Methods for etching via atomic layer deposition (ALD) cycles

1. A method of processing a substrate disposed within a processing volume of a process chamber, comprising:

(a) exposing a metal-containing first layer disposed atop the substrate to a first gas comprising tungsten chloride (WCl x ) for a first period of time and at a first pressure wherein the tungsten chloride (WCl x ) reacts with the metal-containing first layer to form a metal chloride, and wherein x is 5 or 6;

(b) purging the processing volume of the first gas using an inert gas for a second period of time;

(c) etching the metal chloride by exposing the substrate to a hydrogen-containing gas for a third period of time after purging the processing volume of the first gas; and

(d) purging the processing volume of the hydrogen-containing gas using the inert gas for a fourth period of time.

2. The method of claim 1 , further comprising depositing the first layer atop a first surface of the substrate and within a feature formed in the first surface, the feature comprising an opening defined by one or more sidewalls, a bottom surface and upper corners, wherein a thickness of the first layer is greater proximate the upper corners of the opening than at the sidewalls and bottom of the opening.

3. The method of claim 2 , further comprising repeating (a)-(d) to at least partially reduce a thickness of the first layer proximate the upper corners.

4. The method of claim 2 , wherein the first pressure is greater than about 7.5 Torr to conformally etch the first layer from the first surface of the substrate and from the one or more sidewalls, the bottom surface and the upper corners of the opening.

5. The method of claim 2 , wherein the first pressure is less than about 7.5 Torr to selectively etch the first layer from the first surface of the substrate and from the upper corners of the opening.

6. The method of claim 2 , further comprising depositing a conductive layer to fill the feature.

7. The method of claim 6 , further comprising depositing a barrier layer in the feature prior to depositing the conductive layer to fill the feature.

8. The method of claim 7 , further comprising depositing a seed layer atop the barrier layer prior to depositing the conductive layer to fill the feature.

9. The method of claim 8 , further comprising exposing the substrate to a second process gas prior to depositing the conductive layer, wherein the second process gas conditions the first surface to suppress a growth of the conductive layer on the first surface.

10. The method of claim 9 , wherein the second process gas is a nitrogen containing gas.

11. The method of claim 1 , wherein the first period of time is about 0.1 seconds to about 1 second.

12. The method of claim 1 , wherein the second period of time is about 0.1 seconds to about 1 second.

13. The method of claim 1 , wherein the third period of time is about 0.5 seconds to about 2 seconds.

14. The method of claim 1 , wherein the process chamber has a temperature during (a)-(d) of 400° Celsius to 450° Celsius.

15. The method of claim 1 , further comprising exposing the first layer to a second gas for a second period of time prior to exposing the first layer to the first gas, wherein the second gas comprises tungsten chloride (WClx) and an inert gas and wherein x is 5 or 6.

16. The method of claim 1 , further comprising exposing the first layer to an oxygen containing gas prior to exposing a first layer to the first gas.

17. A method of processing a substrate disposed within a processing volume of a process chamber, comprising:

(a) depositing a first layer atop a first surface of the substrate and within a feature formed in the first surface, the feature comprising an opening defined by one or more sidewalls, a bottom surface and upper corners, wherein a thickness of the first layer is greater proximate the upper corners of the opening than at the sidewalls and bottom of the opening;

(b) exposing a first layer disposed atop the substrate to a first gas comprising tungsten chloride (WCl x ) for a first period of time of about 0.1 seconds to about 1 second and at a first pressure, wherein x is 5 or 6;

(c) purging the processing volume of the first gas using an inert gas for a second period of time of about 0.1 seconds to about 1 second;

(d) exposing the substrate to a hydrogen-containing gas for a third period of time to etch the first layer after purging the processing volume of the first gas, wherein the third period of time is about 0.5 seconds to about 2 seconds;

(e) purging the processing volume of the hydrogen-containing gas using the inert gas for a fourth period of time of about 0.1 seconds to about 1 second;

(f) repeating (b)-(f) to etch the first layer to a predetermined thickness; and

(g) depositing a conductive layer to fill the feature.

18. A method of processing a substrate disposed within a processing volume of a process chamber, comprising:

annealing a substrate having a titanium layer disposed atop an underlying silicon layer to form a titanium silicide layer, wherein a portion of the titanium layer does not react with the underlying silicon layer to form titanium silicide and wherein a native oxide layer is formed on the titanium silicide layer; and

selectively etching the unreacted portion of the titanium layer and the native oxide layer with respect to the titanium silicide layer by exposing the substrate to a first gas comprising tungsten chloride (WCl x ) and an inert gas for a first period of time, wherein x is 5 or 6.

19. The method claim 18 , further comprising exposing the titanium layer to an oxygen containing gas prior to exposing the substrate to the first gas.