Method of forming low resistivity fluorine free tungsten film without nucleation
Provided herein are methods of depositing fluorine-free tungsten by sequential CVD pulses, such as by alternately pulsing a chlorine-containing tungsten precursor and hydrogen in cycles of temporally separated pulses, without depositing a tungsten nucleation layer. Methods also include depositing tungsten directly on a substrate surface using alternating pulses of a chlorine-containing tungsten precursor and hydrogen without treating the substrate surface.
1. A method of filling a feature comprising:
(a) providing a substrate in a chamber, the substrate comprising the feature having an untreated surface comprising a metal; and
(b) without treating the untreated surface of the feature and without depositing a tungsten nucleation layer in the feature, exposing the untreated surface to cycles of alternating pulses of hydrogen and a chlorine-containing tungsten precursor introduced to the chamber to deposit bulk tungsten directly on the untreated surface.
2. The method of claim 1 , wherein the chlorine-containing tungsten precursor is selected from the group consisting of tungsten hexachloride and tungsten pentachloride.
3. The method of claim 1 , wherein a pulse of the chlorine-containing tungsten precursor comprises between about 0.1% and about 1.5% of chlorine-containing tungsten precursor by volume.
4. The method of claim 1 , wherein the chamber is purged between each pulse of the hydrogen and the chlorine-containing tungsten precursor.
5. The method of claim 1 , wherein the bulk tungsten is deposited to a thickness of less than about 50 Å and resistivity of the bulk tungsten is less than about 150 μΩ-cm.
6. A method of filling a feature comprising:
(a) providing a substrate in a chamber, the substrate comprising the feature; and
(b) exposing the substrate to cycles of alternating pulses of hydrogen and a chlorine-containing tungsten precursor introduced to the chamber to deposit bulk tungsten directly in the feature without depositing a tungsten nucleation layer,
wherein pressure of the chamber is no more than 10 Torr.
7. The method of claim 6 , further comprising, (c) prior to exposing the substrate to the alternating pulses of the hydrogen and the chlorine-containing tungsten precursor, exposing the substrate to a reducing agent for a soak treatment.
8. The method of claim 6 , further comprising, (c) prior to exposing the substrate to the alternating pulses of the hydrogen and the chlorine-containing tungsten precursor, exposing the substrate to alternating pulses of a reducing agent and the chlorine-containing tungsten precursor to deposit a tungsten nucleation layer on the substrate.
9. The method of claim 6 , wherein each cycle forms a submonolayer of the bulk tungsten having a thickness of at least about 0.3 Å.
10. The method of claim 6 , wherein the chlorine-containing tungsten precursor is tungsten hexachloride.
11. The method of claim 6 , wherein the chlorine-containing tungsten precursor is tungsten pentachloride.
12. The method of claim 6 , wherein the bulk tungsten is deposited at a substrate temperature between about 400° C. and about 600° C.
13. The method of claim 6 , wherein the chamber is purged between each pulse of the hydrogen and the chlorine-containing tungsten precursor.
14. The method of claim 6 , wherein each purge is performed for a duration between about 0.25 seconds and about 30 seconds.
15. The method of claim 6 , wherein a pulse of the chlorine-containing tungsten precursor comprises between about 0.1% and about 1.5% of chlorine-containing tungsten precursor by volume.
16. The method of claim 6 , wherein the bulk tungsten is deposited to a thickness of less than about 50 Å and resistivity of the bulk tungsten is less than about 150 μΩ-cm.
17. A method of filling a feature comprising:
(a) providing a substrate in a chamber, the substrate comprising the feature, the feature comprising a metal-containing surface;
(b) exposing the metal-containing surface to cycles of alternating pulses of hydrogen and a chlorine-containing tungsten precursor introduced to the chamber to deposit bulk tungsten in the feature without depositing a tungsten nucleation layer; and
(c) prior to exposing the metal-containing surface to the alternating pulses of the hydrogen and the chlorine-containing tungsten precursor, exposing the metal-containing surface to a reducing agent for a soak treatment.
18. The method of claim 17 , wherein a pulse of the chlorine-containing tungsten precursor comprises between about 0.1% and about 1.5% of chlorine-containing tungsten precursor by volume.
19. The method of claim 17 , wherein the bulk tungsten is deposited at a substrate temperature between about 400° C. and about 600° C.
20. The method of claim 17 , wherein the chamber is purged between each pulse of the reducing agent and the chlorine-containing tungsten precursor.
21. The method of claim 17 , wherein each purge is performed for a duration between about 0.25 seconds and about 30 seconds.
22. The method of claim 17 , wherein the reducing agent is selected from the group consisting of germane (GeH 4 ), argon (Ar), tungsten hexafluoride (WF 6 ), diborane (B 2 H 6 ), hydrogen (H 2 ), nitrogen (N 2 ) gas, and combinations thereof.
23. The method of claim 17 , wherein the bulk tungsten is deposited to a thickness of less than about 50 Å and resistivity of the bulk tungsten is less than about 150 μΩ-cm.