Silicon oxime film

• US 5,710,067 A
• Filed: 06/07/1995
• Issued: 01/20/1998
• Est. Priority Date: 06/07/1995
• Status: Expired due to Term

• Current Assignee: GlobalFoundries, Inc.
• Original Assignee: Advanced Micro Devices, Inc.
• Inventors: Foote, David K., Gupta, Subash
• Primary Examiner(s): Bowers, Jr., Charles L.
• Assistant Examiner(s): WHIPPLE, MATTHEW LAVERNE
• Application Number:
  US08/479,718
• Time in Patent Office: 958 Days
• Field of Search: 437/238 US, 437/241 US, 427/574, 427/578, 427/579, 423/324, 423/325, 423/344, 257/632, 257/649
• US Class Current: 438/636
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• 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 21/022 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides adhesion layers or buffer layers H01L21/02304, H01L21/02362
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0276 using an anti-reflective coating anti-reflective coating for lithography in general G03F7/09
• CPC Class Codes: H01L 21/3121 Layers comprising organo-silicon compounds
• CPC Class Codes: H01L 21/3144 on silicon
• CPC Class Codes: H01L 21/3145 formed by deposition from a gas or vapour
• CPC Class Codes: H01L 21/76802 by forming openings in dielectrics
• CPC Class Codes: H01L 21/76829 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
• CPC Class Codes: H01L 21/76834 formation of thin insulating films on the sidewalls or on top of conductors H01L21/76831 takes precedence

Abstract

A silicon oxime film is formed by plasma enhanced chemical vapor deposition. The silicon oxime film is useful as an anti-reflection layer during photolithography, as an etch stop, and as a protection layer.

Claims

1. A film comprising a layer of silicon oxime having the formula Si.sub.(1-x-y-z) N_x O_y :

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, wherein the silicon oxime comprises about 10-20 atom percent hydrogen and has a thickness of about 200 Å

to about 600 Å

.

2. The film according to claim 1, comprising a plurality of layers.

3. The film according to claim 2, comprising a semiconductive or conductive layer and a layer of silicon oxime thereon.

4. The film according to claim 3, wherein the semiconductive layer comprises polycrystalline microcrystalline, and/or amorphous silicon.

5. The film according to claim 3, wherein the conductive layer comprises a material selected from the group consisting of aluminum, aluminum-silicon alloys, refractory metals, refractory metal alloys and refractory metal compounds, and semiconductive materials doped with impurities.

6. The film according to claim 3, wherein the conductive layer comprises a barrier layer of titanium, titanium nitride or titanium-tungsten, and a layer of a conductive material thereon.

7. The film according to claim 2, comprising an insulating layer and a layer of silicon oxime thereon.

8. The film according to claim 7, wherein the insulating layer comprises a material selected in the group consisting of silicon dioxide and silicon nitride.

9. A semiconductor device having a semiconductor or conductor feature pattern comprising the film according to claim 4.

10. A semiconductor device having an insulating layer comprising the film according to claim 7.

11. A semiconductor device containing the film according to claim 1.

12. The silicon oxime according to claim 1, having a thickness of about 400 Å

.

13. The silicon oxime according to claim 1, having a light reflectivity at 365 nm not greater than 2%.

14. The film according to claim 1, wherein the silicon oxime comprises about 15 to about 25 atom percent oxygen.

36. The film according to claim 1, having a light reflectivity at 365 nm of about 1% to about 35%.

37. An anti-reflective coating comprising the film according to claim 1 on a substrate for I-line and deep UV applications.

38. The silicon oxime film according to claim 1, wherein the silicon oxime comprises about 15% atomic percent hydrogen.

39. The silicon oxime film according to claim 2, which is soluble in hot phosphoric acid.

40. The silicon oxime film according to claim 2, which has a dry plasma etchability of about 10% of silicon dioxide.

41. The silicon oxime film according to claim 2, having a thickness of about 350 Å

to about 400 Å and

a reflectivity of about 1 to about 5% at 365 nm.

15. A method of producing a film comprising a layer of silicon oxime having the formula Si.sub.(1-x-y-z) :

N_x O_y ;

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, which method comprises reacting sources of silicon, nitrogen, oxygen and hydrogen in the presence of a stoichiometric excess of nitrogen sufficient to substantially prevent bonding between silicon atoms and oxygen atoms, at a temperature of about 275°

C. to about 475°

C. and at a pressure of about 1 to about 10 Torr, wherein the silicon oxime has a thickness of about 100 Å

to about 600 Å

.

16. The method according to claim 15, wherein the amount of nitrogen present is greater than ten times the amount of oxygen present and the silicon oxime comprises about 10-20 atom percent hydrogen.

17. A method of forming a film comprising silicon oxime having the formula of Si.sub.(1-x-y-z) N_x O_y :

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, which method comprises depositing a layer of silicon oxime having the formula Si.sub.(1-x-y-z) N_x O_y ;

H_z on a substrate by plasma enhanced chemical vapor deposition, wherein deposition is conducted at a temperature of about 275°

C. to about 475°

C., and a pressure of from about 1 to about 10 torr, and wherein said silicon oxime layer has a thickness of about 200 Å

to about 600 Å

.

18. The method according to claim 17, conducted under dynamic non-equilibrium conditions in the presence of a stoichiometric excess of nitrogen sufficient to substantially prevent bonding between silicon atoms and oxygen atoms.

19. The method according to claim 18, comprising reacting source gases for silicon and nitrogen.

20. The method according to claim 19, wherein the source gas for silicon is silane and the source gas for nitrogen is nitrous oxide or nitrogen gas.

21. The method according to claim 17, wherein the silicon oxime comprises about 10-20 atom percent hydrogen.

22. The method according to claim 18, wherein deposition is conducted at a temperature of about 350°

C. to about 450°

C. and a pressure of from about 2 to about 3 Torr.

70. The film according to claim 19, comprising a plurality of layers.

71. The film according to claim 70, comprising a semiconductive or conductive layer and a layer of silicon oxime thereon.

72. The film according to claim 71, wherein the semiconductive layer comprises polycrystalline microcrystalline, and/or amorphous silicon.

73. The film according to claim 71, wherein the conductive layer comprises a material selected from the group consisting of aluminum, aluminum-silicon alloys, refractory metals, refractory metal alloys and refractory metal compounds, and semiconductive materials doped with impurities.

74. The film according to claim 71, wherein the conductive layer comprises a barrier layer of titanium, titanium nitride or titanium-tungsten, and a layer of a conductive material thereon.

75. The film according to claim 70, comprising an insulating layer and a layer of silicon oxime thereon.

76. The film according to claim 75, wherein the insulating layer comprises a material selected in the group consisting of silicon dioxide and silicon nitride.

77. A semiconductor device having a semiconductor or conductor feature pattern comprising the film according to claim 71.

78. A semiconductor device having an insulating layer comprising the film according to claim 75.

23. A method of manufacturing a semiconductor device, which method comprises depositing a layer of silicon oxime having the formula Si.sub.(1 x-y-z) N_x O_y :

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, by plasma enhanced chemical vapor deposition on a substrate under dynamic non-equilibrium conditions in the presence of a stoichiometric excess of nitrogen sufficient to substantially prevent bonding between silicon atoms and oxygen atoms, and at a temperature of about 275°

C. to about 475°

C., wherein the silicon oxime comprises about 10-20 atom percent hydrogen and the layer has a thickness of about 200 Å

to about 600 Å

.

24. The method according to claim 23, wherein the substrate comprises a semiconductive or conductive material.

25. The method according to claim 24, wherein the semiconductive material comprises polycrystalline, microcrystalline and/or amorphous silicon.

26. The method according to claim 24, wherein the conductive material comprises aluminum, an aluminum silicon alloy, refractory metals, refractory metal alloys, and refractory metal compounds, and semiconductive materials doped with impurities.

27. The method according to claim 23, further comprising:

depositing a layer of photoresist material on the silicon oxime film;

imagewise exposing the layer of photoresist material through a photomask defining a desired pattern;

developing the exposed photoresist material; and

etching the underlying silicon oxime and substrate to form the pattern.

28. The method according to claim 27, wherein the substrate comprises a layer of conductive material, and the layer of photoresist material is imagewise exposed through a photomask defining a conductive pattern comprising a plurality of conductive lines and an interwiring spacing therebetween of less than about 0.3 microns.

29. The method according to claim 23, wherein the silicon oxime layer functions as an etch stop layer.

30. The method according to claim 23, wherein the substrate comprises an insulating material.

31. The method according to claim 30, wherein the insulating material is silicon dioxide.

32. The method according to claim 23, comprising depositing a silicon oxime anti-reflective coating on a substrate.

33. The method according to claim 32, further comprising:

depositing a layer of photoresist material on the silicon oxime anti-reflective coating;

imagewise exposing the photoresist material through a photomask defining a pattern comprising a plurality of fine features and spaces;

developing the exposed photoresist material; and

dry etching the underlying silicon oxime anti-reflective coating and substrate to form the pattern.

34. The method according to claim 32, wherein the silicon oxime anti-reflective coating has a light reflectivity at 365 nm not greater than about 2%.

35. The method according to claim 33, wherein the silicon oxime anti-reflective coating has a light reflectivity at 365 nm less than about 1%.

42. A multilayer film comprising:

a semiconductive layer comprising polycrystalline, microcrystalline, and/or amorphous silicon; and

a layer of silicon oxime thereon, wherein the silicon oxime has the formula Si.sub.(1-x-y-z) N_x O_y ;

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively.

43. A semiconductor device containing the multilayer film according to claim 42.

44. The multilayer film according to claim 42, wherein the silicon oxime film has a thickness of about 200 Å

to about 600 Å

.

45. The multilayer film according to claim 44, wherein the silicon oxime film has a thickness of about 400 Å

.

46. The multilayer film according to claim 42, wherein the silicon oxime film has a light reflectivity at 365 nm not greater than 2%.

47. The multilayer film according to claim 44, wherein the silicon oxime comprises about 15 to about 25 atom percent oxygen.

48. The multilayer film according to claim 47, wherein the silicon oxime comprises about 10-20 atom percent hydrogen.

49. The multilayer film according to claim 42, wherein the silicon oxime film has a light reflectivity at 365 nm of about 1% to about 35%.

50. The multilayer film according to claim 42, wherein the silicon oxime film comprises an anti-reflective coating on a substrate for I-line and deep UV applications.

51. The multilayer film according to claim 48, wherein the silicon oxime comprises about 15% atomic percent hydrogen.

52. A multilayer film comprising:

a conductive layer comprising a barrier layer of titanium, titanium nitride or titanium-tungsten, a layer of a conductive material thereon; and

a layer of silicon oxime on the conductive layer, wherein the silicon oxime has the formula Si.sub.(1-x-y-z) N_x O_y ;

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively.

53. A semiconductor device containing the multilayer film according to claim 52.

54. The multilayer film according to claim 52, wherein the silicon oxime film has a thickness of about 200 Å

to about 600 Å

.

55. The multilayer film according to claim 54, wherein the silicon oxime film has a thickness of about 400 Å

.

56. The multilayer film according to claim 53, wherein the silicon oxime film has a light reflectivity at 365 nm not greater than 2%.

57. The multilayer film according to claim 54, wherein the silicon oxime comprises about 15 to about 25 atom percent oxygen.

58. The multilayer film according to claim 57, wherein the silicon oxime comprises about 10-20 atom percent hydrogen.

59. The multilayer film according to claim 52, wherein the silicon oxime film has a light reflectivity at 365 nm of about 1% to about 35%.

60. The multilayer film according to claim 52, wherein the silicon oxime film comprises an anti-reflective coating on a substrate for I-line and deep UV applications.

61. The multilayer film according to claim 58, wherein the silicon oxime comprises about 15% atomic percent hydrogen.

62. A method of manufacturing a semiconductor device, which method comprises depositing a layer of silicon oxime having the formula Si.sub.(1-x-y-z) N_x O_y :

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, by plasma enhanced chemical vapor deposition on a semiconductive substrate, comprising polycrystalline, microcrystalline and/or amorphous silicon, under dynamic non-equilibrium conditions in the presence of a stoichiometric excess of nitrogen sufficient to substantially prevent bonding between silicon atoms and oxygen atoms.

63. The method according to claim 62, further comprising:

depositing a layer of photoresist material on the silicon oxime film;

imagewise exposing the layer of photoresist material through a photomask defining a desired pattern;

developing the exposed photoresist material; and

etching the underlying silicon oxime and substrate to form the pattern.

64. The method according to claim 62, wherein the silicon oxime layer functions as an etch stop layer.

65. The method according to claim 62, comprising depositing a silicon oxime anti-reflective coating on the substrate.

66. The method according to claim 62, further comprising:

depositing a layer of photoresist material on the silicon oxime anti-reflective coating;

imagewise exposing the photoresist material through a photomask defining a pattern comprising a plurality of fine features and spaces;

developing the exposed photoresist material; and

dry etching the underlying silicon oxime anti-reflective coating and substrate to form the pattern.

67. The method according to claim 65, wherein the silicon oxime anti-reflective coating has a light reflectivity at 365 nm not greater than about 2%.

68. The method according to claim 66, wherein the silicon oxime anti-reflective coating has a light reflectivity at 365 nm less than about 1%.

80. The silicon oxime according to claim 66, having a thickness of about 200 Å

to about 600 Å

.

81. The silicon oxime according to claim 80, having a thickness of about 400 Å

.

82. The film according to claim 80, wherein the silicon oxime comprises about 15 to about 25 atom percent oxygen.

69. A film comprising a layer of silicon oxime having the formula Si.sub.(1-x-y-z) N_x O_y :

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, wherein the silicon oxime comprises about 10-20 atom percent hydrogen the layer of silicon oxime has a light reflectivity at 365 nm not greater than 2%.

79. A semiconductor device containing the film according to claim 69.

83. A method of producing a film comprising a layer of silicon oxime having the formula Si.sub.(1-x-y-z) N_x O_y :

H_x, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, which method comprises reacting sources of silicon, nitrogen, oxygen and hydrogen in the presence of a stoichiometric excess of nitrogen sufficient to substantially prevent bonding between silicon atoms and oxygen atoms, at a temperature of about 275°

C. to about 475°

C. and at a pressure of about 1 to about 10 Torr, wherein the silicon oxime has a light reflectivity at 365 nm not greater than 2%.

84. The method according to claim 83, wherein the amount of nitrogen present is greater than ten times the amount of oxygen present and the silicon oxime comprises about 10-20 atom percent hydrogen.

85. A method of forming a film comprising silicon oxime having the formula of Si.sub.(1-x-y-z) N_x O_y :

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, which method comprises depositing a layer of silicon oxime having the formula Si.sub.(1-x-y-z) N_x O_y ;

H_z on a substrate by plasma enhanced chemical vapor deposition, wherein deposition is conducted at a temperature of about 275°

C. to about 475°

C., and a pressure of from about 1 to about 10 torr, and the silicon oxime layer has a light reflectivity at 365 nm not greater than 2%.

86. The method according to claim 85, conducted under dynamic non-equilibrium conditions in the presence of a stoichiometric excess of nitrogen sufficient to substantially prevent bonding between silicon atoms and oxygen atoms.

87. The method according to claim 86, comprising reacting source gases for silicon and nitrogen.

88. The method according to claim 87, wherein the source gas for silicon is silane and the source gas for nitrogen is nitrous oxide or nitrogen gas.

89. The method according to claim 88, wherein the silicon oxime comprises about 10-20 atom percent hydrogen.

90. The method according to claim 85, wherein deposition is conducted at a temperature of about 350°

C. to about 450°

C. and a pressure of from about 2 to about 3 Torr.

91. A method of manufacturing a semiconductor device, which method comprises depositing a layer of silicon oxime having the formula Si.sub.(1-x-y-z)N_x O_y :

H_z, wherein x, y and z represent the atomic percentage of nitrogen, oxygen and hydrogen, respectively, by plasma enhanced chemical vapor deposition on a substrate under dynamic non-equilibrium conditions in the presence of a stoichiometric excess of nitrogen sufficient to substantially prevent bonding between silicon atoms and oxygen atoms, and at a temperature of about 275°

C. to about 475°

C., wherein the silicon oxime comprises about 10-20 atom percent hydrogen and the layer has a light reflectivity at 365 nm nut greater than 2%.

92. The method according to claim 91, wherein the substrate comprises a semiconductive or conductive material.

93. The method according to claim 92, wherein the semiconductive material comprises polycrystalline, microcrystalline and/or amorphous silicon.

94. The method according to claim 92, wherein the conductive material comprises aluminum, an aluminum silicon alloy, refractory metals, refractory metal alloys, and refractory metal compounds, and semiconductive materials doped with impurities.

95. The method according to claim 91, further comprising:

depositing a layer of photoresist material on the silicon oxime film;

imagewise exposing the layer of photoresist material through a photomask defining a desired pattern;

developing the exposed photoresist material; and

etching the underlying silicon oxime and substrate to form the pattern.

96. The method according to claim 95, wherein the substrate comprises a layer of conductive material, and the layer of photoresist material is imagewise exposed through a photomask defining a conductive pattern comprising a plurality of conductive lines and an interwiring spacing therebetween of less than about 0.3 microns.

97. The method according to claim 91, wherein the silicon oxime layer functions as an etch stop layer.

98. The method according to claim 91, wherein the substrate comprises an insulating material.

99. The method according to claim 98, wherein the insulating material is silicon dioxide.

100. The method according to claim 91, comprising depositing a silicon oxime anti-reflective coating on a substrate.

101. The method according to claim 100, further comprising:

depositing a layer of photoresist material on the silicon oxime anti-reflective coating;

imagewise exposing the photoresist material through a photomask defining a pattern comprising a plurality of fine features and spaces;

developing the exposed photoresist material; and

dry etching the underlying silicon oxime anti-reflective coating and substrate to form the pattern.