METHOD OF MODIFYING INSULATING FILM

• US 20100105215A1
• Filed: 12/07/2009
• Published: 04/29/2010
• Est. Priority Date: 05/30/2003
• Status: Active Grant

• Current Assignee: Tokyo Electron Limited
• Original Assignee: Tokyo Electron Limited
• Inventors: MATSUYAMA, Seiji, SUGAWARA, Takuya, SASAKI, Masaru, TADA, Yoshihide, FUJIWARA, Tomonori, NAKANISHI, Toshio, OZAKI, Shigenori, NAKAMURA, Genji, NAKAJIMA, Shigeru, HASEBE, Kazuhide
• Granted Patent: US 8,021,987 B2
• Time in Patent Office: Days
• US Class Current: 438/771
• CPC Class Codes: H01L 21/02112 characterised by the material of the layer
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02252 formation by plasma treatment, e.g. plasma oxidation of the substrate after treatment of an insulating film by plasma H01L21/3105 and subgroups
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/28176 with a treatment, e.g. annealing, after the formation of the definitive gate conductor
• CPC Class Codes: H01L 21/28185 with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/28202 in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
• CPC Class Codes: H01L 21/28211 in a gaseous ambient using an oxygen or a water vapour, e.g. RTO, possibly through a layer H01L21/28194 and H01L21/28202 take precedence
• CPC Class Codes: H01L 21/3144 on silicon
• CPC Class Codes: H01L 21/31658 by thermal oxidation, e.g. of SiGe
• CPC Class Codes: H01L 29/518 the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material
• CPC Class Codes: H01L 29/78 with field effect produced by an insulated gate H01L29/7725, H01L29/775, H01L29/778 take precedence

Abstract

An insulting film is modified by subjecting the insulting film to a modification treatment comprising a combination of a plasma treatment and a thermal annealing treatment. There is provided a method of enhancing the characteristic of an insulating film by improving deterioration in the characteristic of the insulating film due to carbon, a suboxide, a dangling bond or the like contained in the insulating film.

Claims

1-33. -33. (canceled)

34. A substrate processing method comprising:

disposing in a processing container a substrate on which is a vapor deposited insulating film,

introducing a gas containing oxygen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the vapor deposited insulating film to a plasma oxidation treatment by the plasma,

subjecting the plasma oxidized insulating film to a thermal nitridation annealing treatment at a temperature of 500 to 1,200°

C.

35. The substrate processing method according to claim 34, wherein the antenna comprises a plane antenna and microwave is introduced into the plane antenna to generate the plasma.

36. The substrate processing method according to claim 34, wherein the gas to be used for the thermal nitridation annealing contains any of nitrogen (N₂) and ammonia (NH₃).

37. The substrate processing method according to claim 34, wherein the vapor deposited insulating film is selected from a low-dielectric material of SiO₂, SiON or Si₃N₄, and a high-dielectric material of Ta₂O₅, Al₂O₃, La₂O₃, TiO₂, Y₂O₃, BST, Pr₂O₃, Gd₂O₃, CeO₂, HfO₂, HfSiO, or ZrSiO.

38. A substrate processing method comprising:

disposing in a processing container a substrate on which is a vapor deposited insulating film,

introducing a gas containing nitrogen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the vapor deposited insulating film to a plasma nitridation treatment by the plasma,

subjecting the plasma nitrided insulating film to a thermal oxidation annealing treatment at a temperature of 500 to 1,200°

C.

39. The substrate processing method according to claim 38, wherein the antenna comprises a plane antenna and microwave is introduced into the plane antenna to generate the plasma.

40. The substrate processing method according to claim 38, wherein the gas to be used for the thermal oxidation annealing contains any of oxygen (O₂) and ozone (O₃).

41. The substrate processing method according to claim 38, wherein the vapor deposited insulating film is selected from a low-dielectric material of SiO₂, SiON or Si₃N₄, and a high-dielectric material of Ta₂O₅, Al₂O₃, La₂O₃, TiO₂, Y₂O₃, BST, Pr₂O₃, Gd₂O₃, CeO₂, HfO₂, HfSiO, or ZrSiO.

42. The substrate processing method according to claim 38, wherein the gas containing nitrogen atom comprises at least one of N₂ and NH₃.

43. A substrate processing method comprising:

disposing in a processing container a substrate on which is a vapor deposited insulating film,

subjecting the vapor deposited insulating film to a thermal oxidation annealing treatment at a temperature of 500 to 1,200°

C.,

introducing a gas containing nitrogen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the thermal oxidation annealed insulating film to a plasma nitridation treatment by the plasma.

44. The substrate processing method according to claim 43, wherein the antenna comprises a plane antenna and microwave is introduced into the plane antenna to generate the plasma.

45. The substrate processing method according to claim 43, wherein the gas to be used for the thermal oxidation annealing contains any of oxygen (O₂) and ozone (O₃).

46. The substrate processing method according to claim 43, wherein the vapor deposited insulating film is selected from a low-dielectric material of SiO₂, SiON or Si₃N₄, and a high-dielectric material of Ta₂O₅, Al₂O₃, La₂O₃, TiO₂, Y₂O₃, BST, Pr₂O₃, Gd₂O₃, CeO₂, HfO₂, HfSiO, or ZrSiO.

47. The substrate processing method according to claim 43, wherein the gas containing nitrogen atom comprises at least one of N₂ and NH₃.

57. A substrate processing method according to claim 43, further comprising:

introducing a gas containing oxygen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the plasma nitrided insulating film to a plasma oxidation treatment by the plasma.

58. The substrate processing method according to claim 57, wherein the antenna comprises a plane antenna and microwave is introduced into the plane antenna to generate the plasma.

59. The substrate processing method according to claim 57, wherein the gas to be used for the thermal oxidation annealing contains any of oxygen (O₂) and ozone (O₃).

60. The substrate processing method according to claim 57, wherein the vapor deposited insulating film is selected from a low-dielectric material of SiO₂, SiON or Si₃N₄, and a high-dielectric material of Ta₂O₅, Al₂O₃, La₂O₃, TiO₂, Y₂O₃, BST, Pr₂O₃, Gd₂O₃, CeO₂, HfO₂, HfSiO, or ZrSiO.

48. A substrate processing method comprising:

disposing in a processing container a substrate on which is a vapor deposited insulating film,

subjecting the vapor deposited insulating film to a thermal nitridation annealing treatment at a temperature of 500 to 1,200°

C.,

introducing a gas containing oxygen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the thermal nitridation annealed insulating film to a plasma oxidation treatment by the plasma.

49. The substrate processing method according to claim 48, wherein the antenna comprises a plane antenna and microwave is introduced into the plane antenna to generate the plasma.

50. The substrate processing method according to claim 48, wherein the gas to be used for the thermal nitridation annealing contains any of nitrogen (N₂) and ammonia (NH₃).

51. The substrate processing method according to claim 48, wherein the vapor deposited insulating film is selected from a low-dielectric material of SiO₂, SiON or Si₃N₄, and a high-dielectric material of Ta₂O₅, Al₂O₃, La₂O₃, TiO₂, Y₂O₃, BST, Pr₂O₃, Gd₂O₃, CeO₂, HfO₂, HfSiO, or ZrSiO.

52. A substrate processing method comprising:

disposing in a processing container a substrate on which is a vapor deposited insulating film,

introducing a gas containing nitrogen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the vapor deposited insulating film to a plasma nitridation treatment by the plasma,

subjecting the plasma nitrided insulating film to a thermal nitridation annealing treatment at a temperature of 500 to 1,200°

C., or introducing a gas containing oxygen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the plasma nitrided insulating film to a plasma oxidation treatment by the plasma,

introducing a gas containing oxygen atom and a rare gas into the processing container and introducing electromagnetic wave into the processing container through an antenna to generate a plasma, thereby subjecting the thermal nitridation annealed insulating film to a plasma oxidation treatment by the plasma or subjecting the plasma oxidized insulating film to a thermal nitridation annealing treatment at a temperature of 500 to 1,200°

C.

53. The substrate processing method according to claim 52, wherein the antenna comprises a plane antenna and microwave is introduced into the plane antenna to generate the plasma.

54. The substrate processing method according to claim 52, wherein the gas to be used for the thermal nitridation annealing contains any of nitrogen (N₂) and ammonia (NH₃).

55. The substrate processing method according to claim 52, wherein the vapor deposited insulating film is selected from a low-dielectric material of SiO₂, SiON or Si₃N₄, and a high-dielectric material of Ta₂O₅, Al₂O₃, La₂O₃, TiO₂, Y₂O₃, BST, Pr₂O₃, Gd₂O₃, CeO₂, HfO₂, HfSiO, or ZrSiO.

56. The substrate processing method according to claim 52, wherein the gas containing nitrogen atom comprises at least one of N₂ and NH₃.