Tungsten for wordline applications
Disclosed herein are methods and related apparatus for formation of tungsten wordlines in memory devices. Also disclosed herein are methods and related apparatus for deposition of fluorine-free tungsten (FFW). According to various embodiments, the methods involve deposition of multi-component tungsten films using tungsten chloride (WCl x ) precursors and boron (B)-containing, silicon (Si)-containing or germanium (Ge)-containing reducing agents.
1. A method of depositing tungsten on a substrate, the method comprising:
pulsing a reducing agent, wherein the reducing agent is boron (B)-containing, silicon (Si)-containing or germanium (Ge)-containing; and
pulsing a tungsten chloride precursor,
wherein the tungsten chloride precursor is reduced by the reducing agent or a product thereof to form a multi-component tungsten-containing film containing one or more of B, Si, and Ge on the substrate, wherein the multi-component tungsten-containing film contains between 5% and 60% (atomic) B, Si, or Ge, and wherein the between 5% and 60% (atomic) B, Si, or Ge is provided by the reducing agent.
2. The method of claim 1 , further comprising pulsing a third reactant to form a ternary tungsten-containing film.
3. The method of claim 1 , wherein the multi-component film is a binary film.
4. The method of claim 1 , wherein the multi-component tungsten-containing film is a diffusion barrier for a wordline.
5. The method of claim 1 , wherein the multi-component tungsten-containing film is a work function layer for a metal gate.
6. The method of claim 1 , wherein the substrate temperature during the tungsten chloride pulse is at least 400° C.
7. The method of claim 1 , wherein the temperature during the tungsten chloride pulse is at least 450° C.
8. The method of claim 1 , wherein the temperature during the tungsten chloride pulse is at least 500° C.
9. The method of claim 1 , wherein the substrate temperature during the reducing agent and tungsten chloride pulses is at least 400° C.
10. The method of claim 1 , wherein the substrate temperature during the reducing agent and tungsten chloride pulses is at least 450° C.
11. The method of claim 1 , wherein the substrate temperature during the reducing agent and tungsten chloride pulses is at least 500° C.
12. The method of claim 1 , further comprising depositing a bulk tungsten (W) layer on the multi-component tungsten-containing film.
13. The method of claim 12 , wherein the bulk W layer is deposited by a chemical vapor deposition (CVD) reaction between a tungsten chloride precursor and a reducing agent.
14. The method of claim 12 , wherein the bulk W layer is deposited directly on the multi-component tungsten-containing film without an intervening layer.
15. The method of claim 1 , wherein the multi-component tungsten-containing film is deposited directly on an insulating film.
16. The method of claim 15 , wherein the insulating film is an oxide or nitride film.
17. The method of claim 1 , wherein the method further comprises decomposition of the reducing agent to form a layer of B, Si, or Ge on the substrate.
18. The method of claim 1 , wherein the multi-component tungsten-containing film contains between 15% and 50% (atomic) B, Si, or Ge.
19. The method of claim 1 , wherein the multi-component tungsten-containing film is selected from the group consisting of WGe x , WGe x N y , WGe x C y , WB x Ge y N z , and WGe x C y N z wherein x, y, and z are numbers greater than zero.
20. A method of depositing tungsten on a substrate, the method comprising:
pulsing a (Ge)-containing reducing agent; and
pulsing a tungsten chloride precursor, wherein the tungsten chloride precursor is reduced by the Ge-containing reducing agent or a product thereof to form a multi-component tungsten-containing film containing between 5% and 60% (atomic) Ge, wherein the between 5% and 60% (atomic) Ge is provided by the Ge-containing reducing agent.