Method of fabricating silicon-doped metal oxide layer using atomic layer deposition technique

• US 20060257563A1
• Filed: 01/11/2006
• Published: 11/16/2006
• Est. Priority Date: 10/13/2004
• Status: Abandoned Application

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Doh, Seok-Joo, Lee, Jung-Hyoung, Lee, Jong-Ho, Kim, Jong-Pyo, Kim, Yun-Seok, Rhee, Shi-Woo
• Application Number:
  US11/329,696
• Publication Number:
  US 20060257563A1
• Time in Patent Office: Days
• US Class Current: 427/248.100
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions

Abstract

There are provided methods of fabricating a silicon-doped metal oxide layer on a semiconductor substrate using an atomic layer deposition technique. The methods include an operation of repeatedly performing a metal oxide layer formation cycle K times and an operation of repeatedly performing a silicon-doped metal oxide layer formation cycle Q times. At least one of the values K and Q is an integer of 2 or more. K and Q are integers ranging from 1 to about 10 respectively. The metal oxide layer formation cycle includes the steps of supplying a metal source gas to a reactor containing the substrate, and then injecting an oxide gas into the reactor. The silicon-doped metal oxide layer formation cycle includes supplying a metal source gas including silicon into a reactor containing the substrate, and then injecting an oxide gas into the reactor. The sequence of operations of repeatedly performing the metal oxide layer formation cycle K times, followed by repeatedly performing the silicon-doped metal oxide layer formation cycle Q times, is performed one or more times until a silicon-doped metal oxide layer with a desired thickness is formed on the substrate. In addition, a method of fabricating a silicon-doped hafnium oxide (Si-doped HfO₂) layer according to a similar invention method is also provided.

Claims

1. A method of fabricating a silicon-doped metal oxide layer on a substrate using an atomic layer deposition technique, said method comprising the sequential steps of:

(a) loading a substrate into a reactor;

(b) supplying a metal source gas containing a desired metal into the reactor having the substrate under reaction conditions to form a chemical adsorption layer including the desired metal on the substrate;

(c) supplying an oxide gas into the reactor under reaction conditions to react with the chemical adsorption layer including the desired metal to form a metal oxide layer including the desired metal on the substrate;

(d) repeatedly performing steps (b) and (c) sequentially K times;

(e) supplying a metal source gas including silicon into the reactor under reaction conditions to form a metal chemical adsorption layer including silicon on the metal oxide layer on the substrate;

(f) supplying an oxide gas into the reactor under reaction conditions to react with the metal oxide layer and the metal chemical adsorption layer including silicon to form a silicon-doped metal oxide layer;

(g) repeatedly performing steps (e) and (f) sequentially Q times, wherein at least one of the values K and Q is an integer of 2 or more; and

(h) performing the operations of steps (b), (c), (d), (e), (f) and (g) sequentially at least one time, thereby forming a silicon-doped metal oxide layer with a desired thickness.

2. The method according to claim 1, further comprising the steps of:

exhausting unreacted metal source gas remaining in the reactor after each step (b) to clean the inside of the reactor before step (c);

exhausting unreacted oxide gas and reaction byproducts remaining in the reactor after each step (c) to clean the inside of the reactor before step (d);

exhausting unreacted metal source gas including silicon remaining in the reactor after each step (e) to clean the inside of the reactor before step (f); and

exhausting unreacted oxide gas and reaction byproducts remaining in the reactor after each step (f) to clean the inside of the reactor before step (g).

3. The method according to claim 1, wherein the value of K and the value of Q ranges from 1 to 10.

4. The method according to claim 1, wherein said reaction conditions include a temperature of the reactor in the range of about 250°

C. to 600°

C.

5. The method according to claim 1, wherein the metal source gas is a material having the general chemical formula MX₄, wherein M is a member selected from the group consisting of Hf, Zr, Ta, Al and Ti, and X is a member selected from the group consisting of F, Cl, Br and I.

6. The method according to claim 1, wherein the metal source gas is a material having the general chemical formula M(NRR′

)₄, wherein M is a member selected from the group consisting of Hf, Zr, Ta, Al and Ti;

R is a member selected from the group consisting of H, Me, Et and ⁱPr; and

R′

is a member selected from the group consisting of H, Me, Et and ⁱPr.

7. The method according to claim 1, wherein the metal source gas is tetrakis (ethylmethylamino) hafnium (TEMAH) having the general chemical formula Hf[N(CH₃)C₂H₅]₄.

8. The method according to claim 1, wherein the oxide gas is at least one member selected from the group consisting of H₂O, O₃, O₂ and H₂O₂.

9. The method according to claim 1, wherein the metal source gas including silicon is a material having the general chemical formula MCl₂[N(Si(CH₃)₃)₂]₂, wherein M is a member selected from the group consisting of Hf, Zr, Ta, Al and Ti.

10. The method according to claim 1, wherein the metal source gas including silicon is a material having the chemical formula HfCl₂[N(Si(CH₃)₃)₂]₂.

11. The method according to claim 1, wherein a composition ratio of a metal element relative to the metal plus silicon in the silicon-doped metal oxide layer is in the range of about 0.85˜

0.95.

12. A method of fabricating a silicon-doped hafnium oxide layer on a substrate using an atomic layer deposition technique, said method comprising the sequential steps of:

(a) loading a substrate into a reactor;

(b) supplying a tetrakis (ethylmethylamino) hafnium (TEMAH) (Hf[N(CH₃)C₂H₅]₄) gas into the reactor having the substrate under reaction conditions to form a chemical adsorption layer including hafnium (Hf) on the substrate;

(c) supplying an oxide gas into the reactor under reaction conditions to react with the chemical adsorption layer including hafnium (Hf), to form a hafnium (Hf) oxide layer on the substrate;

(d) repeatedly performing steps (b) and (c) sequentially K times;

(e) supplying HfCl₂[N(Si(CH₃)₃)₂]₂ gas into the reactor under reaction conditions to form a hafnium (Hf) chemical adsorption layer including silicon on the hafnium (Hf) oxide layer on the substrate;

(f) supplying an oxide gas into the reactor under reaction conditions to react with the hafnium (Hf) oxide layer and the hafnium (Hf) chemical adsorption layer including silicon to form a silicon-doped hafnium oxide (Si-doped HfO₂) layer;

(g) repeatedly performing steps (e) and (f) sequentially Q times; and

(h) performing the operations of steps (b), (c), (d), (e), (f) and (g) sequentially at least one time, thereby forming a silicon-doped hafnium oxide layer with a desired thickness.

13. The method according to claim 12, further comprising the steps of:

exhausting unreacted TEMAH gas remaining in the reactor after each step (b) to clean the inside of the reactor before step (c);

exhausting unreacted oxide gas and reaction byproducts remaining in the reactor after each step (c) to clean the inside of the reactor before step (d);

exhausting unreacted HfCl₂[N(Si(CH₃)₃)₂]₂ gas remaining in the reactor after each step (e) to clean the inside of the reactor before step (f); and

exhausting unreacted oxide gas and reaction byproducts remaining in the reactor after each step (f) to clean the inside of the reactor before step (g).

14. The method according to claim 12, wherein the value of K and the value of Q ranges from 1 to 10.

15. The method according to claim 12, wherein said reaction conditions include a temperature of the reactor in the range of about 250°

C. to 600°

C.

16. The method according to claim 12, wherein the oxide gas is at least one member selected from the group consisting of H₂O, O₃, O₂ and H₂O₂.

17. The method according to claim 12, wherein a composition ratio of hafnium (Hf) element relative to hafnium plus silicon in the silicon-doped hafnium oxide layer is in the range of about 0.85˜

0.95.