US20110143548A1 - Ultra low silicon loss high dose implant strip - Google Patents

Ultra low silicon loss high dose implant strip Download PDF

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Publication number
US20110143548A1
US20110143548A1 US12/636,582 US63658209A US2011143548A1 US 20110143548 A1 US20110143548 A1 US 20110143548A1 US 63658209 A US63658209 A US 63658209A US 2011143548 A1 US2011143548 A1 US 2011143548A1
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Prior art keywords
work piece
plasma
gas
carbon
fluorocarbon
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US12/636,582
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English (en)
Inventor
David Cheung
Haoquan Fang
Jack Kuo
Ilia Kalinovski
Ted Li
Andrew Yao
Anirban Guha
Kirk Ostrowski
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Novellus Systems Inc
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Novellus Systems Inc
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Priority to US12/636,582 priority Critical patent/US20110143548A1/en
Assigned to NOVELLUS SYSTEMS, INC. reassignment NOVELLUS SYSTEMS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OSTROWSKI, KIRK, FANG, HAOQUAN, KALINOVSKI, ILIA, LI, TED, CHEUNG, DAVID, GUHA, ANIRBAN, KUO, JACK, YAO, ANDREW
Priority to PCT/US2010/059388 priority patent/WO2011071980A2/en
Priority to KR1020117012215A priority patent/KR101226411B1/ko
Priority to JP2012543229A priority patent/JP5888652B2/ja
Priority to CN201080056124.1A priority patent/CN102870198B/zh
Priority to SG2011040862A priority patent/SG171962A1/en
Priority to TW099143367A priority patent/TWI559363B/zh
Publication of US20110143548A1 publication Critical patent/US20110143548A1/en
Priority to US14/721,977 priority patent/US9564344B2/en
Abandoned legal-status Critical Current

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    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H01L21/31138—Etching organic layers by chemical means by dry-etching
    • 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
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/31144—Etching the insulating layers by chemical or physical means using masks
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks

Definitions

  • the present invention pertains to methods and apparatuses to remove or strip photoresist material and removing related residues from a work piece surface.
  • this application relates to methods and apparatus for stripping resist after ion implant or plasma assisting doping implant (low dose or high-dose implanted resist).
  • Photoresist is a light sensitive material used in certain fabrication processes to form a patterned coating on a work piece, e.g., a semiconductor wafer, during processing. After exposing the photoresist coated surface to a pattern of high energy radiation, a portion of the photoresist is removed to reveal the surface below, leaving the rest of the surface protected. Semiconductor processes such as etching, depositing, and ion implanting are performed on the uncovered surface and the remaining photoresist. After performing one or more semiconductor processes, the remaining photoresist is removed in a strip operation.
  • dopant ions e.g., ions of boron, boron difluoride, indium, gallium, thallium, phosphorous, arsenic, antimony, bismuth, or germanium
  • the ions implant in exposed regions of the work piece as well as in the remaining photoresist surface.
  • the process may form well regions (source/drain) and lightly doped drain (LDD) and doubled diffused drain (DDD) regions.
  • LDD lightly doped drain
  • DDD doubled diffused drain
  • the ion implant impregnates the resist with the implant species and depletes the surface of hydrogen.
  • the outer layer or crust of the resist forms a carbonized layer that may be much denser than the underlying bulk resist layer. These two layers have different thermal expansion rates and react to stripping processes at different rates.
  • the difference between the outer layer and bulk layer is quite pronounced in post high-dose ion implant resist.
  • the ion dose may be greater than 1 ⁇ 10 15 ions/cm 2 and the energy may be from 10 Kev to greater than 100 keV.
  • Traditional high dose implantation strip (HDIS) processes employ oxygen chemistries where monatomic oxygen plasma is formed away from the process chamber and then directed at the work piece surface. The reactive oxygen combines with the photoresist to form gaseous by-products which is removed with a vacuum pump. For HDIS, additional gases are needed to remove the implanted dopants with oxygen.
  • Residues are commonly found on the substrate surface after HDIS and stripping. They may result from sputtering during the high-energy implant, incomplete removal of crust, and/or oxidation of implant atoms in the resist. After stripping, the surface should be residue free or substantially residue free to ensure high yield and eliminate the need for additional residue removal processing. Residues may be removed by overstripping, i.e., a continuation of the strip process past the point nominally required to remove all photoresist. Unfortunately, in conventional HDIS operations, overstripping sometimes removes some of the underlying functional device structure. At the device layer, even very little silicon loss from the transistor source/drain regions may adversely affect device performance and yield, especially for ultra shallow junction devices fabricated at the ⁇ 32 nm design rule or below.
  • plasma is generated using elemental hydrogen, a fluorine-containing gas and a protectant gas.
  • the plasma-activated gases reacts with the high-dose implant resist, removing both the crust and bulk resist layers, while simultaneously protecting exposed portions of the work piece surface.
  • the work piece surface is left substantially residue free with low silicon loss.
  • FIGS. 1A-1D depict various stages of semiconductor device fabrication before and after ion implantation and stripping operations.
  • FIGS. 2A-2D depict various stages of semiconductor device fabrication before and after ion implantation and stripping operations according to certain embodiments in which the device includes a metal gate.
  • FIG. 3A shows residue remaining as functions of NF3 flow rate and CF4 flow rate.
  • FIG. 3B shows silicon loss as functions of NF3 flow rate and CF4 flow rate.
  • FIGS. 4 and 5 are a process flow diagrams showing various operations in accordance with certain embodiments of the present invention.
  • FIG. 6 shows silicon loss as a function of CO2 flow rate.
  • FIG. 7 shows a multi-station sequential architecture suitable for implementing aspects of the present invention.
  • FIG. 8 is a schematic illustration showing an apparatus suitable for implementing aspects of the present invention.
  • the terms “work piece”, “semiconductor wafer”, “wafer” and “partially fabricated integrated circuit” will be used interchangeably.
  • the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication thereon. The following detailed description assumes the invention is implemented on a wafer. However, the invention is not so limited.
  • the work piece may be of various shapes, sizes, and materials.
  • other work pieces that may take advantage of this invention include various articles such as displays, printed circuit boards, and the like.
  • the methods and apparatus of the invention may be used to efficiently and effectively to remove photoresist materials after high-dose ion implantation.
  • the invention is not limited to high-dose implant strip (HDIS).
  • HDIS high-dose implant strip
  • the invention is also not limited to any particular category of dopants implanted.
  • described methods and apparatus may be effectively used with stripping after medium or low dose implant. Although specific dopant ions such as boron, arsenic, and phosphorous are discussed, the described methods and apparatus may be effectively used to strip resist impregnated with other dopants, such as nitrogen, oxygen, carbon, germanium, and aluminum.
  • the methods and apparatus of the present invention use plasmas that are produced from gases that contain hydrogen.
  • the gases also contain a weak oxidizing agent, a fluorine-containing gas and a protectant gas, such as CF 4 .
  • a weak oxidizing agent such as CF 4
  • the actual species present in the plasma may be a mixture of different ions, radicals, and molecules derived from the hydrogen, weak oxidizing agent, fluorine containing gas and protectant gas.
  • other species may be present in the reaction chamber, such as small hydrocarbons, carbon dioxide, water vapor and other volatile components as the plasma reacts with and breaks down the organic photoresist and other residues.
  • the initial gas/gases introduced into the plasma is/are often different from the gas/gases that exist in the plasma as well as the gas/gases contact the work piece surface during strip.
  • FIG. 1A to 1D depicts various stages of semiconductor fabrication before and after ion implantation and stripping operations.
  • FIG. 1A shows a semiconductor substrate 101 coated with photoresist material 103 .
  • the substrate 101 may include one or more layers of deposited film, e.g., oxide film, silicide contact, and/or polysilicon film, or may be a bare silicon substrate, including for example a silicon-on-insulator type substrate.
  • the photoresist material coats the entire substrate surface.
  • the photoresist is then exposed to patterned radiation generated through a mask and developed to remove a portion of the material, e.g., the opening 104 shown in FIG. 1A between the remaining photoresist materials 103 .
  • the substrate is then exposed to an ion implant process.
  • ion implant the surface of the work piece or wafer is implanted with dopant ions.
  • the process may be, for example, a plasma-immersion ion implantation (PIII) or ion beam implantation.
  • the ions bombard the substrate surface, including the exposed silicon layer 101 and the photoresist 103 .
  • small amounts of the underlying material 107 may be sputtered to the photoresist sidewalls. See FIG. 1B .
  • This material may include some of the implant species, other material in the plasma or ion beam, and by-products of the implantation. They include silicon, aluminum, carbon, fluorine, titanium, other contact materials such as cobalt, and oxygen in both elemental and compound forms.
  • the actual species depend on the composition of the substrate before ion implant, the photoresist, and the implanted species.
  • a doped region 109 is created.
  • the ion energy or intensity of the bombardment determines the depth or thickness of the doped region.
  • the density of the ion flux determines the extent of doping.
  • the ions also impregnate the photoresist surface creating a crust layer 105 .
  • the crust layer 105 may be carbonized and highly cross-linked polymer chains.
  • the crust is usually depleted of hydrogen and impregnated with the implant species.
  • the crust layer 105 is denser than the bulk resist layer 103 .
  • the relative density depends on the ion flux while the thickness of the crust layer depends on the ion energy.
  • This crust layer 105 is harder to strip than the bulk photoresist 103 below. Removal rates of the crust layer may be 50% or 75% slower than the underlying bulk photoresist.
  • the bulk photoresist contains relatively high levels of chemically bonded nitrogen and some of its original casting solvent. At elevated wafer temperature, e.g., above 150 to above 200° C., the bulk resist can outgas and expand relative to the crust layer. The entire photoresist can then “pop” as the underlying bulk photoresist builds up pressure under the crust. Photoresist popping is a source of particles and process defects because the residues are especially hard to clean from the wafer surface and chamber internal parts. With high-dose ion implantation, the density difference between the crust and underlying bulk photoresist layer is even higher. The crust may also be thicker.
  • FIG. 1C shows the substrate after a strip that fails to completely remove the photoresist 103 and the sidewall sputter residue 107 .
  • the sidewall sputter residue 107 may include particles that do not form a volatile compound under conventional strip chemistries. These particles may remain after a conventional strip operation.
  • the residue may also include oxides of implanted species formed with the reactive oxygen used in the conventional strip chemistry, such as boron oxide and arsenic oxide. Portions of the crust 105 may also remain on the substrate. Crust sidewalls and corners at the bottom of photoresist vias may be hard to strip because of geometries.
  • Silicon loss is a function of resist thickness, crust thickness, and percent overstrip. Longer and more aggressive stripping to remove thicker resist can also remove more silicon. For resist with thicker crust, the difference between the crust layer and bulk resist layer is even more pronounced. The thicker crust sidewalls and corners are even harder to strip. Thus, strip processes designed to remove thick crust also tends to remove more silicon.
  • Overstrip may be used to address resist uniformity and geometries in addition to residue removal. Overstrip is a continuation of the strip process past the point nominally required to remove all photoresist. If the photoresist is totally removed in some areas of the wafer but not others, continuation of the strip process would cause additional material, typically silicon and silicon oxide, to be removed from areas that are already stripped. Typical overstrip is about 100%.
  • FIG. 1D shows the substrate after all residue has been removed.
  • the residue is removed without additional silicon loss or oxidation and with minimum delay.
  • the strip process leaves no residue and thus reduces the number of process steps.
  • FIGS. 2A-2D depicts various stages of semiconductor fabrication before and after ion implantation and stripping operations for a particular embodiment in which the device includes a metal gate.
  • FIG. 2A shows the partially fabricated device including metal gate stack 210 and patterned photoresist 203 on semiconductor substrate 201 prior to ion implantation. Note that patterned photoresist 203 partially obscures the view of metal gate stack 210 in the depicted figure.
  • substrate 201 is a silicon-on-insulator substrate.
  • Shallow trench isolation (STI) regions 205 are embedded with substrate 201 and are generally trenches filled with an insulating material such as silicon oxide.
  • FIG. 2B shows the device during implantation, including ion beam flux 214 and resputter flux 216 .
  • STI shallow trench isolation
  • the resputter flux 216 deposits substrate materials (Si, STI and SiN) on the sidewall. After implantation, a crust 215 is formed on the top ( 215 a ) and sidewalls ( 215 b ) of the bulk photoresist 203 as shown in FIG. 2C .
  • the top crust 215 a and side crust 215 b may see different environments during implantation due to the angle of the ion implant beam flux 214 as well as the sidewall deposition from the resputter flux 216 .
  • the bulk photoresist 203 and crust formations 215 a and 215 b are removed, leaving an undamaged metal gate 210 and minimal loss of surface material from the surfaces of substrate 201 and STI regions 205 , as shown in FIG. 2D .
  • the metal gate stack can include one or more of titanium nitride (TiN), Ta, TaN, or W.
  • TiN titanium nitride
  • Ta tantadium
  • TaN tantadium
  • W tantadium
  • a high-k gate dielectric such as hafnium oxide, zirconium oxide and titanium oxide may be disposed between the substrate and metal gate.
  • metal gates are incompatible with conventional oxygen-based strip chemistries.
  • conventional oxygen-based chemistries result in high silicon loss.
  • One aspect of the invention relates to novel strip chemistries for high dose implant resist and residue removal that limit silicon loss.
  • the photoresist and residues are exposed to a plasma formed from molecular hydrogen, a weak oxidizing agent, a fluorine-containing compound and a protectant compound.
  • the disclosed processes achieve a substantially residue free strip process with minimal silicon loss and are compatible with metal gates.
  • fluorine radicals in the plasma combine with hydrogen in the process gas to form hydrogen fluoride (HF) instead of remaining as fluorine radicals.
  • HF hydrogen fluoride
  • the silicon loss is believed to be reduced in part because the protectant compound reacts with the surface silicon to form protective polymerized films, carbides, nitrides or other non-oxide protective layers, which have lower etch rates than oxides in HF.
  • the strip process involves generating a plasma from a gas including various component gases.
  • the strip chemistries described herein are hydrogen-based, rather than oxygen-based.
  • Molecular hydrogen (H 2 ) is the main component of the plasma-generating gas, with 1,000-40,000 sccm, e.g., 1,000-6,000 sccm, H 2 run in the background, with example flow rates of other components of the plasma-generating gas being at least an order of magnitude.
  • the other component gases include a fluorine-containing compound and a protectant compound.
  • carbon dioxide or other weak oxidizing agent is included, though in certain embodiments it is not.
  • weak oxidizing agents include carbon oxides such as carbon dioxide (CO 2 ), carbon monoxide (CO), nitrogen oxides such as nitrous oxide (N 2 O), nitric oxide (NO), nitrogen dioxide (NO 2 ), and sulfur oxides such as sulfur oxide (SO) and sulfur dioxide (SO 2 ).
  • other weak oxides include any oxygen containing hydrocarbons (C X H Y O Z ) and water (H 2 O).
  • the weak oxidizing agent is a carbon-containing compound.
  • carbon dioxide is used as the weak oxidizing agent because it is cheap, safe, and effective.
  • the fluorine-containing gas can be nitrogen trifluoride (NF 3 ), sulfur hexafluoride (SF 6 ), hexafluoroethane (C 2 F 6 ), tetrafluoromethane (CF4), trifluoromethane (CHF 3 ), difluoromethane (CH 2 F 2 ), octofluoropropane (C 3 F 8 ), octofluorocyclobutane (C 4 F 8 ), octofluoro[1-]butane (C 4 F 8 ), octofluoro[2-]butane (C 4 F 8 ), octofluoroisobutylene (C 4 F 8 ), fluorine (F 2 ), and the like.
  • NF 3 nitrogen trifluoride
  • SF 6 sulfur hexafluoride
  • C 2 F 6 hexafluoroethane
  • CF4 tetrafluoromethane
  • CHF 3 triflu
  • the fluorine-containing gas is NF 3 , SF 6 , F 2 , or HF vapor. As described below, it has been found that these gases are superior strip gases than certain carbon-containing etchants such as CF 4 .
  • the fluorine-containing compound is a non-carbon containing compound.
  • NF 3 is used as the fluorine-containing gas.
  • the main etchant component in the chamber during the strip is HF vapor. Accordingly, in certain embodiments, any fluorine-containing gas that readily converts to HF vapor may be used.
  • the protectant compound is generally a carbon-containing compound, though in certain embodiments it may be a nitrogen-containing compound.
  • the protectant gas may also be a fluorine-containing compound.
  • the protectant compound is CF 4 .
  • the process chemistry generally includes both a fluorine-containing compound (e.g., NF 3 ) and a protectant compound (CF4), where these compounds are distinct. That is, even where the protectant compound contains fluorine, a distinct fluorine-containing compound is provided as well.
  • the fluorine-containing compound is a significantly stronger etchant than the protectant compound.
  • the protectant compound is a carbon-containing compound, with examples including CF 4 , and CH 4 .
  • the protectant compound is a nitrogen-containing compound.
  • the protectant compound reacts with, or provides reactant species to react with, the silicon/silicon oxide surfaces, forming for example, carbides and nitrides, that are more resistant to etching.
  • the etch rate of a nitride in HF is on the order of about 50 times less than that of an oxide, with the etch rate of a carbide about at least about an order of magnitude less than that of a nitride.
  • oxygen-containing compounds may be employed as protectant compounds, so long as the compounds are not strong oxidants.
  • the strip chemistry is H 2 /CO 2 /NF 3 /CF 4 , with example relative volumetric ratios being 100/0.1-1/0.5-4/2-5. In one example, a ratio is 3000/32/15/100.
  • the total flow rate of gas, the relative amount of weak oxidizing agent, fluorine-containing gas, protectant gas and other conditions in the strip chamber can vary depending upon, among other factors, plasma type (downstream versus direct), RF power, chamber pressure, substrate (wafer) size and type of weak oxidizing agent, fluorine-containing gas and protectant gas used.
  • the total flow rate of gas may range between about 1,000 sccm and about 40,000 sccm with the flow rate of carbon dioxide about 1 sccm and about 400 sccm and RF power will preferably range between about 300 Watts to about 5000 Watts.
  • Chamber pressures will typically range between about 300 mTorr and about 2 Torr, e.g., between about 800 mTorr and about 1.6 Torr.
  • the ratios of fluorine-containing gas and protectant gas are varied in certain process sequence to provide complete photoresist and residue removal and low silicon loss.
  • the carbon dioxide or other weak oxidizing agent is controlled to reduce silicon loss.
  • process sequences effective to remove the high dose implant crust and residue removal are provided.
  • the process sequences involve varying the ratio of the fluorine-containing gas and the protectant gas during the process sequence to provide the necessary removal.
  • the process sequences involve an operation in which the wafer is exposed to a plasma generated from a gas including a fluorine-containing and protectant component gases followed by an operation in which the wafer is exposed to a plasma generated from a fluorine-containing gas only. In certain embodiments, these operations may be reversed.
  • FIGS. 3A and 3B show experimental results indicating that the fluorine-containing gas (NF3) and a protectant gas (CF4) may be employed to both reduce residue and reduce silicon loss.
  • FIG. 3A shows a residue score, which indicates the amount of residue, as functions of NF3 and CF4 flow rates (with the other compound held at constant flow rate). As flow rate increases, the residue decreases due to the increased presence of fluorine. Note that in embodiments wherein the protectant gas is not a fluorine-containing compound, the curve for the protectant gas may be flattened.
  • FIG. 3B shows silicon loss as functions of NF3 and CF4 flow rates.
  • Silicon loss increases with increasing NF3 flow rate, due to the etching of the surface by activated fluorine species and/or fluorine-containing compounds in the plasma.
  • silicon loss decreases with increasing CF4 flow rate at a fixed NF3 flow rate such as 60 sccm as indicated on FIG. 3B .
  • the slope of the CF4 response is higher or lower depending on NF3 flow rate—illustrating the importance of having the right ratio.
  • the decrease in silicon loss with higher CF4 flow rates may be due to the formation of a carbon-containing protective film at the substrate surface.
  • the protective film may be formed by a polymerization reaction between carbon species and the silicon surface material.
  • the use of a fluorine-containing protective gas allows the protectant gas to simultaneously provide a protective effect as well as (along with the fluorine-containing gas) provide residue removal.
  • the process includes at least one operation that uses a combination of NF3 and CF4.
  • a post-high implant dose (post-HDI) wafer may be placed into a strip chamber. After pre-heating the wafer, H2/CO2/CF4/NF3 gas is introduced in the chamber, and a plasma struck. The wafer is exposed to the plasma for a period of time sufficient to clean the crust, bulk photoresist and other residue.
  • post-HDI post-high implant dose
  • the process sequence varies the relative amount of NF3 (or other fluorine-containing gas) and CF4 (or other protectant gas).
  • NF3 or other fluorine-containing gas
  • CF4 or other protectant gas
  • different process sequences may be employed.
  • sequences or parts of sequences that may be employed to remove parts of the bulk photoresist, crust and sputter residue, along with examples of process sequences for stripping various post-implant photoresist and residue formations.
  • the below description refers to NF3 and CF4, however, it should be understood that other fluorine-containing and protectant gases, respectively may be employed for either of these component gases.
  • a two step process for removing side and top crusts is employed, involving NF3+CF4, followed by NF3 only.
  • H2 and optionally CO2 are run in the background for all strip operations).
  • the two step process is employed to remove the side crust (NF3+CF4) followed by the top crust (NF3 only).
  • the NF3 only operation may involve a fluorine “spike” or “burst” in which the NF3 flow rate is increased by two or more times.
  • the following per-station flow rates may be applied: First operation (side crust): 2-3 liters per minute (lpm) H2; 32 sccm CO2; 100 sccm CF4; 15 sccm NF3.
  • top crust 2-3 lpm H2; 32 sccm CO2; 0 sccm CF4; 50 sccm NF3.
  • the flow rates described may be scaled up or down depending on the size and configuration of the reactor, wafer size, and dose time. It has been found that in certain cases using NF3 only, for an acceptable level of silicon loss, the top crust is removed, but the side crust is not removed. It has also been found that in certain cases using NF3+CF4, for an acceptable level of silicon loss, removes the side crust but not the top crust. Accordingly, employing a two-step process as discussed allows removal of both the side and top crusts.
  • FIG. 4 describes a process flow 400 for removing photoresist and crusts according to various embodiments.
  • the wafer is pre-heated to a temperature low enough to prevent popping, but high enough to provide an acceptable etch rate. According to various embodiments, this may be between 200 C-400 C, more particularly between 240 C-350 C, e.g., at 285 C.
  • the wafer is exposed to a plasma generated from hydrogen, carbon dioxide, nitrogen trifluoride and carbon tetrafluoride (H2/CO2/NF3/CF4).
  • Generating the plasma generally involves introducing the component gases (which may be pre-mixed or not) into a plasma source.
  • the plasma is a remote plasma source though it may also be in-situ (i.e., in the strip chamber).
  • This first operation may remove the side crust and the bulk photoresist, while protecting the surface from silicon loss.
  • the CF4 flow is turned off, and the wafer is exposed to a plasma generated from hydrogen, carbon dioxide and nitrogen trifluoride (H2/CO2/NF3) only. This operation removes the top crust residue.
  • H2/CO2/NF3 hydrogen, carbon dioxide and nitrogen trifluoride
  • the CF4/NF3 ratio may be changed as necessary by increasing or decreasing the flow rates.
  • a combination of CF4 and NF3 is employed to remove the bulk photoresist and/or side crusts.
  • NF3 is spiked at various points in the process to provide additional removal for residues not easily removed. Spiking NF3 may or may not involve reducing or turning the CF4 flow.
  • FIG. 5 shows an example of such a process 500 according to various embodiments. As with the previous example, the wafer is first pre-heated in an operation 501 .
  • the wafer is exposed to a plasma generated from H2/CO2/NF3/CF4, with NF3 spiked, in an operation 503 .
  • This operation may remove the crust while protecting against silicon loss. In certain embodiments, both top and side crusts may be removed.
  • the NF3 flow rate is reduced and the wafer is exposed to a plasma generated from H2/CO2/NF3/CF4 for removal of the bulk photoresist.
  • the CF4 flow is turned off and the wafer is exposed to a plasma generated from H2/CO2/NF3.
  • the NF3 is optionally spiked during this operation. This operation may be an overstrip operation to completely remove any remaining residue.
  • Overstripping refers to a continuation of the strip process past the point nominally required to remove all photoresist, and may involve stripping material from already cleaned surfaces. After removing byproducts (not shown), the process ends at an operation 509 , and the cleaned wafer may be removed.
  • spiking NF3 may be done at different stages in the process. For example, NF3 may be spiked at the beginning of the removal process to facilitate difficult top crust removal. The top crust may be removed at the beginning of the process to prevent the possibility of popping. Bulk photoresist removal may then be performed using a lower NF3 flow rate in combination with CF4. In certain embodiments, NF3 is spiked after removal of the bulk photoresist to facilitate stringer removal. Stringers are long, narrow photoresist residue segments that may be left by non-exposure between two adjacent exposure areas.
  • the NF3 and CF4 ratio during removal of all or part of the bulk photoresist may be considered to be a “base” ratio, with spikes measured relative to this ratio. So for example, taking a NF3:CF4 during bulk photoresist removal to be a “base,” according to various process sequences the ratio may be raised prior to and/or after the bulk photoresist removal.
  • the base ratio is 3:20 (e.g., 15 sccm NF3, 100 sccm CF4) with a spike raising the ratio to 1:2 (50 sccm NF3, 100 sccm CF4), or in cases in which CF4 is not present, infinity.
  • CF4 only and no NF3 may be present for one or more operations, however, in many embodiments, CF4 has been found to provide adequate protection allowing the process to take advantage of the higher removal rate of NF3.
  • a base ratio of 1:50-1:2 may be employed, with a spike being higher than the base ratio.
  • a NF3 spike may involve at least doubling the ratio of NF3:CF4.
  • a CO2 bleed gas is employed, and run at all times with H2. It has been found that for a 300 mm wafer, using 10-15 lpm H2 (2-3 lpm per station), running between about 100 sccm-300 sccm CO2 (20 to 60 sccm per station) results in less silicon loss than outside this range. This is shown in FIG. 6 .
  • the flow rates in FIG. 6 reflect the total CO2 over a 5-station chamber; on a per-station basis, the wafer sees 20 sccm-60 sccm CO2, more particularly 32 sccm.
  • a hydrogen-containing gas is introduced to the plasma source.
  • the gas introduced to the plasma source contains the chemically active species that will be ionized or otherwise in the plasma source to form a plasma.
  • the gas introduced to the plasma source includes a fluorine-containing gas such as elemental fluorine, nitrogen trifluoride, and sulfur hexafluoride.
  • the gas introduced to the plasma includes a protectant gas, typically a carbon-containing protectant gas.
  • the protectant gas is a fluorocarbon gas, such as carbon tetrafluoride, C 2 F 6 or a hydrofluorocarbon.
  • the gas introduced to the plasma source comprises between about 0.1% to about 3% carbon tetrafluoride by volume and about 0.3% to 2% nitrogen trifluoride by volume.
  • the gas introduced to the plasma source may include a weak oxidizing agent such as carbon dioxide, carbon monoxide, nitrogen dioxide, nitrogen oxide and/or water.
  • the weak oxidizing agent is carbon dioxide.
  • the inlet gas may include between about 1 and 99 volume percent, about 80 and 99.9 volume percent, or about 95 volume percent molecular hydrogen, between about 0 and 25 volume percent CO2 or other weak oxidizing agent, between about 0.1 and 3 volume percent nitrogen trifluoride or other non-carbon containing fluorine-containing compound and between about 0.1 and 6% volume percent carbon tetrafluoride or other protectant compound.
  • the gas inlet to the plasma source consists essentially of molecular hydrogen, carbon dioxide or other weak oxidizing agent, non-carbon containing fluorine-containing compound, and protectant compound.
  • the protectant gas flow is shut off in one or more operations in a process sequence
  • the gas inlet to the plasma source consists essentially of molecular hydrogen, carbon dioxide or other weak oxidizing agent and non-carbon containing fluorine-containing compound.
  • an additional one or more gasses may be added to the process gas. For example, an inert gas may be added.
  • the gas introduced to the plasma source may be premixed, partially mixed or unmixed. Individual gas sources may flow into a mixing plenum before being introduced to the plasma source. In other embodiments, the different gases may separately enter the plasma source.
  • the gas introduced to the plasma source may have different compositions when used in different reaction stations of a multistation chamber. For example in a 6-station chamber, station 1 (or station 2 , if station 1 is used for pre-heat) or station 6 may employ process gases with relatively higher amounts of NF3 gas to remove the crust or the residue, respectively. One or more of the other stations may employ process gases with little or no protectant gas. Process gases with no carbon dioxide or weak oxidizing agents may also be used.
  • RF plasma sources may be used in accordance with the invention, including RF, DC, and microwave based plasma sources.
  • a downstream RF plasma source is used.
  • the RF plasma power for a 300 mm wafer ranges between about 300 Watts to about 10 Kilowatts. In some embodiments, the RF plasma power is between about 2000 Watts and 5000 Watts, e.g., 3500 W.
  • the plasma gas is distributed to the work surface via a showerhead assembly.
  • the showerhead assembly may be grounded or have an applied voltage to attract some charge species while not affecting the flow of neutral species to the wafer, e.g., 0-1000 watt bias. Many of the electrically charged species in the plasma recombine at the showerhead.
  • the assembly includes the showerhead itself which may be a metal plate having holes to direct the plasma and inert gas mixture into the reaction chamber.
  • the showerhead redistributes the active hydrogen from the plasma source over a larger area, allowing a smaller plasma source to be used.
  • the number and arrangement of the showerhead holes may be set to optimize strip rate and strip rate uniformity.
  • the showerhead holes are preferably smaller and fewer in the center of the showerhead in order to push the active gases toward the outer regions.
  • the showerhead may have at least 100 holes.
  • Suitable showerhead include the Gamma xPR showerhead or the GxT drop-in showerhead available from Novellus Systems, Inc. of San Jose, Calif. In embodiments in which there is no showerhead assembly, the plasma enters the process chamber directly.
  • the process chamber may be any suitable reaction chamber for the strip operation being performed. It may be one chamber of a multi-chambered apparatus or it may simply be a single chamber apparatus. The chamber may also include multiple stations where different wafers are processed simultaneously. The process chamber may be the same chamber where the implant, etch, or other resist-mediated process takes place. In other embodiments, a separate chamber is reserved for the strip.
  • Process chamber pressure may range from about 600 mTorr to 2 Torr. In certain embodiments, the pressure ranges from about 0.9 Torr to 1.5 Torr.
  • the process chamber includes one or more processing stations on which strip operations are performed.
  • the one or more processing stations includes a preheat station, at least one strip station, and an over-ash station.
  • the wafer support is configured to support the wafer during processing.
  • the wafer support may also transfer heat to and from the wafer during processing to adjust the wafer temperature as necessary.
  • the wafer is supported on a plurality of minimum contacts and does not physically contact the wafer support surface plane.
  • a spindle picks up the wafer and transfers the wafer from one station to another.
  • FIG. 8 is a schematic illustration showing aspects of a downstream plasma apparatus 800 suitable for practicing the present invention on wafers.
  • Apparatus 800 has a plasma producing portion 811 and an exposure chamber 801 separated by a showerhead assembly 817 . Inside exposure chamber 801 , a wafer 803 rests on a platen (or stage) 805 . Platen 805 is fitted with a heating/cooling element. In some embodiments, platen 805 is also configured for applying a bias to wafer 803 . Low pressure is attained in exposure chamber 401 via vacuum pump via conduit 807 . Sources of gaseous hydrogen (with or without dilution/carrier gas) and carbon dioxide (or other weak oxidizing agent) provide a flow of gas via inlet 809 into plasma producing portion 811 of the apparatus.
  • gaseous hydrogen with or without dilution/carrier gas
  • carbon dioxide or other weak oxidizing agent
  • Plasma producing portion 811 is surrounded in part by induction coils 813 , which are in turn connected to a power source 815 .
  • gas mixtures are introduced into plasma producing portion 811 , induction coils 813 are energized and a plasma is generated in plasma producing portion 811 .
  • showerhead assembly 817 may have an applied voltage or be grounded directs the flow of species into exposure chamber 801 .
  • wafer 803 may be temperature controlled and/or a RF bias may be applied.
  • Various configurations and geometries of the plasma source 811 and induction coils 813 may be used. For example, induction coils 813 may loop around the plasma source 811 in an interlaced pattern.
  • the plasma source 811 may be shaped as a dome instead of a cylinder.
  • a controller 850 may be connected to components of the process chamber, and control process gas composition, pressure, temperature and wafer indexing of the stripping operations.
  • Machine-readable media may be coupled to the controller and contain instructions for controlling process conditions for these operations.
  • Suitable plasma chambers and systems include the Gamma 2100, 2130 I 2 CP (Interlaced Inductively Coupled Plasma), G400, and GxT offered by Novellus Systems, Inc. of San Jose, Calif.
  • Other systems include the Fusion line from Axcelis Technologies Inc. of Rockville, Md., TERA21 from PSK Tech Inc. in Korea, and the Aspen from Mattson Technology Inc. in Fremont, Calif.
  • various strip chambers may be configured onto cluster tools. For example, a strip chamber may be added to a Centura cluster tool available from Applied Materials of Santa Clara, Calif.
  • the work piece used in accordance with the methods and apparatus of the invention is a semiconductor wafer. Any size wafer may be used. Most modern wafer fabrication facilities use either 200 mm or 300 mm wafers.
  • the process and apparatus disclosed herein strips photoresist after a processing operation such as etching, ion implant, or deposition.
  • the present invention is suitable for wafers having very small features or critical dimensions, e.g., sub 100 nm, at 65 nm, or at or less than 45 nm.
  • the low silicon loss feature of the HDIS as disclosed is particularly suitable for very shallow junctions of advanced logic devices.
  • the present invention is also specifically suitable for wafers undergoing front end of the line (FEOL) ion implantation, especially high-dose ion implantation.
  • FEOL front end of the line
  • the plasma-activated species reacts with the photoresist and sputter residue on the wafer.
  • the reactive gas may include a number of plasma activated species, the inert gas, radicals, charged species, and gas by-products.
  • the volume concentration of various hydrogen species may be about 20-80% of the gas at the wafer.
  • the volume concentration of various fluorine species may be 0.01% to about 2% or less than 1%.
  • the volume concentration of various species from the weak oxidizing agent may be 0.05 to about 5% or about 1.2%.
  • These species may include H 2 *, H 2 + , H + , H*, e ⁇ , OH, O*, CO, CO 2 , H 2 O, HF, F*, F ⁇ , CF, CF 2 , and CF 3 .
  • Process conditions may vary depending upon the wafer size. In some embodiments of the invention, it is desired to keep the work piece at a particular temperature during the application of plasmas to its surface. Wafer temperatures can range between about 110 degrees and about 500 degrees Celsius. To reduce the likelihood of photoresist popping described above, wafer temperature is preferably increased slowly until enough crust has been removed and photoresist popping ceases to be a concern. Initial station temperature may be about 110 degrees to about 260 degrees Celsius, for example, about 240 degrees Celsius. Later stations can use higher temperatures such as 285 degrees Celsius and about 350 degrees Celsius successfully with good strip rates. In certain embodiments, the temperature is increased during NF3 spikes to reduce Si loss associated with these spikes.
  • FIG. 7 is a simplified schematic showing a top view of such an apparatus including stations 1 , 2 , 3 , 4 , 5 and 6 . Wafers enter the apparatus at station 1 via chamber 701 , are transferred to each station in sequence for a processing operation at that station and exit from station 6 via chamber 702 after the process is complete.
  • the architecture allows hydrogen based residue free high dose implant strip process with low silicon loss and TiN metal gate compatibility.
  • the above process is an example of a process sequence including a NF3 spike in station 6 .
  • the above process is an example of a process sequence including a NF3 spike for half of the exposure time in station 2 , during crust removal.
  • a wafer may be in the station for 18 seconds, with NF3 spiked for the second 9 seconds.
  • the above process is an example of a process in which CF4 is shut off at a point during the station 2 exposure time, e.g., to aid in crust removal.
  • the above process sequences provide examples showing how the strip may be controlled by modifying the relative NF3 and CF4 flow rates.

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