Gate stack structure and method for forming the same
Embodiments of the present disclosure provide a method of cleaning a lanthanum containing substrate without formation of undesired lanthanum compounds during processing. In one embodiment, the cleaning method includes treating the lanthanum containing substrate with an acidic solution prior to cleaning the lanthanum containing substrate with a HF solution. The cleaning method permits using lanthanum doped high-k dielectric layer to modulate effective work function of the gate stack, thus, improving device performance.
1. A method of forming a semiconductor device, the method comprising:
forming a dielectric layer over a first channel region and a second channel region;
forming a doping layer on the dielectric layer over the first channel region and the second channel region;
removing the doping layer over the second channel region;
annealing to drive dopants from the doping layer into the dielectric layer over the first channel region;
performing a first process to treat remaining portions of the doping layer with an acidic solution; and
after performing the first process, performing a second process to remove the remaining portions of the doping layer, wherein the first process is different than the second process.
2. The method of claim 1 , wherein the first process comprises disposing the acidic solution over a surface of the doping layer and the dielectric layer.
3. The method of claim 1 , wherein the acidic solution comprises carbonic acid (H 2 CO 3 ), hydrochloric acid (HCl), phosphoric acid (H 3 PO 4 ), or acetic acid (CH 3 COOH).
4. The method of claim 3 , wherein performing the first process is performed at a temperature in a range from 20° C. to 80° C.
5. The method of claim 1 , wherein the acidic solution is an aqueous solution of with a ratio of CH 3 COOH:water in a range from 1:5 to 1:25.
6. The method of claim 1 further comprising annealing the dielectric layer and the doping layer at a temperature in a range from about 800 to about 850 degrees Celsius.
7. The method of claim 1 , wherein the doping layer is a lanthanum-containing layer.
8. The method of claim 1 , wherein after annealing, the dielectric layer comprises HfO 2 , HfZrO, HfSiO, SiO, HMO, HMO, TiO, and Ta 2 O 5 doped with lanthanum.
9. A method of forming a semiconductor device, the method comprising:
forming a dielectric layer over a first channel region of a p-type transistor and a second channel region of an n-type transistor of a substrate, the dielectric layer being a metal oxide layer;
forming a lanthanum-doping layer on the dielectric layer over the first channel region and the second channel region;
forming one or more capping layers over the lanthanum-doping layer over the first channel region and the second channel region;
removing the one or more capping layers and the lanthanum-doping layer from over the second channel region;
driving lanthanum atoms into the dielectric layer from the lanthanum-doping layer over the first channel region, an unconsumed portion of the lanthanum-doping layer remaining after driving the lanthanum atoms into the dielectric layer;
softening a surface of the unconsumed portion of the lanthanum-doping layer using a first process, the first process comprising exposing the unconsumed portion of the lanthanum-doping layer to a first acidic solution; and
after softening, removing the unconsumed portion of the lanthanum-doping layer using a second process, wherein the first process is different than the second process.
10. The method of claim 9 , wherein the softening is performed at least in part by dispensing the first acidic solution over the substrate while spinning the substrate.
11. The method of claim 9 , wherein removing the unconsumed portion of the lanthanum-doping layer comprises using a second acidic solution.
12. The method of claim 11 , wherein the second acidic solution is stronger than the first acidic solution.
13. The method of claim 11 , wherein the second acidic solution comprises a halogen-containing solution.
14. The method of claim 11 , wherein softening the surface of the unconsumed portion of the lanthanum-doping layer and removing the unconsumed portion of the lanthanum-doping layer are performed in a same spin-rinse dry tool.
15. The method of claim 11 , wherein removing the unconsumed portion of the lanthanum-doping layer comprises applying the second acidic solution while the substrate is spinning.
16. A method of forming a semiconductor device, the method comprising:
forming a dielectric layer over a first channel region and a second channel region of a substrate;
forming a doping layer on the dielectric layer over the first channel region and the second channel region, wherein the doping layer comprises lanthanum;
removing the doping layer over the second channel region;
annealing to drive dopants from the doping layer into the dielectric layer over the first channel region, an unconsumed portion of the doping layer remaining after annealing;
exposing the unconsumed portion of the doping layer to an acidic solution while spinning the substrate; and
after exposing, cleaning the substrate to remove the unconsumed portion of the doping layer using a halogen-containing solution.
17. The method of claim 16 , wherein cleaning the substrate comprises applying the halogen-containing solution while the substrate is spinning.
18. The method of claim 17 , wherein the halogen-containing solution comprises a hydrofluoric acid solution.
19. The method of claim 18 , wherein the hydrofluoric acid solution comprises an aqueous HF solution at a concentration of 0.097%.
20. The method of claim 19 , wherein the acidic solution has a PH value in a range from 5.0 to 7.0.