In-situ hybrid deposition of high dielectric constant films using atomic layer deposition and chemical vapor deposition

• US 7,816,278 B2
• Filed: 03/28/2008
• Issued: 10/19/2010
• Est. Priority Date: 03/28/2008
• Status: Expired due to Fees

• Current Assignee: Tokyo Electron Limited
• Original Assignee: Tokyo Electron Limited
• Inventors: Reid, Kimberly G., Dip, Anthony
• Primary Examiner(s): LE, DUNG ANH
• Application Number:
  US12/058,470
• Publication Number:
  US 20090246971A1
• Time in Patent Office: 935 Days
• Field of Search: 438681-689, 438/758, 438/763
• US Class Current: 438/758
• CPC Class Codes: C23C 16/02 Pretreatment of the material to be coated C23C16/04 takes precedence
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/44 characterised by the method of coating C23C16/04 takes precedence
• CPC Class Codes: C23C 16/45546 specially adapted for a substrate stack in the ALD reactor
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02312 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/3144 on silicon
• CPC Class Codes: H01L 21/3162 on a silicon body
• CPC Class Codes: H01L 21/31637 Deposition of Tantalum oxides, e.g. Ta2O5
• CPC Class Codes: H01L 21/31641 Deposition of Zirconium oxides, e.g. ZrO2
• CPC Class Codes: H01L 21/31645 Deposition of Hafnium oxides, e.g. HfO2

Abstract

An in-situ hybrid film deposition method for forming a high-k dielectric film on a plurality of substrates in a batch processing system. The method includes loading the plurality of substrates into a process chamber of the batch processing system, depositing by atomic layer deposition (ALD) a first portion of a high-k dielectric film on the plurality of substrates, after depositing the first portion, and without removing the plurality of substrates from the process chamber, depositing by chemical vapor deposition (CVD) a second portion of the high-k dielectric film on the first portion, and removing the plurality of substrates from the process chamber. The method can further include alternatingly repeating the deposition of the first and second portions until the high-k dielectric film has a desired thickness. The method can still further include pre-treating the substrates and post-treating the high-k dielectric film in-situ prior to the removing.

Claims

1. An in-situ hybrid film deposition method, comprising:

loading a plurality of substrates into a process chamber of a batch processing system;

depositing a first portion of a high-k dielectric film on the plurality of substrates by atomic layer deposition (ALD);

after depositing the first portion, and without removing the plurality of substrates from the process chamber, depositing a second portion of the high-k dielectric film on the first portion by chemical vapor deposition (CVD);

prior to removing the plurality of substrates from the process chamber, post-treating the first portion or the second portion of the high-k dielectric film, wherein the post-treating is selected from one or any sequential combination of;

(a) a high temperature anneal at a substrate temperature between about 500°

C. and about 1000°

C. with no gaseous environment;

(b) a high temperature oxidation at substrate temperature between about 500°

C. and about 1000°

C. in the presence of a fourth oxidizer selected from an oxygen-containing gas or an oxygen- and nitrogen-containing gas;

or

(c) a high temperature anneal at a substrate temperature between about 500°

C. and about 1000°

C. in the presence of a non-oxidizing gas; and

removing the plurality of substrates from the process chamber.

2. The method of claim 1, further comprising:

prior to the deposition of the first portion, pre-treating the plurality of substrates in the process chamber with a first oxidizer selected from an oxygen-containing gas or an oxygen- and nitrogen-containing gas at a substrate temperature between 100°

C. and 1000°

C.

3. The method of claim 2, wherein the pre-treating is performed at higher substrate temperatures than the deposition of the first and second portions.

4. The method of claim 2, wherein the first oxidizer is selected from O₂, O₃, N₂O, NO, or H₂O vapor, or a combination thereof.

5. The method of claim 1, wherein depositing the first portion comprises:

performing a plurality of deposition cycles, each cycle comprising alternating exposures of the plurality of substrates in the process chamber to a second oxidizer and a metal precursor with optional purging in-between, wherein the second oxidizer is selected from an oxygen-containing gas or an oxygen- and nitrogen-containing gas.

6. The method of claim 5, wherein the second oxidizer is selected from O₂, O₃, N₂O, NO, or H₂O vapor, or a combination thereof.

7. The method of claim 1, wherein the deposition of the second portion comprises:

simultaneously exposing the plurality of substrates in the process chamber to a third oxidizer and a metal precursor, wherein the third oxidizer is selected from an oxygen-containing gas or an oxygen- and nitrogen-containing gas.

8. The method of claim 7, wherein the third oxidizer is selected from O₂, O₃, N₂O, NO, or H₂O vapor, or a combination thereof.

9. The method of claim 1, wherein the post-treating is performed at a higher substrate temperature than the deposition of the first and second portions.

10. The method of claim 1, wherein the fourth oxidizer is selected from O₂, O₃, N₂O, NO, or H₂O vapor, or a combination thereof.

11. The method of claim 1, further comprising:

alternatingly repeating the deposition of the first and second portions, wherein each first portion has a first thickness and each second portion has a second thickness.

12. The method of claim 11, wherein each of the first portions, each of the second portions, or each of the first and second portions have substantially the same thickness.

13. The method of claim 11, wherein at least one of the second portions has a first thickness that is smaller or greater than the other second portions.

14. The method of claim 1, wherein the deposition of the first and the second portions is performed at substantially the same substrate temperature.

15. The method of claim 1, wherein the deposition of the first and second portions is performed at different substrate temperatures.

16. An in-situ hybrid film deposition method, comprising:

loading a plurality of substrates into a process chamber of a batch processing system;

depositing a first portion of a high-k dielectric film on the plurality of substrates by atomic layer deposition (ALD);

after depositing the first portion, and without removing the plurality of substrates from the process chamber, depositing a second portion of the high-k dielectric film on the first portion by chemical vapor deposition (CVD); and

removing the plurality of substrates from the process chamber, wherein the deposition of the first portion utilizes a second oxidizer, depositing the second portion utilizes a third oxidizer that is different than the second oxidizer, and each of the second and third oxidizers are selected from O₂, O₃, N₂O, NO, or H₂O vapor, or a combination thereof.

17. An in-situ hybrid film deposition method, comprising:

loading a plurality of substrates into a process chamber of a batch processing system;

pre-treating the plurality of substrates in the process chamber with a first oxidizer at a substrate temperature between 500°

C. and 1000°

C.;

following the pre-treating, depositing a first portion of a HfO₂ film on the plurality of substrates by atomic layer deposition (ALD), wherein the depositing a first portion includes performing a plurality of deposition cycles, each cycle comprising alternating exposure of the plurality of substrates in the process chamber to a second oxidizer and a metal precursor with optional purging in-between;

depositing a second portion of the HfO₂ film on the first portion by chemical vapor deposition (CVD), wherein the depositing by CVD includes simultaneously exposing the plurality of substrates to a third oxidizer and the metal precursor;

post-treating the plurality of substrates containing the HfO₂ film by performing a high temperature oxidation anneal at a substrate temperature between about 500°

C. and about 1000°

C. in the presence of a fourth oxidizer, wherein the first, second, third, and fourth oxidizers are each selected from O₂, O₃, N₂O, NO, or H₂O vapor, or a combination thereof, and wherein the pre-treating, depositing the first portion, depositing the second portion, and the post-treating are performed without removing the plurality of substrates from the process chamber; and

removing the plurality of substrates from the process chamber.

18. The method of claim 17, wherein the pre-treating and post-treating are performed at higher substrate temperatures than the deposition of the first and second portions.

19. The method of claim 17, wherein the deposition of the first and second portions is performed at different substrate temperatures.