Low temperature molybdenum film deposition utilizing boron nucleation layers
View Patent ↗The disclosure relates to a method of making molybdenum films utilizing boron and molybdenum nucleation layers. The resulting molybdenum films have low electrical resistivity, are substantially free of boron, and can be made at reduced temperatures compared to conventional chemical vapor deposition processes that do not use the boron or molybdenum nucleation layers. The molybdenum nucleation layer formed by this process can protect the substrate from the etching effect of MoCl 5 or MoOCl 4 , facilitates nucleation of subsequent CVD Mo growth on top of the molybdenum nucleation layer, and enables Mo CVD deposition at lower temperatures. The nucleation layer can also be used to control the grain sizes of the subsequent CVD Mo growth, and therefore controls the electrical resistivity of the Mo film.
1. A method of making a molybdenum layer, the method comprising:
reaction of a boron comprising nucleation layer on a substrate with a vapor composition comprising molecules containing molybdenum and chlorine atoms, the substrate being at a temperature of between from 450° C. to 550° C.; said reaction consuming at least a portion of the boron nucleation layer and forming a molybdenum nucleation layer atop the substrate.
2. The method of claim 1 wherein the thickness of the boron comprising nucleation layer is between from about 5Å to about 50Å.
3. A method of making a molybdenum layer, the method comprising:
reaction of a boron comprising nucleation layer on a substrate with a vapor composition comprising molecules containing molybdenum and chlorine atoms, the substrate being at a temperature of between from 450° C. to 550° C.; said reaction consuming at least a portion of the boron nucleation layer and forming a molybdenum nucleation layer atop the substrate, wherein the boron comprising nucleation layer is substantially consumed by said reaction, such that the molybdenum layer comprises less than 5 wt % boron, optionally less than 1 wt % boron, by elemental analysis.
4. The method of claim 3 comprising depositing the boron comprising nucleation layer atop the substrate, the substrate being at a temperature of between from 300° C. to 550° C.
5. The method of claim 3 further comprising:
depositing a further boron comprising nucleation layer atop said molybdenum nucleation layer atop said substrate, the substrate being at a temperature of between from 300° C. to 550° C.; and
reaction of the further boron comprising nucleation layer with a vapor composition comprising molecules containing molybdenum and chlorine atoms, the substrate being at a temperature of between from 450° C. to 550° C.; said reaction consuming at least a portion of the further boron nucleation layer and forming a further molybdenum nucleation layer.
6. The method of claim 5 wherein the thickness of the further boron comprising nucleation layer is between from about 5Å to about 50Å.
7. The method of claim 5 , wherein the deposited thickness of the further boron comprising nucleation layer is less than the deposited thickness of the boron comprising nucleation layer atop the substrate.
8. The method of claim 5 comprising vapor depositing the boron comprising nucleation layer atop the substrate for a first period of time and vapor depositing the further boron comprising nucleation layer for a second period of time, the second period of time being shorter than the first period of time.
9. The method of claim 5 , wherein the further boron comprising nucleation layer is substantially consumed by said reaction, such that the further molybdenum layer comprises less than 5 wt % boron, optionally less than 1 wt % boron by elemental analysis.
10. The method of claim 5 wherein the steps of depositing and reaction are repeated thereby forming a plurality of further molybdenum nucleation layers.
11. The method of claim 3 , wherein the temperature of the substrate is between from 450° C. to 480° C. during the reaction of the boron comprising nucleation layer(s).
12. The method of claim 3 , wherein the vapor composition is at a pressure of from between 10 torr to 60 torr.
13. The method of claim 3 , wherein the vapor composition is substantially free of a reducing gas.
14. The method of claim 3 , wherein the molybdenum nucleation layer atop the substrate, or a further molybdenum nucleation layer, constitutes a top molybdenum nucleation layer.
15. The method of claim 14 , comprising vapor depositing a molybdenum complex to form a bulk molybdenum layer atop the top molybdenum nucleation layer at a temperature between from 450° C. to 550° C.
16. The method of claim 15 , wherein the molybdenum complex comprises MoCl 5 or MoOCl 4 .
17. The method as claim 15 , wherein the thickness of the molybdenum film is 200 angstroms or more and the resistivity of the bulk molybdenum layer is ±20% of the resistivity of a bulk molybdenum layer of substantially similar thickness ±20% deposited from said molybdenum complex on a substrate at 700° C. that is absent the molybdenum nucleation layer.
18. The method of claim 15 , comprising making a molybdenum film comprising the bulk molybdenum layer and one or more molybdenum nucleation layers, the film having an electrical resistivity measured at room temperature that is less than 20 μΩ·cm for a molybdenum film thickness of 200 angstroms or more.
19. The method of claim 3 , wherein the substrate comprises one or more molybdenum nucleation layers.
20. The method of claim 3 , wherein the substrate comprises a semiconductor substrate.