Source: http://patents.com/us-7501352.html
Timestamp: 2019-03-25 17:54:36
Document Index: 151767485

Matched Legal Cases: ['Application No. 095109279', 'Application No. 095109279', 'Application No. 95109788', 'Application No. 95109788', 'Application No. 200680010825', 'Application No. 200680010882', 'Application No. 200680010825', 'Application No. 200680010882']

US Patent # 7,501,352. Method and system for forming an oxynitride layer - Patents.com
United States Patent 7,501,352
Igeta , et al. March 10, 2009
Method and system for forming an oxynitride layer
Inventors: Igeta; Masanobu (Fishkill, NY), Wajda; Cory (Sand Lake, NY), O'Meara; David L. (Poughkeepsie, NY), Scheer; Kristen (Milton, NY), Eurakawa; Toshihara (Essex Junction, VT)
Assignee: Tokyo Electron, Ltd. (Tokyo, JP)
International Business Machines Corporation ("IBM") (Armonk, NY)
Appl. No.: 11/093,260
Current U.S. Class: 438/769 ; 257/E21.267; 438/786
Field of Search: 438/769-772,775-778,782-798 257/E21.267
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1. A method for preparing an oxynitride film on a substrate, comprising: oxidizing a surface of said substrate to form an oxide film by exposing said surface of said substrate to oxygen radicals formed by ultraviolet (UV) radiation induced dissociation of a first process gas comprising at least one molecular composition comprising oxygen; nitriding said oxide film to form the oxynitride film by exposing said oxide film to nitrogen radicals formed by plasma induced dissociation of a second process gas comprising at least one molecular composition comprising nitrogen using plasma based on microwave irradiation via a plane antenna member having a plurality of slits; and annealing the oxynitride film, subsequent to forming the oxynitride film and before forming any layer on the oxynitride film, by exposing the oxynitride film to oxygen radicals and nitrogen radicals formed by ultraviolet (UV) radiation induced dissociation of an annealing gas comprising at least one molecular composition comprising oxygen and nitrogen.
3. The method of claim 1, wherein the molecular composition in the first process gas comprises O.sub.2, NO, N.sub.2O, or NO.sub.2, or any combination of two or more thereof and optionally at least one gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
4. The method of claim 1, wherein the molecular composition in the first process gas comprises O.sub.2, and the oxygen radicals are produced from ultraviolet radiation induced dissociation of the O.sub.2.
6. The method of claim 1, wherein the oxide film has a thickness variation .sigma. of about 0.2% to about 4%.
9. The method of claim 1, wherein the oxidizing is carried out at a substrate temperature of about 200.degree. C. to about 1000.degree. C.
11. The method of claim 1, wherein the molecular composition in the first process gas comprises O.sub.2, and the oxidizing is carried out at an O.sub.2 flow rate of about 30 sccm to about 5 slm.
12. The method of claim 1, wherein the molecular composition in the first process gas further comprises at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein a flow rate of the second gas is about 0 slm to about 5 slm.
15. The method of claim 1, wherein the ultraviolet radiation in said ultraviolet radiation induced dissociation during the oxidizing originates from an ultraviolet radiation source operating at a power of about 5 mW/cm.sup.2 to about 50 mW/cm.sup.2.
19. The method of claim 1, wherein the oxide film has the formula SiO.sub.2.
20. The method of claim 1, wherein the molecular composition in the second process gas comprises N.sub.2 and optionally at least one gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
21. The method of claim 1, wherein the molecular composition in the second process gas comprises N.sub.2 and H.sub.2 and optionally at least one gas selected from the group consisting of Ar, He, Ne, Xe, or Kr, or any combination thereof.
22. The method of claim 1, wherein the molecular composition in the second process gas comprises N.sub.2, or NH.sub.3, or both, and the nitrogen radicals are produced from plasma induced dissociation of the N.sub.2, or NH.sub.3, or both.
24. The method of claim 1, wherein the oxynitride film has a thickness variation .sigma. of about 0.2% to about 4%.
26. The method of claim 1, wherein the nitriding is carried out at a substrate temperature of about 20.degree. C. to about 1000.degree. C.
28. The method of claim 1, wherein the molecular composition in the second process gas comprises N.sub.2, and the nitriding is carried out at an N.sub.2 flow rate of about 2 sccm to about 5 slm.
29. The method of claim 1, wherein the molecular composition in the second process gas further comprises at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein a flow rate of the second gas is about 100 sccm to about 5 slm.
32. The method of claim 1, wherein the plasma for the nitriding has a density of about 1.times.10.sup.11 to about 1.times.10.sup.13 and density uniformity of about .+-.3% or less.
34. The method of claim 1, wherein the plasma is generated by a microwave output of about 0.5 W/cm.sup.2 to about 5 W/cm.sup.2.
45. The method of claim 1, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen, wherein said upstream plasma induced dissociation. comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas, and wherein the second nitriding step is carried out at a substrate temperature of about 20.degree. C. to about 1200.degree. C.
47. The method of claim 1, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen, wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas, wherein the upstream molecular composition comprises N.sub.2 flowing at an N.sub.2 flow rate of about 2 sccm to about 20 slm.
48. The method of claim 1, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen and optionally at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas.
49. The method of claim 1, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas, and wherein the second gas has a flow rate of about 100 sccm to about 20 slm.
56. The method of claim 1, wherein the annealing of the oxynitride film occurs at a temperature of about 500.degree. C. to about 1200.degree. C.
57. The method of claim 1, wherein the annealing gas further compromises H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
58. The method of claim 1, wherein the annealing gas comprises N.sub.2 at an N.sub.2 flow rate of about 0 slm to about 20 slm.
59. The method of claim 1, wherein the annealing gas comprises O.sub.2 at an O.sub.2 flow rate of about 0 slm to about 20 slm.
64. The method of claim 1, wherein the annealing gas comprises at least one molecular composition comprising oxygen. and nitrogen selected from the group consisting of O.sub.2, N.sub.2, NO, NO.sub.2, and N.sub.2O , or any combination thereof.
65. The method of claim 1, wherein the annealing gas further comprises H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
69. The method of claim 1, wherein the annealing is carried out at a temperature of about 400.degree. C. to about 1200.degree. C.
73. The method of claim 1, wherein the ultraviolet radiation in the ultraviolet radiation induced dissociation during the annealing originates from an ultraviolet radiation source operating at a power of about 5 mW/cm.sup.2 to about 50 mW/cm.sup.2.
78. The method of claim 1, wherein the annealing of the oxynitride, film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen, and wherein the upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to the upstream annealing gas, and wherein the annealing is carried out is carried out at a substrate temperature of about 20.degree. C. to about 1200.degree. C.
80. The method of claim 1, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen, and wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream annealing gas, and wherein the annealing is carried out under N.sub.2 flowing at an N.sub.2 flow rate of about 2 sccm to about 20 slm.
81. The method of claim 1, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream annealing gas.
82. The method of claim 1, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream annealing gas, and wherein the second gas has a flow rate of about 100 sccm to about 20 slm.
83. The method of claim 1, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power having a frequency of about 40 kHz to about 4 MHz to said upstream annealing gas.
86. A method for preparing an oxynitride film on a silicon substrate, comprising: oxidizing a surface of said silicon substrate to form an oxide film by exposing said surface of said substrate to oxygen radicals formed by ultraviolet (UV) radiation induced dissociation of a first process gas comprising at least one molecular composition comprising oxygen; nitriding said oxide film to form the oxynitride film by exposing said oxide film to nitrogen radicals formed by plasma induced dissociation of a second process gas comprising at least one molecular composition comprising nitrogen using plasma based on microwave irradiation via a plane antenna member having a plurality of slits; and annealing the oxynitride film, subsequent to forming the oxynitride film and before forming any layer on the oxynitride film by exposing the oxynitride film to oxygen radicals and nitrogen radicals formed by ultraviolet (UV) radiation induced dissociation of an annealing gas comprising at least one molecular composition comprising oxygen and nitrogen at a temperature of about 800.degree. C. to about 1100.degree. C. and for a time period of about 5 seconds to about 5 minutes.
87. The method of claim 86, wherein the molecular composition in the first process gas comprises O.sub.2, NO, N.sub.2O , or NO.sub.2, or any combination of two or more thereof and optionally at least one gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
88. The method of claim 86, wherein the molecular composition in the first process gas comprises O.sub.2, and the oxygen radicals are produced from ultraviolet radiation induced dissociation of the O.sub.2.
90. The method of claim 86, wherein the oxide film has a thickness variation .sigma. of about 0.2% to about 4%.
93. The method of claim 86, wherein the oxidizing is carried out at a substrate temperature of about 200.degree. C. to about 1000.degree. C.
95. The method of claim 86, wherein the molecular composition in the first process gas comprises O.sub.2, and the oxidizing is carried out at an O.sub.2 flow rate of about 30 sccm to about 5 slm.
96. The method of claim 86, wherein the molecular composition in the first process gas further comprises at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein a flow rate of the second gas, is about 0 slm to about 5 slm.
99. The method of claim 86, wherein the ultraviolet radiation in said ultraviolet radiation induced dissociation during the oxidizing originates from an ultraviolet radiation source operating at a power of about 5 mW/cm.sup.2 to about 50 mW/cm.sup.2.
103. The method of claim 86, wherein the oxide film has the formula SiO.sub.2.
104. The method of claim 86, wherein the molecular composition in the second process gas comprises N.sub.2 and optionally at least one gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
105. The method of claim 86, wherein the molecular composition in the second process gas comprises N.sub.2 and H.sub.2 and optionally at least one gas selected from the group consisting of Ar, He, Ne, Xe, or Kr, or any combination thereof.
106. The method of claim 86, wherein the molecular composition in the second process gas comprises N.sub.2, or NH.sub.3, or both, and the nitrogen radicals are produced from plasma induced dissociation of the N.sub.2, or NH.sub.3, or both.
108. The method of claim 86, wherein the oxynitride film has a thickness variation .sigma. of about 0.2% to about 4%.
110. The method of claim 86, wherein the nitriding is carried out at a substrate temperature of about 20.degree. C. to about 1000.degree. C.
112. The method of claim 86, wherein the molecular composition in the second process gas comprises N.sub.2, and the nitriding is carried out at an N.sub.2 flow rate of about 2 sccm to about 5 slm.
113. The method of claim 86, wherein the molecular composition in the second process gas further comprises at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein a flow rate of the second gas is about 100 sccm to about 5 slm.
116. The method of claim 86, wherein the plasma for the nitriding has a density of about 1.times.10.sup.11 to about 1.times.10.sup.13 and density uniformity of about .+-.3% or less.
118. The method of claim 86, wherein the plasma is generated by a microwave output of about 0.5 W/cm.sup.2 about 5 W/cm.sup.2.
129. The method of claim 86, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen, wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas, and wherein the second nitriding step is carried out at a substrate temperature of about 20.degree. C. to about 1200.degree. C.
131. The method of claim 86, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen, wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas, wherein the upstream molecular composition comprises N.sub.2 flowing at an N.sub.2 flow rate of about 2 sccm to about 20 slm.
132. The method of claim 86, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen and optionally at least one second gas selected from The group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas.
133. The method of claim 86, wherein the nitriding further comprises a second nitriding step of exposing the oxide film or oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, wherein said upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to said upstream process gas, and wherein the second gas has a flow rate of about 100 sccm to about 20 slm.
140. The method of claim 86, wherein the annealing gas further comprises H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
141. The method of claim 86, wherein the annealing gas comprises N.sub.2 at an N.sub.2 flow rate of about 0 slm to about 20 slm.
142. The method of claim 86, wherein the annealing gas comprises O.sub.2 at an O.sub.2 flow rate of about 0 slm to about 20 slm.
146. The method of claim 86, wherein the annealing gas comprises at least one molecular composition comprising oxygen and nitrogen selected from the group consisting of O.sub.2, N.sub.2, NO, NO.sub.2, and N.sub.2O , or any combination thereof.
147. The method of claim 86, wherein annealing gas further comprises H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
153. The method of claim 86, wherein the ultraviolet radiation in the ultraviolet radiation induced dissociation during the annealing originates from an ultraviolet radiation source operating at a power of about 5 mW/cm.sup.2 to about 50 mW/cm.sup.2.
158. The method of claim 86, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen, and wherein the upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to the upstream annealing gas, and wherein the annealing is carried out under N.sub.2 flowing at an N.sub.2 flow rate of about 2 sccm to about 20 slm.
159. The method of claim 86, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein the upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to the upstream annealing gas.
160. The method of claim 86, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein the upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power to the upstream annealing gas, and wherein the second gas has a flow rate of about 100 sccm to about 20 slm.
161. The method of claim 86, wherein the annealing of the oxynitride film includes exposing the oxynitride film to second nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen and at least one second gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof, and wherein the upstream plasma induced dissociation comprises using plasma generated via the coupling of radio frequency (RF) power having a frequency of about 40 kHz to about 4 MHz to the upstream annealing gas.
163. A method for making a semiconductor or electronic device, comprising the method of claim 86.
UVO.sub.2 Oxidation
According to one embodiment, FIG. 2 presents a schematic diagram of a processing system for performing an oxidation process. The processing system 101 comprises a process chamber 110 having a substrate holder 120 configured to support a substrate 125 having a silicon (Si) surface. The process chamber 110 further contains an electromagnetic radiation assembly 130 for exposing the substrate 125 to electromagnetic radiation. Additionally, the processing system 101 contains a power source 150 coupled to the electromagnetic radiation assembly 130, and a substrate temperature control system 160 coupled to substrate holder 120 and configured to elevate and control the temperature of substrate 125. A gas supply system 140 is coupled to the process chamber 110, and configured to introduce a process gas to process chamber 110. For example, in an oxidation process, the process gas can include an oxygen containing gas, such as, for example, O.sub.2, NO, NO.sub.2 or N.sub.2O. The process gas can be introduced at a flow rate of about 30 sccm to about 5 slm, which includes 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (sccm), 2, 3, 4, or 5 (slm), or any combination thereof. Additionally (not shown), a purge gas can be introduced to process chamber 110. The purge gas may comprise an inert gas, such nitrogen or a noble gas (i.e., helium, neon, argon, xenon, krypton). The flow rate of the purge gas can be about 0 slm to about 5 slm, which includes 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (sccm), 2, 3, 4, or 5 (slm), or any combination thereof.
The electromagnetic radiation assembly 130 can, for example, comprise an ultraviolet (UV) radiation source. The UV source may be monochromatic or polychromatic. Additionally, the UV source can be configured to produce radiation at a wavelength sufficient for dissociating the process gas, i.e., O.sub.2. In one embodiment, the ultraviolet radiation can have a wavelength from about 145 nm to about 192 nm, which includes 145, 147, 150, 155, 171, 172, 173, 175, 180, 185, 190, and 192 nm as appropriate for the binding energy of the molecule which is dissociated. The electromagnetic radiation assembly 130 can operate at a power of about 5 mW/cm.sup.2 to about 50 mW/cm.sup.2, which includes 5, 6, 7, 8, 9, 10, 11, 13, 15, 17, 19, 20, 30, 40, 50 mW/cm.sup.2, or any combination thereof. The electromagnetic radiation assembly 130 can include one, two, three, four, or more radiation sources. The sources can include lamps or lasers or a combination thereof.
Still referring to FIG. 2, controller 170 can comprise a microprocessor, memory, and a digital I/O port capable of generating control voltages sufficient to communicate and activate inputs to processing system 101 as well as monitor outputs from processing system 101. For example, a program stored in the memory may be utilized to activate the inputs to the aforementioned components of the processing system 101 according to a process recipe in order to perform process. One example of the controller 170 is a DELL PRECISION WORKSTATION 610.TM., available from Dell Corporation, Austin, Tex.
The processing conditions can further include a substrate temperature between about 0.degree. C. and about 1000.degree. C. Alternately, the substrate temperature can be between about 200.degree. C. and about 700.degree. C. Thus, the oxidizing can be carried out at a substrate temperature of 200, 225, 250, 275, 300, 325, 350, 375, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000.degree. C., or any combination thereof.
The oxygen radicals associate with the surface of substrate 125 to oxidize the surface of the substrate. The composition of the surface can be SiO.sub.2.
TABLE-US-00001 UVO.sub.2 Parameter Typical Low High Pressure 0.1 T 0.01 T 20 T Temperature 700 C. 400 C. 800 C. Gas Ar 0 0 2 slm Gas O.sub.2 450 sccm 100 sccm 2 slm Time 60 sec 10 sec 5 min
FIG. 4 is a simplified block-diagram of a plasma processing system containing a slot plane antenna (SPA) plasma source for nitridation process according to an embodiment of the invention. The plasma produced in the plasma processing system 400 is characterized by low electron temperature (less than about 1.5 eV) and high plasma density (e.g., >about 1.times.10.sup.12/cm.sup.3), that enables damage-free processing of gate stacks according to the invention. The plasma processing system 400 can, for example, be a TRIAS.TM. SPA processing system from Tokyo Electron Limited, Akasaka, Japan. The plasma processing system 400 contains a process chamber 450 having an opening portion 451 in the upper portion of the process chamber 450 that is larger than a substrate 125. A cylindrical dielectric top plate 454 made of quartz or aluminum nitride or aluminum oxide is provided to cover the opening portion 451. Gas lines 472 are located in the side wall of the upper portion of process chamber 450 below the top plate 454. In one example, the number of gas lines 472 can be 16 (only two of which are shown in FIG. 4). Alternately, a different number of gas feed lines 472 can be used. The gas lines 472 can be circumferentially arranged in the process chamber 450, but this is not required for the invention. A process gas can be evenly and uniformly supplied into the plasma region 459 in process chamber 450 from the gas lines 472. Alternatively, a feed line 472 on the upstream side of the substrate relative to the exhaust may be configured as a remote RF plasma source suitable for nitridation.
For nitridation, a gas containing a molecular composition having nitrogen may be introduced into any of system 20 (FIG. 1), process chambers 110 (FIG. 2), 210 (FIG. 3), and/or 450 (FIG. 4). Any nitrogen containing composition is suitable, e.g., any of N.sub.2, NH.sub.3, NO, N.sub.2O, NO.sub.2, alone or in combination. Once introduced, the nitrogen containing composition may be dissociated via either microwave radiation plasma induced dissociation based on microwave irradiation via a plane antenna having a plurality of slits or in-chamber plasma induced dissociation, or, alternatively, it may be dissociated by an RF plasma source located upstream of the substrate via the coupling of RF power to the nitrogen containing composition.
Any nitrogen containing composition is suitable, e.g., any of N.sub.2, NO, N.sub.2O, NO.sub.2, alone or in combination. In one embodiment, the molecular composition in the nitriding, oxynitriding, or annealing process gas may include N.sub.2 and optionally at least one gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof. In one embodiment, the molecular composition in the second process gas comprises N.sub.2 and H.sub.2 and optionally at least one gas selected from the group consisting of H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof. The nitrogen containing molecular composition in the process gas may suitably comprise N.sub.2, and the nitrogen radicals are produced from plasma induced dissociation of the N.sub.2.
The oxynitride film obtained under nitridation may have a thickness of about 0.1 nm to about 5 nm, which range includes 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.8, 4, 4.1, 4.5, or 5 nm, or any combination thereof. The oxynitride film may have a thickness variation .sigma. of about 0.2% to about 4%, which includes 0.2, 0.3, 0.5, 0.7, 0.9, 1, 2, 3, or 4%.
The nitriding may be carried out at a substrate temperature of about 20.degree. C. to about 1000.degree. C., which range includes 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000.degree. C., or any combination thereof.
The flow rate of the nitrogen containing molecular composition N.sub.2 may range from 2 sccm to 5 slm, and that of the second gas may be about 100 sccm to about 5 slm. These ranges include 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (sccm), 2, 3, 4, or 5 (slm), or any combination thereof.
The nitriding plasma may be generated by a microwave output of about 0.5 W/cm.sup.2 to about 5 W/cm.sup.2, which includes 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.3, 1.5, 1.7, 1.9, 2, 3, 4, or 5 W/cm.sup.2, or any combination thereof.
In this embodiment, the plasma may comprise an electron temperature of less than about 3 eV, which includes 0.1, 0.3, 0.5, 0.7, 0.9, 1, 1.5, 2, 2.5, or 3 eV, or any combination thereof. The plasma may have a density of about 1.times.10.sup.11/cm.sup.3 to about 1.times.10.sup.13/cm.sup.3 or higher, and a density uniformity of about .+-.3% or less, which includes .+-.1, .+-.2, and .+-.3%.
TABLE-US-00002 SPAN Parameter Typical Low High Pressure 50 mT 10 mT 10 T Temperature 400 C. 25 C. 800 C. Gas Ar 1 slm 100 slm 5 slm Gas N2 40 sccm 5 sccm 1 slm Time 20 sec 5 sec 5 min
TABLE-US-00003 RFN Parameter Typical Low High Pressure 200 mT 10 mT 10 T Temperature 400 C. 25 C. 1000 C. Gas Ar 1 slm 500 sccm 10 slm Gas N2 100 sccm 10 sccm 1 slm Time 60 sec 5 sec 5 min
The LP annealing may be carried out at a temperature of about 500.degree. C. to about 1200.degree. C., which includes 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, or 1200.degree. C., or any combination thereof.
The LP annealing may be carried out under an annealing gas comprising at least one molecular composition comprising oxygen, nitrogen, H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof at a flow rate of 0 to 20 slm. In one embodiment, LP annealing is effected under N.sub.2 at an N.sub.2 flow rate of about 0 slm to about 20 slm, which includes 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (sccm), 2, 3, 4, 5, 10, 15, or 20 (slm), or any combination thereof.
TABLE-US-00004 LP Anneal Parameter Typical Low High Pressure 1 T 50 mT 760 T Temperature 1000 C. 800 C. 1100 C. Gas N2 1 slm 0 10 slm Gas O2 1 slm 0 10 slm Time 15 sec 5 sec 5 min
UVO.sub.2/N.sub.2 Post Anneal
The UVO.sub.2/N.sub.2 post anneal alternatively suitably anneals the oxynitride film by exposing the film to oxygen radicals and nitrogen radicals formed by ultraviolet (UV) radiation induced dissociation of an annealing gas comprising at least one molecular composition comprising oxygen and nitrogen.
The UVO.sub.2/N.sub.2 Post Anneal suitably anneals the oxynitride film by exposing said oxynitride film to oxygen radicals and nitrogen radicals formed by ultraviolet (UV) radiation induced dissociation of an annealing gas comprising at least one molecular composition comprising oxygen and nitrogen. The oxygen and nitrogen radicals are dissociated from an annealing gas comprising at least one molecular composition comprising oxygen and nitrogen selected from the group consisting of O2, N2, NO, NO2, and N2O, or any combination thereof. Other gases may be present for example one or more of H2, Ar, He, Ne, Xe, or Kr, or any combination thereof.
The annealing may be carried out at a temperature of about 400.degree. C. to about 1200.degree. C., which includes 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, or 1200.degree. C., or any combination thereof.
It may originate from an ultraviolet radiation source operating at a power of about 5 mW/cm.sup.2 to about 50 mW/cm.sup.2, which includes 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.3, 1.5, 1.7, 1.9, 2, 3, 4, or 5 W/cm.sup.2, or any combination thereof. One or more ultraviolet sources may be used.
The annealing may be suitably carried out at a substrate temperature of about 20.degree. C. to about 1200.degree. C., which includes 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, or 1200.degree. C., or any combination thereof.
The annealing may be carried out under N.sub.2 at an N.sub.2 flow rate of about 2 sccm to about 20 slm, which includes 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (sccm), 2, 3, 4, 5, 10, 15, or 20 (slm), or any combination thereof.
The annealing may also be carried out in the presence of other gases, for example, H.sub.2, Ar, He, Ne, Xe, or Kr, or any combination thereof. The flow rate of these other gases may be about 100 sccm to about 20 slm, which includes 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (sccm), 2, 3, 4, 5, 10, 15, or 20 (slm), or any combination thereof.
Other suitable systems and methods are described in the following references, the entire contents of each of which are independently incorporated by reference: JP 2001-012917, filed Jan. 22, 2001; JP 2001-374631, filed Dec. 7, 2001; JP 2001-374632, filed Dec. 7, 2001; JP 2001-374633, filed Dec. 7, 2001; JP 2001-401210, filed Dec. 28, 2001; JP 2002-118477, filed Apr. 19, 2002; US 2004/0142577 A1, filed Jan. 22, 2002; and US 2003/0170945 A1, filed Dec. 6, 2002.
The present invention is not limited to the above embodiments and may be practiced or embodied in still other ways without departing from the scope and spirit thereof.
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