US20140216498A1 - Methods of dry stripping boron-carbon films - Google Patents
Methods of dry stripping boron-carbon films Download PDFInfo
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- US20140216498A1 US20140216498A1 US13/760,845 US201313760845A US2014216498A1 US 20140216498 A1 US20140216498 A1 US 20140216498A1 US 201313760845 A US201313760845 A US 201313760845A US 2014216498 A1 US2014216498 A1 US 2014216498A1
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- boron
- carbon
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- hydrogen
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- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 239000001301 oxygen Substances 0.000 claims abstract description 69
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 68
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000001257 hydrogen Substances 0.000 claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 34
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 25
- 229910052796 boron Inorganic materials 0.000 claims description 25
- 239000012159 carrier gas Substances 0.000 claims description 10
- 150000001722 carbon compounds Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims 5
- 210000002381 plasma Anatomy 0.000 abstract description 82
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract description 44
- 229920000642 polymer Polymers 0.000 abstract description 28
- 238000005530 etching Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 23
- 239000001272 nitrous oxide Substances 0.000 abstract description 20
- 238000010586 diagram Methods 0.000 description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- 239000011737 fluorine Substances 0.000 description 16
- 229910052731 fluorine Inorganic materials 0.000 description 16
- 230000001965 increasing effect Effects 0.000 description 10
- -1 oxygen ions Chemical class 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000003989 dielectric material Substances 0.000 description 8
- 239000001307 helium Substances 0.000 description 8
- 229910052734 helium Inorganic materials 0.000 description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910001882 dioxygen Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 239000003039 volatile agent Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical class B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012035 limiting reagent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/427—Stripping or agents therefor using plasma means only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
- H01J37/32853—Hygiene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
Definitions
- Embodiments of the invention generally relate to methods of dry stripping boron-carbon films.
- Boron-carbon films such as boron-doped carbon have demonstrated superior patterning performance as compared to amorphous carbon when being used as an etching hardmask.
- boron-carbon films are not easily stripped, since boron-carbon films cannot be ashed using an oxygen plasma.
- Boron carbon films can be dry stripped using fluorine or chlorine along with oxygen; however, fluorine and chlorine are corrosive to dielectric materials such as silicon oxide, silicon nitride, and silicon oxynitride commonly found on semiconductor substrates.
- a wet etch solution containing sulfuric acid and hydrogen peroxide can also remove the boron-carbon films; however, the wet etch solution can damage exposed metal surfaces or embedded metals also commonly found on semiconductor substrates.
- Embodiments of the invention generally relate to methods of dry stripping boron-carbon films using oxygen-containing oxidizing agents in combination with hydrogen-containing reducing agents.
- alternating plasmas of hydrogen and oxygen are used to remove a boron-carbon film.
- co-flowed oxygen and hydrogen plasma is used to remove a boron-carbon containing film.
- a nitrous oxide plasma may be used in addition to or as an alternative to either of the above oxygen plasmas.
- a plasma generated from water vapor is used to remove a boron-carbon film.
- the boron-carbon removal processes may also include an optional polymer removal process prior to removal of the boron-carbon films.
- the polymer removal process includes exposing the boron-carbon film to a plasma formed from an oxygen-containing gas, a fluorine-containing gas, or a combination thereof to remove from the surface of the boron-carbon film any carbon-based polymers generated during a substrate etching process.
- a method for stripping a film from a substrate comprises positioning a substrate having a film thereon in a chamber, wherein the film includes at least one of boron or carbon. The film is then exposed to oxygen ions or radicals and hydrogen ions or radicals to generate one or more volatile compounds, and the one or more volatile compounds are exhausted from the chamber.
- a method for stripping a boron-carbon film from a substrate positioned in a chamber comprises exposing a substrate comprising boron and carbon to a plasma containing oxygen radicals or ions and hydrogen radicals or ions.
- the hydrogen radicals or ions are reacted with the boron to form a volatile boron species, and the oxygen radicals or ions are reacted with the carbon to form a volatile carbon species.
- the volatile boron species and the volatile carbon species are then removed from the chamber.
- a method for stripping a film from a substrate positioned in a chamber comprises exposing a substrate to a plasma formed from a compound comprising H x O y , where x and y are integers or non-integers greater than 1. The film is then contacted with the plasma to form one or more volatile species, and the volatile species are removed from the chamber.
- FIG. 1 is a flow diagram illustrating a method of removing a boron-carbon film using alternating hydrogen and oxygen plasmas according to one embodiment of the invention.
- FIG. 2 is a flow diagram illustrating a method of removing a boron-carbon film using a plasma containing both oxygen and hydrogen according to one embodiment of the invention.
- FIGS. 3A and 3B illustrate the effect of chamber pressure and RF power on etch rate when using a plasma containing oxygen and hydrogen.
- FIG. 4 is a flow diagram illustrating a method of removing a boron-carbon film using plasma generated from hydrogen and nitrous oxide according to one embodiment of the invention.
- FIG. 5 is a flow diagram illustrating a method of removing a boron-carbon film using plasma generated from water vapor according to one embodiment of the invention.
- FIG. 6 illustrates the etching selectivity of water vapor plasma.
- Embodiments of the invention generally relate to methods of dry stripping boron-carbon films using oxygen-containing oxidizing agents in combination with hydrogen-containing reducing agents.
- alternating plasmas of hydrogen and oxygen are used to remove a boron-carbon film.
- co-flowed oxygen and hydrogen plasma is used to remove a boron-carbon containing film.
- a nitrous oxide plasma may be used in addition to or as an alternative to either of the above oxygen plasmas.
- a plasma generated from water vapor is used to remove a boron-carbon film.
- the boron-carbon removal processes may also include an optional polymer removal process prior to removal of the boron-carbon films.
- the polymer removal process includes exposing the boron-carbon film to a plasma formed from an oxygen-containing gas, a fluorine-containing gas, or a combination thereof to remove from the surface of the boron-carbon film any carbon-based polymers generated during a substrate etching process.
- Embodiments of the invention may be practiced in the Producer® SE or Producer® GT chambers available from Applied Materials, Inc., of Santa Clara, Calif. It is contemplated that other chambers, including those produced by other manufacturers, may benefit from embodiments described herein.
- FIG. 1 is a flow diagram 100 illustrating a method of removing a boron-carbon film using alternating hydrogen and oxygen plasmas according to one embodiment of the invention.
- Flow diagram 100 begins at operation 102 , in which a substrate having a boron-carbon film thereon, such as a boron-carbon hardmask, is positioned on a substrate support within a stripping chamber.
- the substrate and the boron-carbon film thereon are heated to a temperature less than about 750° C., such as about 200° C. to about 400° C.
- the boron-carbon film may be a boron-doped carbon, or a hydrogenated boron carbide having an atomic ratio of boron to carbide of about 2:1 or less.
- the substrate is generally a silicon-containing substrate, such as a 300 millimeter silicon wafer, and may have one or more dielectric or conductive metal layers disposed thereon.
- the substrate may have a silicon dioxide layer disposed thereon, over which the boron-carbon layer is disposed to act as an etching hardmask during a previously performed etching of the silicon dioxide layer. It is contemplated that substrates other than silicon-containing substrates may be used.
- carbon-based polymers located on the boron-carbon film are optionally removed in a polymer removal operation 104 .
- the carbon-based polymers are generated on the upper surface of the boron-carbon layer during a previously performed etching process in which the boron-carbon layer acts as an etching hardmask.
- an etchant such as C 4 F 8
- the substrate and the boron-carbon layer thereon are exposed to an etchant, such as C 4 F 8 , to etch a desired pattern into the substrate. Due to polymerization of carbon and fluorine, the etching process produces a carbon-based polymer, which may also include silicon and/or oxygen.
- the carbon-based polymer is generally removed prior to the stripping process to remove higher molecular weight molecules to allow for more efficient stripping of the boron-carbon film.
- the carbon-based polymer is removed from the surface of the boron-carbon film by exposing the carbon-based polymer to a plasma formed from a fluorine-containing gas, an oxygen-containing gas, or a combination thereof.
- the carbon-based polymer may be removed using a plasma formed from oxygen gas and NF 3 having a ratio of about 100:1.
- the amount of fluorine desired in the plasma increases with the amount of silicon present in the carbon-based polymer. Since oxygen-containing plasmas are capable of removing the carbon-based polymer, especially when the carbon-based polymer contains relatively low amounts of silicon, operation 104 can be omitted due to the exposure of the substrate to an oxygen-containing plasma in operation 106 (discussed below).
- a remotely generated plasma using oxygen gas and NF 3 gas is provided to the stripping chamber at a flow rate of about 1 SCCM to about 15,000 SCCM per 300 millimeter substrate, for example, about 100 SCCM to about 5,000 SCCM.
- the ratio of oxygen to NF 3 is about 100:1 to about 1000:1.
- the pressure within the stripping chamber is maintained at a pressure within a range from about 1 millitorr to about 760 Torr, such as about 4 millitorr to about 10 Torr, while the substrate is maintained at a temperature less than 750° C.
- the oxygen and the NF 3 react with the carbon-based polymer to form a volatile compound which is then exhausted from the stripping chamber. Under such conditions, the carbon-based polymer is removed at a rate of about 2,000 angstroms per minute to about 10,000 angstroms per minute. It is contemplated that the carbon-based polymer may be over-etched to ensure removal from the surface of the substrate.
- Operation 106 includes two sub-operations, 106 A and 106 B.
- sub-operation 106 A the boron-carbon layer is exposed to an ionized oxygen-containing compound, such as oxygen plasma, and then subsequently, in sub-operation 106 B, the substrate is exposed to an ionized hydrogen-containing compound, such as hydrogen plasma.
- sub-operation 106 A the oxygen ions react with the carbon of the boron-carbon film to form a volatile compound (e.g., CO 2 ) which is exhausted from the chamber.
- a volatile compound e.g., CO 2
- the boron-carbon film forms a relatively higher concentration of boron near the surface of the film due to the removal of carbon.
- the removal rate of the boron-carbon film begins to decrease due to the reduction of available carbon on the surface of the film.
- the flow rate of the oxygen-containing compound to the stripping chamber is halted, and the remaining oxygen-containing compound is exhausted from the stripping chamber.
- sub-operation 106 B the boron-carbon layer is exposed to a hydrogen-containing compound plasma which reacts with the boron in the boron-carbon layer to form a volatile compound (e.g., B 2 H 6 ) which is then exhausted from the chamber.
- the boron-carbon layer is exposed to the hydrogen plasma for about 10 seconds to about 50 seconds, until the boron-carbon film has a relatively higher concentration of carbon near the surface of the boron-carbon film.
- the flow of hydrogen gas is halted, and sub-operation 106 A is then repeated.
- Operation 106 which includes sub-operations 106 A and 106 B, may be repeated a desired amount of times in order to sufficiently remove the boron-carbon film from the substrate surface.
- Each of the hydrogen-containing compound and the oxygen-containing compound are provided to the stripping chamber at flow rate of about 5 SCCM to about 15,000 SCCM per 300 millimeter substrate.
- the hydrogen gas and the oxygen gas may be provided to the stripping chamber at a flow rate of about 500 SCCM to about 10,000 SCCM and about 250 SCCM to about 5000 SCCM, respectively.
- the hydrogen-containing compound and the oxygen-containing compound are ionized using an RF generator operating at 13.56 MHz which applies about 100 watts to about 3,000 watts of power, for example, about 1,000 watts to about 3,000 watts.
- the pressure within the stripping chamber is maintained at a pressure within a range from about 1 millitorr to about 760 Torr, such as about 50 millitorr to about 10 Torr, or about 5 Torr to about 100 Torr.
- the exposure times of each compound can be tailored based on the atomic composition of the boron-carbon film to effect a desired removal rate. For example, if the boron concentration in the boron-carbon film is about twice the concentration of the carbon in the film, then the hydrogen exposure time may be greater than the oxygen exposure time, such as about two times greater (assuming both plasmas have about the same etch rate).
- Flow diagram 100 illustrates one embodiment for removing a boron-carbon film; however, other embodiments are also contemplated.
- operations 102 , 104 , and 106 are all performed in the same chamber.
- operation 104 may occur in a separate chamber, such as an etching chamber, and may occur before positioning the substrate in a stripping chamber.
- the plasma of operation 104 can be a capacitively coupled or inductively coupled in addition to or as an alternative to a remotely generated.
- a capacitively coupled plasma may be generated from a fluorine-containing gas and an oxygen-containing gas.
- a capacitively coupled plasma may be generated from water vapor and an inert gas.
- water vapor may be introduced to the chamber at a flow rate between about 10 SCCM and 10,000 SCCM, such as about 4,000 SCCM.
- the inert gas may be provided to the chamber at a flow rate of about 3,000 SCCM.
- fluorine-containing gases can be used in operation 104 .
- CF 4 , C 3 F 6 , CHF 3 , CH 2 F 2 , and CH 3 F may be utilized.
- the NF 3 plasma of operation 104 or the oxygen-containing or hydrogen-containing plasmas of operation 106 can be generated in situ via inductive coupling or may be remotely generated.
- the oxygen-containing compound and hydrogen-containing compound of operation 106 may be carried to the stripping chamber using a carrier gas, such as argon, helium or nitrogen.
- the carrier gases may be provided to the stripping chamber containing a 300 millimeter substrate at a flow rate of about 5 SCCM to about 15,000 SCCM.
- the chamber may be flushed between sub-operations 106 A and 106 B using a carrier gas to avoid reaction between the hydrogen and the oxygen.
- sub-operation 106 B may be performed prior to sub-operation 106 A.
- any compound which provides oxygen such as O 2 , N 2 O, CO 2 , NO, or NO 2 , may be used in operation 106 .
- other hydrogen-containing compounds may be used in addition to or as alternatives to hydrogen gas in operation 106 .
- ammonia may be used in addition to or as an alternative to hydrogen gas.
- a boron-carbon film having a thickness of about 2000 angstroms is exposed to 1500 SCCM of hydrogen plasma for 30 seconds at a chamber pressure of 7 Torr and substrate temperature of 400° C.
- the boron-carbon film is then exposed to 1500 SCCM of oxygen plasma for 30 seconds at a chamber pressure of 7 Torr and substrate temperature of 400° C.
- the boron-carbon film is further exposed to alternating hydrogen and oxygen plasmas until the film is removed.
- the boron-carbon film was removed in about 20 minutes.
- FIG. 2 is a flow diagram 200 illustrating a method of removing a boron-carbon film using a plasma containing both oxygen and hydrogen according to one embodiment of the invention.
- Flow diagram 200 includes operations 102 , 104 , and 206 .
- Operations 102 and 104 are similar to operations 102 and 104 described with reference to flow diagram 100 .
- the substrate and the boron-carbon film thereon are exposed to a plasma or ionized gas formed from a hydrogen-containing compound, such as diatomic hydrogen, and an oxygen-containing compound, such as diatomic oxygen, in operation 206 .
- operation 106 of flow diagram 100 exposes the boron-carbon film to a cycle alternating hydrogen-containing and oxygen-containing plasmas
- operation 206 exposes the boron-carbon film to simultaneous hydrogen-containing and oxygen-containing plasmas.
- the hydrogen-containing compound and oxygen-containing compound are provided to the stripping chamber at flow rate of about 5 SCCM to about 15,000 SCCM per 300 millimeter substrate to remove a boron-carbon layer from the surface of the substrate.
- the hydrogen-containing compound and the oxygen-containing compound may be provided at a flow rate of about 200 SCCM to about 4,000 SCCM.
- the hydrogen-containing compound and the oxygen-containing compound are ionized using an RF generator operating at 13.56 MHz and applying about 100 watts to about 3,000 watts of power, such as about 1,500 watts to about 2,000 watts of power.
- the substrate is maintained at a temperature less than 750° C., such as at about 400° C.
- the pressure within the stripping chamber is generally maintained at a pressure less than about 20 Torr, such as about 7 Torr to about 19 Torr.
- a pressure less than about 20 Torr such as about 7 Torr to about 19 Torr.
- the hydrogen-containing plasma and the oxygen-containing plasma within the chamber contact the boron-carbon film and react to form volatile compounds which are then exhausted from the chamber. Since the oxygen generally forms a volatile compound with the carbon in the boron-carbon film, and the hydrogen forms a volatile compound with the boron, it is contemplated that the relative ratio of oxygen to hydrogen (and/or flow rates of oxygen and hydrogen) can be adjusted depending on the composition of the boron-carbon film to effect the desired removal rate. Table 1 illustrates the change in removal rate of a boron-carbon film from the surface of a 300 millimeter substrate using varied process parameters.
- Example 1 19 1500 400 1000 500 140
- Example 2 19 1900 400 1000 500 155
- Example 3 19 1900 400 1500 750 152
- Example 4 19 1900 400 700 350 151
- Example 5 19 1900 400 400 200 141
- Example 6 19 1900 400 1250 250 116
- Example 7 19 1900 400 750 750 102
- Example 8 19 1900 400 250 1250 119
- Example 9 19 1900 400 300 300 104
- Example 10 19 1900 400 200 400 101
- Example 12 19 1500 400 500 1000 88
- etching rate With respect to increased oxygen or hydrogen flow rates, excess oxygen or hydrogen in the plasma generally has little effect on etching rate.
- the rate of etching is limited by the amount of boron or carbon present on the surface of the boron-carbon film with which the oxygen or hydrogen can form a volatile compound, and generally is not significantly increased with the inclusion of excess process gas.
- the etching rate can be increased through the inclusion of additional process gas when the process gas is the limiting reactant (e.g., excess reactant sites are present on the surface of the boron-carbon film).
- Flow diagram 200 illustrates one embodiment of stripping a boron-carbon film; however, other embodiments are also contemplated.
- the oxygen-containing compound and hydrogen-containing compound in operation 206 may be introduced to the stripping chamber using a carrier gas, such as argon, helium, or nitrogen, having a flow rate less than 15,000 SCCM per 300 millimeter substrate.
- a carrier gas such as argon, helium, or nitrogen
- the inclusion of carrier gas to the processing volume may decrease the rate at which the boron-carbon film is etched, but may also increase plasma uniformity and stability.
- FIGS. 3A and 3B illustrate the effect of chamber pressure and RF power on etch rate when using a plasma containing oxygen and hydrogen.
- a boron-carbon film at 400° C. was removed from a substrate using a plasma formed from 2,000 SCCM of hydrogen gas and 1,000 SCCM of oxygen gas at 1,000 watts of RF power.
- the etching rate of the boron-carbon film is correspondingly increased.
- etch rate of the boron-carbon film may be controlled by adjusting the pressure within the chamber.
- FIG. 3B a boron-carbon film at 400° C. was removed using plasma formed from 2,000 SCCM of hydrogen gas and 1,000 SCCM of oxygen gas.
- the chamber pressure was maintained at 9 Torr.
- the RF power applied to the plasma is increased, the etching rate of the boron-carbon film is correspondingly increased.
- FIG. 4 is a flow diagram illustrating a method of removing a boron-carbon film using plasma generated from hydrogen and nitrous oxide according to one embodiment of the invention.
- Flow diagram 400 includes operations 102 , 104 , and 406 .
- Operations 102 and 104 are similar to operations 102 and 104 described with reference to flow diagram 100 .
- the substrate and the boron-carbon film thereon are exposed to a plasma formed from hydrogen and nitrous oxide in operation 406 .
- flow diagram 200 uses oxygen as an oxidizing agent to remove carbon from the boron-carbon film
- flow diagram 400 uses nitrous oxide as an oxidizing agent.
- the use of nitrous oxide as an oxidizing agent allows the pressure within the chamber to be increased, thus increasing etch rate, while reducing the probability of undesired reactions occurring within the processing environment as is likely when using oxygen as an oxidizing agent.
- hydrogen gas and nitrous oxide gas are provided to the stripping chamber at flow rate of about 5 SCCM to about 15,000 SCCM for a 300 millimeter substrate to remove a boron-carbon layer from the surface of the substrate.
- the hydrogen gas and the nitrous oxide gas may each be provided at a flow rate of about 200 SCCM to about 4,000 SCCM.
- the hydrogen gas and the nitrous oxide gas are ionized using an RF generator operating at 13.56 MHz and applying about 100 watts to about 3,000 watts of power, such as about 1,500 watts to about 2,000 watts of power.
- the substrate is maintained at a heater temperature less than 750° C., such as at about 400° C.
- the pressure within the stripping chamber is maintained at less than 760 Torr, such as about 40 Torr to about 60 Torr.
- the nitrous oxide plasma and the hydrogen plasma react with the boron-carbon film to form volatile compounds which are then exhausted from the chamber.
- Table 2 illustrates some exemplary process recipes for removing a boron-carbon film from the surface of a 300 millimeter substrate using a plasma formed from hydrogen and nitrous oxide.
- nitrous oxide As illustrated in Table 2, the use of nitrous oxide as an oxidizing agent generally yields a greater etching rate than when using oxygen as an oxidizing agent. This is due partly to the higher chamber pressures which can be utilized when using nitrous oxide.
- the oxidizing gas may be a mixture of nitrous oxide and oxygen, in which case, the pressure in the chamber may be permitted to exceed 20 Torr.
- flow diagram 400 is described with reference to co-flowing nitrous oxide and hydrogen gas, it is contemplated that the nitrous oxide and hydrogen gas be independently provided to the chamber in a cyclical manner.
- carbon dioxide may be used in addition to or as an alternative to nitrous oxide.
- FIG. 5 is a flow diagram 500 illustrating a method of removing a boron-carbon film using plasma generated from water vapor according to one embodiment of the invention.
- Flow diagram 500 includes operations 102 , 104 , and 506 .
- Operations 102 and 104 are similar to operations 102 and 104 described with reference to flow diagram 100 .
- the substrate and the boron-carbon film thereon are exposed to a plasma formed from water vapor in operation 506 .
- water vapor is produced by a water vapor generator (WVG) and is provided to a stripping chamber where the water vapor is ignited into a plasma to etch a boron-carbon film from the surface of a substrate.
- WVG water vapor generator
- the water vapor is introduced to the stripping chamber at a flow rate of about 5 SCCM to about 15,000 SCCM per 300 millimeter substrate.
- the substrate is maintained at a temperature less than about 750° C., such as about 300° C. to about 500° C., for example about 400° C., while the pressure in the chamber is maintained at less than about 760 Torr, such as about 10 Torr to about 760 Torr, such as about 10 Torr to about 100 Torr, for example about 65 Torr.
- RF power within a range of about 10 watts to 3,000 watts, for example about 2,700 watts, is applied to the water vapor to generate a plasma containing oxygen, hydrogen, and hydroxyl ions or radicals, which react with the boron-carbon film to form volatile compounds which are exhausted from the chamber.
- Flow diagram 500 illustrates one embodiment for stripping a boron-carbon film; however, additional embodiments are also contemplated.
- the water vapor may be generated via in situ steam generation.
- non-stoichiometric combinations of oxygen and hydrogen e.g., H x O y , where x and y may be integers or non-integers both greater than zero
- H x O y may be integers or non-integers both greater than zero
- some hydrogen peroxide may be generated by the water vapor generator.
- oxygen gas, helium gas, nitrogen gas, argon gas, nitrous oxide gas, and or/hydrogen gas may be provided to the stripping chamber in addition to water vapor.
- the addition of hydrogen has been found to increase the removal rate of the boron-carbon film, especially in boron-carbon films containing a higher concentration of boron as compared to carbon.
- the addition of other carrier gases, such as helium has been observed to lower the rate of removal of the boron-carbon film, while simultaneously improving etch uniformity.
- the water vapor may be used to strip a carbon film, such as amorphous carbon, containing substantially no boron.
- the water vapor may be used to strip a boron film, such as amorphous boron, containing substantially no carbon.
- a fluorine-containing gas or a chlorine-containing gas may be ionized in operation 506 in combination with the water vapor to increase the etching rate of the boron-carbon film.
- operation 104 may be omitted.
- the fluorine-containing gas or the chlorine-containing gas is generally provided to the chamber at a flow rate between about 10 SCCM and 50 SCCM.
- the flow rate of the fluorine-containing gas or the chlorine-containing gas is tapered, reduced, or eliminated when approaching the end of operation 506 . It is believed that reduction in flow rate near the end of operation 106 does not undesirably etch exposed dielectric materials due to the mechanism in which the fluorine-containing gas or the chlorine-containing gas assists in removal of the boron-carbon layer.
- dielectric material on the substrate is exposed in vias or trenches formed into the substrate during a previous etching process, while boron-carbon material is exposed on the upper surface of the substrate.
- the fluorine-containing gas or the chlorine-containing gas which enters the chamber and is ignited into a plasma generally contacts and reacts with the boron-carbon layer prior to contacting the dielectric material in the vias or trenches.
- the probability of the fluorine-containing gas or the chlorine-containing gas contacting and undesirably removing the dielectric material is increased. Therefore, the flow rate of the fluorine-containing gas or the chlorine-containing gas is reduced as the thickness of the boron-containing layer decreases in order to reduce the probability of etching the dielectric material.
- the spacing between the substrate and a face place located within the chamber may be within a range of about 20 mils to about 600 mils, for example about 170 mils.
- Reduced spacing between the substrate is beneficial when processing substrates in larger volumes (for example, when processing large area substrates) under higher pressures (for example, greater than about 7 Torr).
- the reduced spacing facilitates plasma sustainability.
- the spacing between the substrate and the face plate may be about 300 mils.
- the spacing between the substrate and the face plate may be within a range of about 240 mils to about 270 mils.
- the spacing between the substrate and the face plate may be less than 200 mils.
- the spacing may be about 170 mils.
- Table 3 illustrates a change in etch rate of a boron-carbon film in response to a change in process gas flow rate.
- Each of Examples 23-30 in Table 3 includes at least 500 SCCM of helium gas as a carrier gas to increase etch uniformity, and may contain additional carrier gas, as noted in Table 3.
- Example 23 50 1900 400 1000 250 0 679
- Example 24 50 1900 400 1000 400 0 613
- Example 25 50 1900 400 1000 250 150 H 2 720
- Example 26 50 1900 400 1000 250 350 H 2 630
- Example 27 50 1900 400 1000 250 150 Ar 617
- Example 28 50 1900 400 1000 250 350 Ar 527
- Example 29 50 1900 400 1000 250 750 Ar 389
- Example 30 50 1900 400 1000 500 0 546
- Example 29 which contains the highest total flow rate of carrier gas (250 SCCM of helium and 750 SCCM of argon) has the lowest etch rate.
- Table 4 includes some examples of boron-carbon film stripping recipes at higher severity.
- High severity conditions include pressures above 50 Torr, high gas flow rates of at least 7 sLm, and higher power input of at least about 2000 watts. Such high severity conditions can maintain a water vapor plasma, optionally with excess hydrogen, at a spacing less than 200 mils.
- FIG. 6 illustrates the etching selectivity of water vapor plasma.
- Plasma A includes 1,000 SCCM of water vapor and 500 SCCM of helium generated into a plasma using 1900 watts of RF power.
- the stripping chamber is maintained at 50 Torr, and the substrate is maintained at 400° C.
- Plasma A etched the boron-carbon film at a rate of about 570 angstroms per minute, and did not etch silicon oxide, silicon nitride, or amorphous silicon.
- Plasma B includes 1,000 SCCM of water vapor, 250 SCCM of helium, and 150 SCCM of hydrogen generated into a plasma using 1900 watts of RF power.
- the stripping chamber is maintained at 50 Torr, and the substrate is maintained at 400° C.
- Plasma B etched the boron-carbon film at a rate of about 770 angstroms per minute, and did not etch silicon oxide, silicon nitride, or amorphous silicon.
- Benefits of the methods described herein include stripping boron-carbon films without damaging dielectric materials or underlying metal layers located on a substrate.
- the stripping methods allow for etching rate, as well as etching uniformity to be controlled by varying plasma composition.
Abstract
Embodiments of the invention generally relate to methods of dry stripping boron-carbon films. In one embodiment, alternating plasmas of hydrogen and oxygen are used to remove a boron-carbon film. In another embodiment, co-flowed oxygen and hydrogen plasma is used to remove a boron-carbon containing film. A nitrous oxide plasma may be used in addition to or as an alternative to either of the above oxygen plasmas. In another embodiment, a plasma generated from water vapor is used to remove a boron-carbon film. The boron-carbon removal processes may also include an optional polymer removal process prior to removal of the boron-carbon films. The polymer removal process includes exposing the boron-carbon film to NF3 to remove from the surface of the boron-carbon film any carbon-based polymers generated during a substrate etching process.
Description
- This application claims benefit of U.S. provisional patent application Ser. No. 61/485,534, filed May 12, 2011, which is herein incorporated by reference.
- 1. Field of the Invention
- Embodiments of the invention generally relate to methods of dry stripping boron-carbon films.
- 2. Description of the Related Art
- Boron-carbon films, such as boron-doped carbon, have demonstrated superior patterning performance as compared to amorphous carbon when being used as an etching hardmask. However, boron-carbon films are not easily stripped, since boron-carbon films cannot be ashed using an oxygen plasma. Boron carbon films can be dry stripped using fluorine or chlorine along with oxygen; however, fluorine and chlorine are corrosive to dielectric materials such as silicon oxide, silicon nitride, and silicon oxynitride commonly found on semiconductor substrates. A wet etch solution containing sulfuric acid and hydrogen peroxide can also remove the boron-carbon films; however, the wet etch solution can damage exposed metal surfaces or embedded metals also commonly found on semiconductor substrates.
- Therefore, there is a need for an improved method of removing boron-carbon films from substrates.
- Embodiments of the invention generally relate to methods of dry stripping boron-carbon films using oxygen-containing oxidizing agents in combination with hydrogen-containing reducing agents. In one embodiment, alternating plasmas of hydrogen and oxygen are used to remove a boron-carbon film. In another embodiment, co-flowed oxygen and hydrogen plasma is used to remove a boron-carbon containing film. A nitrous oxide plasma may be used in addition to or as an alternative to either of the above oxygen plasmas. In another embodiment, a plasma generated from water vapor is used to remove a boron-carbon film. The boron-carbon removal processes may also include an optional polymer removal process prior to removal of the boron-carbon films. The polymer removal process includes exposing the boron-carbon film to a plasma formed from an oxygen-containing gas, a fluorine-containing gas, or a combination thereof to remove from the surface of the boron-carbon film any carbon-based polymers generated during a substrate etching process.
- In one embodiment, a method for stripping a film from a substrate comprises positioning a substrate having a film thereon in a chamber, wherein the film includes at least one of boron or carbon. The film is then exposed to oxygen ions or radicals and hydrogen ions or radicals to generate one or more volatile compounds, and the one or more volatile compounds are exhausted from the chamber.
- In another embodiment, a method for stripping a boron-carbon film from a substrate positioned in a chamber comprises exposing a substrate comprising boron and carbon to a plasma containing oxygen radicals or ions and hydrogen radicals or ions. The hydrogen radicals or ions are reacted with the boron to form a volatile boron species, and the oxygen radicals or ions are reacted with the carbon to form a volatile carbon species. The volatile boron species and the volatile carbon species are then removed from the chamber.
- In another embodiment, a method for stripping a film from a substrate positioned in a chamber comprises exposing a substrate to a plasma formed from a compound comprising HxOy, where x and y are integers or non-integers greater than 1. The film is then contacted with the plasma to form one or more volatile species, and the volatile species are removed from the chamber.
- So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
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FIG. 1 is a flow diagram illustrating a method of removing a boron-carbon film using alternating hydrogen and oxygen plasmas according to one embodiment of the invention. -
FIG. 2 is a flow diagram illustrating a method of removing a boron-carbon film using a plasma containing both oxygen and hydrogen according to one embodiment of the invention. -
FIGS. 3A and 3B illustrate the effect of chamber pressure and RF power on etch rate when using a plasma containing oxygen and hydrogen. -
FIG. 4 is a flow diagram illustrating a method of removing a boron-carbon film using plasma generated from hydrogen and nitrous oxide according to one embodiment of the invention. -
FIG. 5 is a flow diagram illustrating a method of removing a boron-carbon film using plasma generated from water vapor according to one embodiment of the invention. -
FIG. 6 illustrates the etching selectivity of water vapor plasma. - To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
- Embodiments of the invention generally relate to methods of dry stripping boron-carbon films using oxygen-containing oxidizing agents in combination with hydrogen-containing reducing agents. In one embodiment, alternating plasmas of hydrogen and oxygen are used to remove a boron-carbon film. In another embodiment, co-flowed oxygen and hydrogen plasma is used to remove a boron-carbon containing film. A nitrous oxide plasma may be used in addition to or as an alternative to either of the above oxygen plasmas. In another embodiment, a plasma generated from water vapor is used to remove a boron-carbon film. The boron-carbon removal processes may also include an optional polymer removal process prior to removal of the boron-carbon films. The polymer removal process includes exposing the boron-carbon film to a plasma formed from an oxygen-containing gas, a fluorine-containing gas, or a combination thereof to remove from the surface of the boron-carbon film any carbon-based polymers generated during a substrate etching process.
- Embodiments of the invention may be practiced in the Producer® SE or Producer® GT chambers available from Applied Materials, Inc., of Santa Clara, Calif. It is contemplated that other chambers, including those produced by other manufacturers, may benefit from embodiments described herein.
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FIG. 1 is a flow diagram 100 illustrating a method of removing a boron-carbon film using alternating hydrogen and oxygen plasmas according to one embodiment of the invention. Flow diagram 100 begins atoperation 102, in which a substrate having a boron-carbon film thereon, such as a boron-carbon hardmask, is positioned on a substrate support within a stripping chamber. The substrate and the boron-carbon film thereon are heated to a temperature less than about 750° C., such as about 200° C. to about 400° C. The boron-carbon film may be a boron-doped carbon, or a hydrogenated boron carbide having an atomic ratio of boron to carbide of about 2:1 or less. The substrate is generally a silicon-containing substrate, such as a 300 millimeter silicon wafer, and may have one or more dielectric or conductive metal layers disposed thereon. For example, the substrate may have a silicon dioxide layer disposed thereon, over which the boron-carbon layer is disposed to act as an etching hardmask during a previously performed etching of the silicon dioxide layer. It is contemplated that substrates other than silicon-containing substrates may be used. - After positioning the substrate on a support, carbon-based polymers located on the boron-carbon film are optionally removed in a
polymer removal operation 104. The carbon-based polymers are generated on the upper surface of the boron-carbon layer during a previously performed etching process in which the boron-carbon layer acts as an etching hardmask. During the etching, the substrate and the boron-carbon layer thereon are exposed to an etchant, such as C4F8, to etch a desired pattern into the substrate. Due to polymerization of carbon and fluorine, the etching process produces a carbon-based polymer, which may also include silicon and/or oxygen. The carbon-based polymer is generally removed prior to the stripping process to remove higher molecular weight molecules to allow for more efficient stripping of the boron-carbon film. - The carbon-based polymer is removed from the surface of the boron-carbon film by exposing the carbon-based polymer to a plasma formed from a fluorine-containing gas, an oxygen-containing gas, or a combination thereof. For example, the carbon-based polymer may be removed using a plasma formed from oxygen gas and NF3 having a ratio of about 100:1. Generally, the amount of fluorine desired in the plasma increases with the amount of silicon present in the carbon-based polymer. Since oxygen-containing plasmas are capable of removing the carbon-based polymer, especially when the carbon-based polymer contains relatively low amounts of silicon,
operation 104 can be omitted due to the exposure of the substrate to an oxygen-containing plasma in operation 106 (discussed below). - During the polymer removal process, a remotely generated plasma using oxygen gas and NF3 gas is provided to the stripping chamber at a flow rate of about 1 SCCM to about 15,000 SCCM per 300 millimeter substrate, for example, about 100 SCCM to about 5,000 SCCM. The ratio of oxygen to NF3 is about 100:1 to about 1000:1. The pressure within the stripping chamber is maintained at a pressure within a range from about 1 millitorr to about 760 Torr, such as about 4 millitorr to about 10 Torr, while the substrate is maintained at a temperature less than 750° C. The oxygen and the NF3 react with the carbon-based polymer to form a volatile compound which is then exhausted from the stripping chamber. Under such conditions, the carbon-based polymer is removed at a rate of about 2,000 angstroms per minute to about 10,000 angstroms per minute. It is contemplated that the carbon-based polymer may be over-etched to ensure removal from the surface of the substrate.
- After removal of the carbon-based polymer layer from the boron-carbon layer, the boron-carbon layer is stripped from the surface of the substrate in
operation 106.Operation 106 includes two sub-operations, 106A and 106B. Insub-operation 106A, the boron-carbon layer is exposed to an ionized oxygen-containing compound, such as oxygen plasma, and then subsequently, in sub-operation 106B, the substrate is exposed to an ionized hydrogen-containing compound, such as hydrogen plasma. Insub-operation 106A, the oxygen ions react with the carbon of the boron-carbon film to form a volatile compound (e.g., CO2) which is exhausted from the chamber. After about 10 seconds to about 50 seconds of exposure to the ionized oxygen, the boron-carbon film forms a relatively higher concentration of boron near the surface of the film due to the removal of carbon. The removal rate of the boron-carbon film begins to decrease due to the reduction of available carbon on the surface of the film. At this point, the flow rate of the oxygen-containing compound to the stripping chamber is halted, and the remaining oxygen-containing compound is exhausted from the stripping chamber. - In
sub-operation 106B, the boron-carbon layer is exposed to a hydrogen-containing compound plasma which reacts with the boron in the boron-carbon layer to form a volatile compound (e.g., B2H6) which is then exhausted from the chamber. The boron-carbon layer is exposed to the hydrogen plasma for about 10 seconds to about 50 seconds, until the boron-carbon film has a relatively higher concentration of carbon near the surface of the boron-carbon film. After a predetermined time, the flow of hydrogen gas is halted, andsub-operation 106A is then repeated.Operation 106, which includes sub-operations 106A and 106B, may be repeated a desired amount of times in order to sufficiently remove the boron-carbon film from the substrate surface. - Each of the hydrogen-containing compound and the oxygen-containing compound are provided to the stripping chamber at flow rate of about 5 SCCM to about 15,000 SCCM per 300 millimeter substrate. For example, the hydrogen gas and the oxygen gas may be provided to the stripping chamber at a flow rate of about 500 SCCM to about 10,000 SCCM and about 250 SCCM to about 5000 SCCM, respectively. The hydrogen-containing compound and the oxygen-containing compound are ionized using an RF generator operating at 13.56 MHz which applies about 100 watts to about 3,000 watts of power, for example, about 1,000 watts to about 3,000 watts. The pressure within the stripping chamber is maintained at a pressure within a range from about 1 millitorr to about 760 Torr, such as about 50 millitorr to about 10 Torr, or about 5 Torr to about 100 Torr.
- It is to be noted that since the oxygen-containing compound reacts with carbon, and the hydrogen-containing compound reacts with boron, the exposure times of each compound can be tailored based on the atomic composition of the boron-carbon film to effect a desired removal rate. For example, if the boron concentration in the boron-carbon film is about twice the concentration of the carbon in the film, then the hydrogen exposure time may be greater than the oxygen exposure time, such as about two times greater (assuming both plasmas have about the same etch rate).
- Flow diagram 100 illustrates one embodiment for removing a boron-carbon film; however, other embodiments are also contemplated. In one embodiment,
operations operation 104 may occur in a separate chamber, such as an etching chamber, and may occur before positioning the substrate in a stripping chamber. In another embodiment, it is contemplated that the plasma ofoperation 104 can be a capacitively coupled or inductively coupled in addition to or as an alternative to a remotely generated. For example, it is contemplated that a capacitively coupled plasma may be generated from a fluorine-containing gas and an oxygen-containing gas. Alternatively, a capacitively coupled plasma may be generated from water vapor and an inert gas. In such an embodiment, water vapor may be introduced to the chamber at a flow rate between about 10 SCCM and 10,000 SCCM, such as about 4,000 SCCM. The inert gas may be provided to the chamber at a flow rate of about 3,000 SCCM. - In another embodiment, it is contemplated that other fluorine-containing gases can be used in
operation 104. For example, it is contemplated that CF4, C3F6, CHF3, CH2F2, and CH3F may be utilized. In another embodiment, it is contemplated that the NF3 plasma ofoperation 104 or the oxygen-containing or hydrogen-containing plasmas ofoperation 106 can be generated in situ via inductive coupling or may be remotely generated. In yet another embodiment, it is contemplated that the oxygen-containing compound and hydrogen-containing compound ofoperation 106 may be carried to the stripping chamber using a carrier gas, such as argon, helium or nitrogen. The carrier gases may be provided to the stripping chamber containing a 300 millimeter substrate at a flow rate of about 5 SCCM to about 15,000 SCCM. In another embodiment, it is contemplated that the chamber may be flushed betweensub-operations sub-operation 106B may be performed prior tosub-operation 106A. - In another embodiment, it is contemplated that any compound which provides oxygen, such as O2, N2O, CO2, NO, or NO2, may be used in
operation 106. Additionally, it is also contemplated that other hydrogen-containing compounds may be used in addition to or as alternatives to hydrogen gas inoperation 106. For example, it is contemplated that ammonia may be used in addition to or as an alternative to hydrogen gas. - In one example, a boron-carbon film having a thickness of about 2000 angstroms is exposed to 1500 SCCM of hydrogen plasma for 30 seconds at a chamber pressure of 7 Torr and substrate temperature of 400° C. The boron-carbon film is then exposed to 1500 SCCM of oxygen plasma for 30 seconds at a chamber pressure of 7 Torr and substrate temperature of 400° C. The boron-carbon film is further exposed to alternating hydrogen and oxygen plasmas until the film is removed. The boron-carbon film was removed in about 20 minutes.
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FIG. 2 is a flow diagram 200 illustrating a method of removing a boron-carbon film using a plasma containing both oxygen and hydrogen according to one embodiment of the invention. Flow diagram 200 includesoperations Operations operations operation 102, and removing the carbon-based polymer inoperation 104, the substrate and the boron-carbon film thereon are exposed to a plasma or ionized gas formed from a hydrogen-containing compound, such as diatomic hydrogen, and an oxygen-containing compound, such as diatomic oxygen, inoperation 206. Thus, whileoperation 106 of flow diagram 100 exposes the boron-carbon film to a cycle alternating hydrogen-containing and oxygen-containing plasmas,operation 206 exposes the boron-carbon film to simultaneous hydrogen-containing and oxygen-containing plasmas. - In
operation 206, the hydrogen-containing compound and oxygen-containing compound are provided to the stripping chamber at flow rate of about 5 SCCM to about 15,000 SCCM per 300 millimeter substrate to remove a boron-carbon layer from the surface of the substrate. For example, the hydrogen-containing compound and the oxygen-containing compound may be provided at a flow rate of about 200 SCCM to about 4,000 SCCM. The hydrogen-containing compound and the oxygen-containing compound are ionized using an RF generator operating at 13.56 MHz and applying about 100 watts to about 3,000 watts of power, such as about 1,500 watts to about 2,000 watts of power. The substrate is maintained at a temperature less than 750° C., such as at about 400° C. The pressure within the stripping chamber is generally maintained at a pressure less than about 20 Torr, such as about 7 Torr to about 19 Torr. By maintaining the chamber pressure at less than about 20 Torr, the probability of oxygen plasma and hydrogen plasma undesirably and dangerously reacting within the stripping chamber is greatly reduced. - The hydrogen-containing plasma and the oxygen-containing plasma within the chamber contact the boron-carbon film and react to form volatile compounds which are then exhausted from the chamber. Since the oxygen generally forms a volatile compound with the carbon in the boron-carbon film, and the hydrogen forms a volatile compound with the boron, it is contemplated that the relative ratio of oxygen to hydrogen (and/or flow rates of oxygen and hydrogen) can be adjusted depending on the composition of the boron-carbon film to effect the desired removal rate. Table 1 illustrates the change in removal rate of a boron-carbon film from the surface of a 300 millimeter substrate using varied process parameters.
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TABLE 1 H2 O2 Etch P Power Flow rate Flow rate rate (Torr) (watts) T (° C.) (SCCM) (SCCM) (Å/min) Example 1 19 1500 400 1000 500 140 Example 2 19 1900 400 1000 500 155 Example 3 19 1900 400 1500 750 152 Example 4 19 1900 400 700 350 151 Example 5 19 1900 400 400 200 141 Example 6 19 1900 400 1250 250 116 Example 7 19 1900 400 750 750 102 Example 8 19 1900 400 250 1250 119 Example 9 19 1900 400 300 300 104 Example 10 19 1900 400 200 400 101 Example 11 19 1500 400 400 200 149 Example 12 19 1500 400 500 1000 88 Example 13 9 1500 400 1000 500 107 - With respect to increased oxygen or hydrogen flow rates, excess oxygen or hydrogen in the plasma generally has little effect on etching rate. The rate of etching is limited by the amount of boron or carbon present on the surface of the boron-carbon film with which the oxygen or hydrogen can form a volatile compound, and generally is not significantly increased with the inclusion of excess process gas. However, it should be noted that the etching rate can be increased through the inclusion of additional process gas when the process gas is the limiting reactant (e.g., excess reactant sites are present on the surface of the boron-carbon film).
- Flow diagram 200 illustrates one embodiment of stripping a boron-carbon film; however, other embodiments are also contemplated. In another embodiment, it is contemplated that the oxygen-containing compound and hydrogen-containing compound in
operation 206 may be introduced to the stripping chamber using a carrier gas, such as argon, helium, or nitrogen, having a flow rate less than 15,000 SCCM per 300 millimeter substrate. The inclusion of carrier gas to the processing volume may decrease the rate at which the boron-carbon film is etched, but may also increase plasma uniformity and stability. -
FIGS. 3A and 3B illustrate the effect of chamber pressure and RF power on etch rate when using a plasma containing oxygen and hydrogen. InFIG. 3A , a boron-carbon film at 400° C. was removed from a substrate using a plasma formed from 2,000 SCCM of hydrogen gas and 1,000 SCCM of oxygen gas at 1,000 watts of RF power. As the pressure within the chamber is increased, the etching rate of the boron-carbon film is correspondingly increased. Thus, in all methods described herein, etch rate of the boron-carbon film may be controlled by adjusting the pressure within the chamber. InFIG. 3B , a boron-carbon film at 400° C. was removed using plasma formed from 2,000 SCCM of hydrogen gas and 1,000 SCCM of oxygen gas. The chamber pressure was maintained at 9 Torr. As the RF power applied to the plasma is increased, the etching rate of the boron-carbon film is correspondingly increased. -
FIG. 4 is a flow diagram illustrating a method of removing a boron-carbon film using plasma generated from hydrogen and nitrous oxide according to one embodiment of the invention. Flow diagram 400 includesoperations Operations operations operation 102, and removing the carbon-based polymer inoperation 104, the substrate and the boron-carbon film thereon are exposed to a plasma formed from hydrogen and nitrous oxide inoperation 406. Thus, while flow diagram 200 uses oxygen as an oxidizing agent to remove carbon from the boron-carbon film, flow diagram 400 uses nitrous oxide as an oxidizing agent. The use of nitrous oxide as an oxidizing agent allows the pressure within the chamber to be increased, thus increasing etch rate, while reducing the probability of undesired reactions occurring within the processing environment as is likely when using oxygen as an oxidizing agent. - In
operation 406, hydrogen gas and nitrous oxide gas are provided to the stripping chamber at flow rate of about 5 SCCM to about 15,000 SCCM for a 300 millimeter substrate to remove a boron-carbon layer from the surface of the substrate. For example, the hydrogen gas and the nitrous oxide gas may each be provided at a flow rate of about 200 SCCM to about 4,000 SCCM. The hydrogen gas and the nitrous oxide gas are ionized using an RF generator operating at 13.56 MHz and applying about 100 watts to about 3,000 watts of power, such as about 1,500 watts to about 2,000 watts of power. The substrate is maintained at a heater temperature less than 750° C., such as at about 400° C. The pressure within the stripping chamber is maintained at less than 760 Torr, such as about 40 Torr to about 60 Torr. The nitrous oxide plasma and the hydrogen plasma react with the boron-carbon film to form volatile compounds which are then exhausted from the chamber. - Table 2 illustrates some exemplary process recipes for removing a boron-carbon film from the surface of a 300 millimeter substrate using a plasma formed from hydrogen and nitrous oxide.
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TABLE 2 H2 N2O Etch P Power Flow rate Flow rate rate (Torr) (watts) T (° C.) (SCCM) (SCCM) (Å/min) Example 14 49 1500 400 1500 750 104 Example 15 49 1500 400 1000 500 121 Example 16 49 1500 400 500 250 143 Example 17 49 1500 400 250 125 129 Example 18 60 2000 400 1500 1000 190 Example 19 60 2000 400 1125 750 215 Example 20 60 2000 400 750 500 239 Example 21 60 2000 400 375 250 244 Example 22 60 2000 400 225 150 241 - As illustrated in Table 2, the use of nitrous oxide as an oxidizing agent generally yields a greater etching rate than when using oxygen as an oxidizing agent. This is due partly to the higher chamber pressures which can be utilized when using nitrous oxide. In another embodiment, it is contemplated that the oxidizing gas may be a mixture of nitrous oxide and oxygen, in which case, the pressure in the chamber may be permitted to exceed 20 Torr. Furthermore, although flow diagram 400 is described with reference to co-flowing nitrous oxide and hydrogen gas, it is contemplated that the nitrous oxide and hydrogen gas be independently provided to the chamber in a cyclical manner. In yet another embodiment, it is contemplated that carbon dioxide may be used in addition to or as an alternative to nitrous oxide.
-
FIG. 5 is a flow diagram 500 illustrating a method of removing a boron-carbon film using plasma generated from water vapor according to one embodiment of the invention. Flow diagram 500 includesoperations Operations operations operation 102, and removing the carbon-based polymer inoperation 104, the substrate and the boron-carbon film thereon are exposed to a plasma formed from water vapor inoperation 506. - In
operation 506, water vapor is produced by a water vapor generator (WVG) and is provided to a stripping chamber where the water vapor is ignited into a plasma to etch a boron-carbon film from the surface of a substrate. The water vapor is introduced to the stripping chamber at a flow rate of about 5 SCCM to about 15,000 SCCM per 300 millimeter substrate. The substrate is maintained at a temperature less than about 750° C., such as about 300° C. to about 500° C., for example about 400° C., while the pressure in the chamber is maintained at less than about 760 Torr, such as about 10 Torr to about 760 Torr, such as about 10 Torr to about 100 Torr, for example about 65 Torr. RF power within a range of about 10 watts to 3,000 watts, for example about 2,700 watts, is applied to the water vapor to generate a plasma containing oxygen, hydrogen, and hydroxyl ions or radicals, which react with the boron-carbon film to form volatile compounds which are exhausted from the chamber. - Flow diagram 500 illustrates one embodiment for stripping a boron-carbon film; however, additional embodiments are also contemplated. For example, it is contemplated that the water vapor may be generated via in situ steam generation. In another embodiment, it is contemplated that non-stoichiometric combinations of oxygen and hydrogen (e.g., HxOy, where x and y may be integers or non-integers both greater than zero) may be input to or generated by the WVG. In such an embodiment, some hydrogen peroxide may be generated by the water vapor generator. In another embodiment, it is contemplated that oxygen gas, helium gas, nitrogen gas, argon gas, nitrous oxide gas, and or/hydrogen gas may be provided to the stripping chamber in addition to water vapor. In such an embodiment, the addition of hydrogen has been found to increase the removal rate of the boron-carbon film, especially in boron-carbon films containing a higher concentration of boron as compared to carbon. The addition of other carrier gases, such as helium, has been observed to lower the rate of removal of the boron-carbon film, while simultaneously improving etch uniformity. In another embodiment, it is contemplated that the water vapor may be used to strip a carbon film, such as amorphous carbon, containing substantially no boron. Alternatively, it is contemplated that the water vapor may be used to strip a boron film, such as amorphous boron, containing substantially no carbon.
- In another embodiment, it is contemplated that a fluorine-containing gas or a chlorine-containing gas may be ionized in
operation 506 in combination with the water vapor to increase the etching rate of the boron-carbon film. In such an embodiment,operation 104 may be omitted. The fluorine-containing gas or the chlorine-containing gas is generally provided to the chamber at a flow rate between about 10 SCCM and 50 SCCM. In order to avoid undesirably etching dielectric materials present on the substrate, the flow rate of the fluorine-containing gas or the chlorine-containing gas is tapered, reduced, or eliminated when approaching the end ofoperation 506. It is believed that reduction in flow rate near the end ofoperation 106 does not undesirably etch exposed dielectric materials due to the mechanism in which the fluorine-containing gas or the chlorine-containing gas assists in removal of the boron-carbon layer. - Generally, dielectric material on the substrate is exposed in vias or trenches formed into the substrate during a previous etching process, while boron-carbon material is exposed on the upper surface of the substrate. Thus, the fluorine-containing gas or the chlorine-containing gas which enters the chamber and is ignited into a plasma generally contacts and reacts with the boron-carbon layer prior to contacting the dielectric material in the vias or trenches. However, as the boron-carbon film is removed, the probability of the fluorine-containing gas or the chlorine-containing gas contacting and undesirably removing the dielectric material is increased. Therefore, the flow rate of the fluorine-containing gas or the chlorine-containing gas is reduced as the thickness of the boron-containing layer decreases in order to reduce the probability of etching the dielectric material.
- In another embodiment, when generating a capacitively coupled water vapor plasma, the spacing between the substrate and a face place located within the chamber may be within a range of about 20 mils to about 600 mils, for example about 170 mils. Reduced spacing between the substrate is beneficial when processing substrates in larger volumes (for example, when processing large area substrates) under higher pressures (for example, greater than about 7 Torr). When processing substrates at pressures greater than about 7 Torr, the reduced spacing facilitates plasma sustainability. In one example, when processing a substrate at about 30 Torr, the spacing between the substrate and the face plate may be about 300 mils. At 40 Torr, the spacing between the substrate and the face plate may be within a range of about 240 mils to about 270 mils. At a pressure of about 50 Torr, the spacing between the substrate and the face plate may be less than 200 mils. At a pressure above 50 Torr, for example about 65 Torr, the spacing may be about 170 mils. Performing a stripping operation as described herein above a pressure of 50 Torr results in
- Table 3 illustrates a change in etch rate of a boron-carbon film in response to a change in process gas flow rate. Each of Examples 23-30 in Table 3 includes at least 500 SCCM of helium gas as a carrier gas to increase etch uniformity, and may contain additional carrier gas, as noted in Table 3.
-
TABLE 3 Power H2O Flow He Flow Carrier Etch rate P (Torr) (watts) T (° C.) rate (SCCM) rate (SCCM) gas (SCCM) (Å/min) Example 23 50 1900 400 1000 250 0 679 Example 24 50 1900 400 1000 400 0 613 Example 25 50 1900 400 1000 250 150 H2 720 Example 26 50 1900 400 1000 250 350 H2 630 Example 27 50 1900 400 1000 250 150 Ar 617 Example 28 50 1900 400 1000 250 350 Ar 527 Example 29 50 1900 400 1000 250 750 Ar 389 Example 30 50 1900 400 1000 500 0 546 - As shown in Table 3, Example 29, which contains the highest total flow rate of carrier gas (250 SCCM of helium and 750 SCCM of argon) has the lowest etch rate.
- Table 4 includes some examples of boron-carbon film stripping recipes at higher severity. High severity conditions include pressures above 50 Torr, high gas flow rates of at least 7 sLm, and higher power input of at least about 2000 watts. Such high severity conditions can maintain a water vapor plasma, optionally with excess hydrogen, at a spacing less than 200 mils.
-
TABLE 4 H2O Flow He Flow Hydrogen Power Spacing rate rate Flow Rate P (Torr) (watts) (mils) T (° C.) (mgm) (SCCM) (mgm) Example 31 65 2700 170 400 5400 2400 0 Example 32 65 2700 170 400 5400 2400 30 Example 33 65 2700 170 400 5400 2400 600
As noted above, it is thought that adding hydrogen in excess of the stoichiometric proportions of water may accelerate reactions with boron and accelerate the overall rate of removal of boron-carbon films. The exact amount of excess hydrogen that is most beneficial depends on the amount of boron in the carbon film. -
FIG. 6 illustrates the etching selectivity of water vapor plasma. Plasma A includes 1,000 SCCM of water vapor and 500 SCCM of helium generated into a plasma using 1900 watts of RF power. The stripping chamber is maintained at 50 Torr, and the substrate is maintained at 400° C. Plasma A etched the boron-carbon film at a rate of about 570 angstroms per minute, and did not etch silicon oxide, silicon nitride, or amorphous silicon. - Plasma B includes 1,000 SCCM of water vapor, 250 SCCM of helium, and 150 SCCM of hydrogen generated into a plasma using 1900 watts of RF power. The stripping chamber is maintained at 50 Torr, and the substrate is maintained at 400° C. Plasma B etched the boron-carbon film at a rate of about 770 angstroms per minute, and did not etch silicon oxide, silicon nitride, or amorphous silicon.
- Benefits of the methods described herein include stripping boron-carbon films without damaging dielectric materials or underlying metal layers located on a substrate. The stripping methods allow for etching rate, as well as etching uniformity to be controlled by varying plasma composition.
- While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (8)
1. A method for stripping a film from a substrate, comprising:
positioning a substrate having a film thereon in a chamber, the film comprising boron and carbon;
exposing the film to a water vapor plasma at a pressure above 50 Torr to generate one or more volatile compounds from the boron and carbon; and
exhausting the one or more volatile compounds from the chamber.
2. The method of claim 1 , wherein an atomic ratio of boron to carbon in the film is within a range of about 1:1 to about 3:1.
3. The method of claim 1 , wherein the water vapor plasma is formed from a precursor gas comprising water vapor and a carrier gas, and a flow rate of the precursor gas is at least about 7 sLm.
4. The method of claim 2 , wherein the plasma is maintained at a power input of at least 2,000 watts and spacing less than 200 mils.
5. The method of claim 4 , wherein the water vapor plasma comprises excess hydrogen.
6. A method of removing a boron-carbon film, comprising:
exposing the boron-carbon film to a water vapor plasma containing excess hydrogen in a processing chamber;
maintaining a pressure in the processing chamber above 50 Torr;
reacting oxygen in the water vapor plasma with carbon in the boron-carbon film to form volatile carbon species;
reacting hydrogen in the water vapor plasma with boron in the boron-carbon film to form volatile boron species; and
removing the volatile carbon species and the volatile boron species from the processing chamber.
7. The method of claim 6 , wherein the water vapor plasma is formed from a precursor gas comprising the excess hydrogen, and the precursor gas is provided to the processing chamber at a flow rate of at least 7 sLm.
8. The method of claim 7 , wherein the water vapor plasma is formed by applying at least 2,000 watts of power to the precursor gas.
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US15/000,857 US20160133443A1 (en) | 2013-02-06 | 2016-01-19 | Methods of dry stripping boron-carbon films |
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US10510518B2 (en) | 2019-12-17 |
US20160064209A1 (en) | 2016-03-03 |
US20160133443A1 (en) | 2016-05-12 |
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