Method and apparatus for surface treatment by plasma

• US 4,579,623 A
• Filed: 08/21/1984
• Issued: 04/01/1986
• Est. Priority Date: 08/31/1983
• Status: Expired due to Term

• Current Assignee: Hitachi, Ltd.
• Original Assignee: Hitachi, Ltd.
• Inventors: Suzuki, Keizo, Ninomiya, Ken, Okudaira, Sadayuki, Okada, Osami, Nishimatsu, Shigeru
• Primary Examiner(s): Powell, William A.
• Application Number:
  US06/642,801
• Time in Patent Office: 588 Days
• Field of Search: 156/643, 156/646, 156/651, 156/653, 156/656, 156/657, 156/345, 156/659.1, 156/662, 156/626, 156/627, 204/164, 204/192 EC, 204/192 E, 204/298, 204/192, 427/38, 427/39, 118/715, 118/728, 118/50.1, 118/620, 252/79.1
• US Class Current: 438/7
• CPC Class Codes: C23C 16/4404 Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
• CPC Class Codes: C23C 16/511 using microwave discharges
• CPC Class Codes: H01J 37/32935 Monitoring and controlling tubes by information coming from the object and/or discharge
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/30655 comprising alternated and repeated etching and passivation steps, e.g. Bosch process
• CPC Class Codes: H01L 21/3185 of siliconnitrides
• CPC Class Codes: H01L 21/32135 by vapour etching only
• CPC Class Codes: H01L 21/32136 using plasmas
• CPC Class Codes: H01L 21/32137 of silicon-containing layers

Abstract

A gas is introduced into a vacuum chamber after the vacuum chamber is evacuated, and a plasma is generated within at least part of the vacuum chamber. The specimen surface is exposed to the plasma so that the surface is treated. A plurality of different gases, such as SF₆, N₂, and the like, are used as the gas being introduced. The quantity of the gas is changed during the surface treatment. A controller is used as a mechanism for changing the quantity of gas introduced. The controller is operated in accordance with a predetermined program, or by signals obtained by detecting the surface conditions of the specimen during the surface treatment.

Claims

1. In a method of treating the surface of a specimen in which a vacuum chamber is evacuated, a gas is introduced into said vacuum chamber, a plasma is generated within at least part of said vacuum chamber, and the surface of said specimen is treated by said plasma, a plasma surface treatment method characterized in that a first quantity of said gas is introduced, and the quantity of gas introduced is changed during the surface treatment of said specimen, the introducing of the first quantity of gas and the changed quantity of gas constituting a cycle, and wherein said cycle is repeated at least once.

2. The plasma surface treatment method as defined in claim 1 wherein the quantity of said gas introduced is changed in accordance with a predetermined program.

3. The surface treatment method as defined in claim 1 wherein the quantity of said gas introduced is changed in accordance with the conditions of said surface treatment.

15. The plasma surface treatment method as defined in claim 1 wherein in introducing one of said first quantity of gas and the changed quantity of gas the surface of the specimen is treated under a discharge condition for promoting etching, and in introducing the other of the first quantity of gas and the changed quantity of gas the surface of the specimen is treated under a discharge condition for changing the characteristics of the surface of the specimen.

16. The plasma surface treatment method as defined in claim 15 wherein in introducing the first quantity of gas the surface of the specimen is treated under a discharge condition for promoting etching, and in introducing the changed quantity of gas the surface of the specimen is treated under a discharge condition for changing the characteristics of the surface of the specimen.

17. The plasma surface treatment method as defined in claim 16 wherein the first quantity of gas includes a halogen-containing gas.

18. The plasma surface treatment method as defined in claim 17 wherein the halogen-containing gas is SF₆.

19. The plasma surface treatment method as defined in claim 17 wherein the changed quantity of gas includes at least one of elemental nitrogen, carbon or oxygen, or a compound containing oxygen, nitrogen or carbon.

20. The plasma surface treatment method as defined in claim 16 wherein the changed quantity of gas includes at least one of elemental nitrogen, carbon or oxygen, or a compound containing oxygen, nitrogen or carbon.

21. The plasma surface treatment method as defined in claim 20 wherein the changed quantity of gas consists essentially of at least one rare gas and H₂ in addition to at least one of elemental nitrogen, carbon or oxygen, or a compound containing oxygen, nitrogen or carbon.

22. The plasma surface treatment method as defined in claim 16 wherein the cycle is repeated at least ten times.

23. The plasma surface treatment method as defined in claim 22 wherein, for each cycle, the first quantity of gas is introduced for a longer period of time than the period of time that the changed quantity of gas is introduced.

24. The plasma surface treatment method as defined in claim 1 wherein the surface of the specimen is made of a material selected from the group consisting of Si, Mo, W, Al, and silicides of Mo, W and Al.

25. The plasma surface treatment method as defined in claim 1 wherein in introducing the first quantity of gas the surface of the specimen is treated under a discharge condition for depositing a coating on the surface, and in introducing the changed quantity of gas the specimen is treated under a discharge condition for changing the characteristics of the coating.

26. The plasma surface treatment method as defined in claim 25 wherein the first quantity of gas includes SiF₄ and N₂, and the changed quantity of gas includes N₂ with no SiF₄.

27. The plasma surface treatment method as defined in claim 26 wherein the coating deposited during each cycle of introducing the first quantity of gas is at most 10 nm in thickness.

4. In an apparatus consisting essentially of a vacuum chamber, means for evacuating said vacuum chamber, means for introducing a gas into said vacuum chamber, means for generating plasma within at least part of said vacuum chamber, and means for holding a specimen being surface-treated by said plasma, a plasma surface treatment apparatus characterized in that said gas introduction means is equipped with a mechanism for changing the quantity of said gas introduced during surface treatment, to introduce a first quantity of gas and then a changed quantity of gas during surface treatment, the introduction of the first quantity of gas and the changed quantity of gas being a cycle of gas introduction, the gas introduction means further including means to repeat said cycle at least once.

5. The plasma surface treatment apparatus as defined in claim 4 wherein said mechanism for changing the quantity of said gas introduced is a controller.

6. The plasma surface treatment apparatus as defined in claim 4 wherein said mechanism for changing the quantity of said gas introduced changes the quantity of said gas introduced in accordance with a predetermined program.

7. The plasma surface treatment apparatus as defined in claim 6 wherein the change in said gas introduced is periodical.

8. The plasma surface treatment apparatus as defined in claim 7 wherein the period of said change is longer than the time during which gas molecules or atoms remain within said vacuum chamber.

9. The plasma surface treatment apparatus as defined in claim 7 wherein said mechanism for changing the quantity of said gas introduced changes the quantity of said gas introduced in accordance with a program which measures the condition of the progress of said surface treatment, and feeds back said condition.

28. The plasma surface treatment apparatus as defined in claim 4 further comprising cooling means for cooling the specimen during plasma surface treatment to prevent temperature rise of the specimen.

29. The plasma surface treatment apparatus as defined in claim 4 wherein said means for holding a specimen comprises a rotatable means for holding a plurality of specimens.

30. The plasma surface treatment apparatus as defined in claim 29 further comprising means for rotating said rotatable means, and wherein said means for rotating said rotatable means and said gas introduction means are interlocked.

31. The plasma surface treatment apparatus as defined in claim 4 further comprising means for treating the surface of the specimen under a discharge condition for promoting etching when one of the first quantity and changed quantity of gas is introduced, and means for treating the surface of the specimen under a discharge condition for changing the characteristics of the surface of the specimen when the other of the first quantity and changed quantity of gas are introduced.

10. In an apparatus consisting essentially of a vacuum chamber, means for evacuating said vacuum chamber, means for introducing a gas into said vacuum chamber, means for generating plasma within at least part of said vacuum chamber, means for holding a specimen being surface-treated by said plasma, and means for applying an external voltage to said specimen, a plasma surface treatment apparatus characterized in that said gas introduction means is equipped with a mechanism for changing the quantity of said gas introduced during said surface treatment, to introduce a first quantity of gas and then a changed quantity of gas during said surface treatment, the introduction of the first quantity of gas and the changed quantity of gas being a cycle of gas introduction, the gas introduction means further including means to repeat said cycle at least once.

11. The plasma surface treatment apparatus as defined in claim 10 wherein said external voltage is a radio-frequency (RF) voltage.

12. The plasma surface treatment apparatus as defined in claim 10 or 11 wherein said mechanism for changing the quantity of said gas introduced changes the application of said voltage in accordance with said change in the quantity of said gas introduced.

13. The plasma surface treatment apparatus as defined in claim 10 wherein said mechanism for changing the quantity of said gas introduced changes intermittently the plasma radiation onto said specimen in accordance with said change in the quantity of said gas introduced.

32. The plasma surface treatment apparatus as defined in claim 10 further comprising means for treating the surface of the specimen under a discharge condition for promoting etching when one of the first quantity and changed quantity of gas is introduced, and means for treating the surface of the specimen under a discharge condition for changing the characteristics of the surface of the specimen when the other of the first quantity and changed quantity of gas are introduced.

14. In an apparatus consisting essentially of a vacuum chamber, means for evacuating said vacuum chamber, means for introducing a gas into said vacuum chamber, means for generating plasma within at least part of said vacuum chamber, and means for holding a specimen being surface-treated by said plasma, a plasma surface treatment apparatus characterized by including a mechanism for changing the quantity of said gas introduced, to introduce a first quantity of gas and then a changed quantity of gas into the vacuum chamber during the plasma surface treatment, the introduction of the first quantity of gas and the changed quantity of gas being a cycle of gas introduction, the mechanism further including means to repeat said cycle at least once, and means for detecting the end point of the surface treatment of said specimen from signals from said mechanism.

33. The plasma surface treatment apparatus as defined in claim 14 further comprising means for treating the surface of the specimen under a discharge condition for promoting etching when one of the first quantity and changed quantity of gas is introduced, and means for treating the surface of the specimen under a discharge condition for changing the characteristics of the surface of the specimen when the other of the first quantity and changed quantity of gas are introduced.