agents in the second self-protective layer.

9. The semiconductor device of claim 8 , wherein the boron comprising complex agents are silicon-boronate complex agents.

10. The semiconductor device of claim 1 , wherein the first material of the first gate dielectric layer is a Ta containing material.

11. The semiconductor device of claim 1 , wherein the second material of the second gate dielectric layer is silicon containing material.

12. The semiconductor device of claim 1 , wherein the first material of the first gate dielectric layer is at least one of TaN, TaON, TaO, HfN, ZrN, or a combination thereof and the second material of the second gate dielectric layer is at least one of TaSiN, TiSiN, WSiN, HfSiN, ZrSiN, or a combination thereof.

13. The semiconductor device of claim 1 , wherein the first and the second self-protective layers have a thickness in a range from 10 Å to 20 Å.

14. A semiconductor device structure, comprising:

a gate structure formed on a substrate, wherein the gate structure comprises:

a gate dielectric layer;

a self-protective layer on the gate dielectric layer, the self-protective layer comprising metal phosphate or boron comprising complex agents, wherein the metal phosphate has a common metal element with the gate dielectric layer or the boron comprising complex agents has a common silicon element with the gate dielectric layer; and

a work function tuning layer formed on the self-protective layer.

15. The semiconductor device structure of claim 14 , wherein the boron comprising complex agents comprise silicon-boronate complex agents.

16. The semiconductor device structure of claim 15 , wherein the self-protective layer has a thickness in a range from 10 Å to 20 Å.

17. The semiconductor device structure of claim 15 , wherein the gate dielectric layer further comprises a first portion comprising the metal element and a second portion comprising the silicon element.

18. A semiconductor device, comprising:

a first gate structure over a first fin, the first gate structure disposed in a P-type device region, wherein the first gate structure comprises:

a first gate dielectric layer over the first fin;

a first self-protective layer over the first gate dielectric layer, the first self-protective layer comprising metal phosphate; and

a first work function layer over the first self-protective layer; and

a second gate structure over the first fin, the second gate structure disposed in an N-type device region, wherein the second gate structure comprises:

a second gate dielectric layer over the first fin, the second gate dielectric layer having a different composition from the first gate dielectric layer;

a second self-protective layer over the second gate dielectric layer, the second self-protective layer comprising silicon-boron complex agents; and

the first work function layer over the second self-protective layer.

19. The semiconductor device of claim 18 , wherein the first gate dielectric layer and the first self-protective layer share a common metal element, wherein the second gate dielectric layer and the second self-protective layer share a common silicon element.

20. The semiconductor device of claim 19 , wherein the first gate dielectric layer comprises tantalum (Ta), zirconium (Zr), or hafnium (Hf), and the second gate dielectric layer comprises silicon (Si).