Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K13/00—Etching, surface-brightening or pickling compositions
  • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B6/00—Cleaning by electrostatic means
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K13/00—Etching, surface-brightening or pickling compositions
  • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
  • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/042—Acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • 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
  • G03F7/422—Stripping or agents therefor using liquids only
  • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
• • 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
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • 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
  • G03F7/422—Stripping or agents therefor using liquids only

Definitions

• the present invention relates to supercritical fluid-based compositions useful in semiconductor manufacturing for the removal of organic and inorganic bottom anti-reflection coatings (BARCs) from substrates having such BARC layers thereon, and to methods of using such compositions for removal of BARC layers from semiconductor substrates.
• BARCs bottom anti-reflection coatings
• the mask has directed therethrough a beam of monochromatic radiation, such as ultraviolet (UV) light or deep UV (DUV) light (-250 nm), to make the exposed photoresist material more or less soluble in a selected rinsing solution.
• a beam of monochromatic radiation such as ultraviolet (UV) light or deep UV (DUV) light (-250 nm)
• UV ultraviolet
• DUV deep UV
• the soluble photoresist material is then removed, or "developed,” thereby leaving behind a pattern identical to the mask.
• BARCs bottom anti- reflective coatings
• organic BARCs including, but not limited to, polysulfones, polyureas, polyurea sulfones, polyacrylates and poly(vinyl pyridine), are typically 600- 1200A thick and deposited using spin-on coating techniques.
• organic BARCs are planarizing layers, filling up the vias evenly, because the polymeric materials used do not readily crosslink.
• Organic BARCs prevent light reflection by matching the reflective index of the BARC layer with that of the photoresist layer while simultaneously absorbing radiation thereby preventing further penetration to the deeper interfaces.
• inorganic BARCs including silicon oxynitrides (SiO x N y ), are deposited using CVD deposition techniques and as such, conformal coverage of the substrate is achieved with good uniform thickness of the BARC layer.
• Inorganic BARCs reduce transmissivity and reflectivity by destructive interference wherein the light reflected from the BARC-photoresist interface cancels out the light reflected from the BARC-substrate interface.
• SCF Supercritical fluids
• SCFs provide an alternative method for removing BARC layers from the semiconductor surface.
• SCFs diffuse rapidly, have low viscosity, near zero surface tension, and can penetrate easily into deep trenches and vias. Further, because of their low viscosity, SCFs can rapidly transport dissolved species.
• SCFs are highly non-polar and as such, many species are not adequately solubilized therein.
• the present invention relates to supercritical fluid-based compositions useful in semiconductor manufacturing for the removal of bottom anti-reflection coatings (BARCs) layers from substrates having same thereon, and to methods of using such compositions for removal of BARC layers from semiconductor substrates.
• BARC bottom anti-reflection coating
• the invention relates to a bottom anti-reflection coating (BARC) removal composition, comprising at least one SCF, at least one co-solvent, at least one etchant and at least one surfactant.
• the invention relates to a bottom anti-reflection coating (BARC) removal composition, comprising supercritical carbon dioxide (SCCO ), triethylamine trihydrofluoride, a fluorosurfactant and isopropyl alcohol.
• SCCO supercritical carbon dioxide
• the invention relates to a method of removing a bottom anti-reflection coating (BARC) layer from a substrate having same thereon, said method comprising contacting the substrate having the BARC layer thereon with an SCF-based removal composition comprising at least one SCF, at least one co-solvent, at least one etchant, and at least one surfactant, for sufficient time and under sufficient contacting conditions to at least partially remove the BARC layer from the substrate.
• the invention relates to a method of removing an ion implanted photoresist layer and a bottom anti-reflection coating (BARC) layer from a substrate having same thereon, said method comprising contacting the substrate having the photoresist layer and the BARC layer thereon with a SCF-based removal composition comprising at least one SCF, at least one co-solvent, at least one etchant, and at least one surfactant, for sufficient time and under sufficient contacting conditions to at least partially remove the photoresist layer and the BARC layer from the substrate.
• a SCF-based removal composition comprising at least one SCF, at least one co-solvent, at least one etchant, and at least one surfactant, for sufficient time and under sufficient contacting conditions to at least partially remove the photoresist layer and the BARC layer from the substrate.
• Figure 1 is a scanning electron microscope (SEM) image at 50k magnification of a cross-section of the control wafer showing the 70 nm BARC layer sandwiched between the silicon substrate and the photoresist layer.
• Figure 2 is an optical image of a plan view of the sample in Figure 1.
• Figure 3 is an optical image of the wafer of Figure 2, processed using a
• SCCO 2 /fluoride/ fluorinated surfactant composition showing removal of the photoresist layer.
• Figure 4 is an optical image of the wafer of Figure 2, processed using a
• SCCO 2 /fluoride/ fluorinated surfactant/methanol composition showing removal of the photoresist layer and the BARC layer.
• the present invention is based on the discovery of a supercritical carbon fluid-based composition that is highly efficacious for the removal of photoresist and bottom anti-reflection coatings (BARCs) layers from patterned semiconductor wafers on which same are present. Specifically, the present invention relates to the removal of photoresist and BARC layers from patterned ion implanted semiconductor wafers.
• supercritical carbon dioxide SCCO 2
• SCCO 2 is a preferred SCF in the broad practice of the present invention, although the invention may be practiced with any suitable SCF species, with the choice of a particular SCF depending on the specific application involved.
• SCF species useful in the practice of the invention include oxygen, argon, krypton, xenon, and ammonia.
• SCCO 2 hereinafter in the broad description of the invention is meant to provide an illustrative example of the present invention and is not meant to limit the same in any way.
• SCCO 2 is often regarded as an attractive reagent for removal of unwanted layers from the surface of a semiconductor wafer, since SCCO 2 has the characteristics of both a liquid and a gas. Like a gas, it diffuses rapidly, has low viscosity, near-zero surface tension, and penetrates easily into deep trenches and vias. Like a liquid, it has bulk flow capability as a "wash" medium.
• supercritical CO 2 is non- polar. Accordingly, it will not solubilize many species, including the inorganic BARCs, e.g., SiO x N y , or polar organic BARC compounds, e.g., polysulfones and polyureas, that must be removed from the semiconductor substrate prior to subsequent processing.
• the non-polar character of SCCO 2 thus poses an impediment to the use of such reagent for complete and efficient BARC removal.
• the present invention is based on the discovery that disadvantages associated with the non-polarity of SCCO 2 and other SCFs can be overcome by appropriate formulation of SCCO 2 -based removal compositions with additives as hereinafter more fully described, and the accompanying discovery that removing photoresist and BARC layers from a substrate with a SCCO 2 -based removal medium is highly effective and achieves damage-free, residue-free removal of the photoresist and BARC layers from the substrate, e.g., a patterned ion implanted semiconductor wafer, having same thereon.
• the invention relates to SCCO 2 -based removal compositions useful in removing photoresist and/or BARC layers from a semiconductor substrate.
• the formulation of the present invention comprises SCCO 2 , at least one co-solvent, at least one etchant, and at least one surfactant, present in the following ranges, based on the total weight of the composition: component of % by weight SCCO 2 about 60.0% to about 90.0% co-solvent about 10.0% to about 30.0% etchant about 0.01% to about 5.0% surfactant about 0.01% to about 5.0%
• the SCCO 2 -based removal composition may comprise, consist of, or consist essentially of SCCO 2 , at least one co- solvent, at least one etchant and at least one surfactant.
• SCCO 2 -based removal composition may comprise, consist of, or consist essentially of SCCO 2 , at least one co- solvent, at least one etchant and at least one surfactant.
• the specific proportions and amounts of SCCO 2 , co-solvent, etchant, and surfactant, in relation to each other may be suitably varied to provide the desired removal action of the SCCO 2 - based composition for the photoresist and/or BARC layer species and/or processing equipment, as readily determinable within the skill of the art without undue effort.
• the inclusion of the co-solvent with SCCO 2 serves to increase the solubility of the composition for photoresist and/or BARC constituent species, e.g., SiO x N y , polysulfones and polyureas.
• the co-solvent used in the SCCO 2 -based removal composition can be an alkanol or an amine, or a combination thereof.
• the co-solvent includes a straight-chain or branched Cp C ⁇ 5 alkanol (i.e., methanol, ethanol, isopropanol, etc.), or a mixture of two or more of such alcohol species.
• the co-solvent is an amine including, but not limited to, monoethanolamine, triethanolamine, triethylenediamine, methyldiethanolamine, pentamethyldiethylenetriamine, or a glycol amine such as diglycolamine, N-methylpyrrolidone (NMP), N-octylpyrrolidone, N- phenylpyrrolidone and vinyl pyrrolidone.
• the alcohol is isopropanol (IP A).
• the ion implanted photoresist is advantageously removed from the substrate using an etchant, including hydrogen peroxide, acids, fluoride ion source compounds, or a combination thereof.
• the etchant(s) is added to the solution in an effective concentration, as readily determinable within the skill of the art, by the simple expedient of contacting the ion implant hardened photoresist with compositions of varying concentrations of the etchant(s), and determining the corresponding respective removal levels for the photoresist.
• Preferred acids include nitric acid, acetic acid and sulfuric acid.
• Preferred fluoride ion sources include hydrofluoric acid (HF), ammonium fluoride (NH 4 F) and triethylamine trihydrofluoride ((C 2 H 5 ) 3 N-3HF).
• the fluoride ion source is triethylamine trihydrofluoride.
• the surfactants contemplated in the SCCO 2 -based removal composition of the present invention may include nonionic surfactants, such as fluoroalkyl surfactants, ethoxylated fluorosurfactants, polyethylene glycols, polypropylene glycols, polyethylene or polypropylene glycol ethers, carboxylic acid salts, dodecylbenzenesulfonic acid or salts thereof, polyacrylate polymers, dinonylphenyl polyoxyethylene, silicone or modified silicone polymers, acetylenic diols or modified acetylenic diols, and alkylammonium or modified alkylammonium salts, as well as combinations comprising at least one of the foregoing.
• nonionic surfactants such as fluoroalkyl surfactants, ethoxylated fluorosurfactants, polyethylene glycols, polypropylene glycols, polyethylene or polypropylene glycol ethers, carboxylic acid salts,
• the surfactant is an ethoxylated fluorosurfactant such as ZONYL® FSO-100 fluorosurfactant (DuPont Canada Inc., Mississauga, Ontario, Canada).
• the surfactants may include anionic surfactants, or a mixture of anionic and non-ionic surfactants.
• Anionic surfactants contemplated in the SCF- based composition of the present invention include, but are not limited to, fluorosurfactants such as ZONYL® UR and ZONYL® FS-62 (DuPont Canada Inc., Mississauga, Ontario, Canada), sodium alkyl sulfates, ammonium alkyl sulfates, alkyl (Cio-Cis) carboxylic acid ammonium salts, sodium sulfosuccinates and esters thereof, e.g., dioctyl sodium sulfosuccinate, and alkyl (Cin- s) sulfonic acid sodium salts.
• fluorosurfactants such as ZONYL® UR and ZONYL® FS-62 (DuPont Canada Inc., Mississauga, Ontario, Canada)
• sodium alkyl sulfates such as ZONYL® UR and ZONYL® FS-62 (DuPont Canada Inc
• the specific proportions and amounts of SCCO 2 , co-solvent, etchant and surfactant in relation to each other may be suitably varied to provide the desired solubilizing (solvating) action of the SCCO 2 /co-solvent/ etchant/ surfactant solution for the specific photoresist and/or BARC layers to be cleaned from the substrate.
• Such specific proportions and amounts are readily determinable by simple experiment within the skill of the art without undue effort.
• the removal efficiency of the SCCO 2 /co-solvent/etchant/surfactant composition may be enhanced by use of elevated temperature conditions in the contacting of the photoresist and/or BARC layers to be removed with the SCCO -based removal composition.
• the SCCO 2 -based removal compositions of the invention may optionally be formulated with additional components to further enhance the removal capability of the composition, or to otherwise improve the character of the composition. Accordingly, the composition may be formulated with stabilizers, chelating agents, oxidation inhibitors, complexing agents, etc. [0036] In one embodiment, the SCF-based removal composition of the invention includes SCCO 2 , IPA, triethylamine trihydrofluoride, and a fluorosurfactant.
• the invention relates to methods of removal of photoresist and/or BARC layers, e.g., SiO x N y , polysulfones, polyureas, polyurea sulfones, polyacrylates and poly(vinyl pyridine), from a semiconductor wafer surface using the SCCO -based removal compositions described herein.
• photoresist and/or BARC layers e.g., SiO x N y , polysulfones, polyureas, polyurea sulfones, polyacrylates and poly(vinyl pyridine
• the SCCO 2 -based removal compositions of the present invention overcome the disadvantages of the prior art BARC removal techniques by minimizing the volume of chemical reagents needed, thus reducing the quantity of waste, while simultaneously providing a composition and method having recyclable constituents, e.g., the SCFs.
• the appropriate SCCO 2 -based removal composition can be employed to contact a wafer surface having photoresist and/or BARC layers thereon at a pressure in a range of from about 1500 to about 4500 psi for sufficient time to effect the desired removal of the layers, e.g., for a contacting time in a range of from about 1 minutes to about 20 minutes and a temperature of from about 30°C to about 100°C, although greater or lesser contacting durations and temperatures may be advantageously employed in the broad practice of the present invention, where warranted.
• the contacting temperature is in the range of from about 50°C to about 90°C, preferably about 70°C.
• the process conditions other than temperature may be selected and optimal or otherwise advantageous conditions determined within the skill of the art, including the superatmospheric pressure at which the supercritical fluid composition is contacted with the photoresist and/or BARC material to be removed from the substrate, the flow and/or static character of the SCCO 2 -based removal composition contacting, and the duration of the contacting.
• the wafer surface containing the photoresist and/or BARC layer may be processed by dynamically flowing or statically soaking the SCCO 2 -based removal composition over the wafer surface containing the photoresist and/or BARC layer.
• a "dynamic" contacting mode involves continuous flow of the composition over the wafer surface, thus maximizing the mass transfer gradient and affecting complete removal of the BARC layers from the surface.
• a "static soak” contacting mode involves contacting the wafer surface with a static volume of the composition, maintaining contact therewith for a continued (soaking) period of time.
• the removal process in a particularly preferred embodiment includes sequential processing steps including dynamic flow of the SCCO 2 -based removal composition over the wafer surface containing the photoresist and/or BARC layer, followed by a static soak of the wafer in the SCCO 2 -based removal composition, with the respective dynamic flow and static soak steps being carried out alternatingly and repetitively, in a cycle of such alternating steps.
• the dynamic flow/static soak steps may be carried out for four successive cycles in the aforementioned illustrative embodiment, as including a sequence of 2.5 min-10 min dynamic flow, 2.5 min-5 min high pressure static soak, e.g., about 3000 psi to about 4500 psi, 2.5 min-10 min dynamic flow, and 2.5 min-10 min low pressure static soak, e.g., about 1500 psi to about 2900 psi.
• the sequence consists of a 2.5 min dynamic flow, a 2.5 min static soak at 4500 psi, a 2.5 min dynamic flow, and a 2.5 min static soak at 1500 psi.
• the wafer thereafter preferably is washed with copious amounts of SCF/ methanol/deionized water solution in a first washing step, to remove any residual precipitated chemical additives from the region of the wafer surface in which particle removal has been effected, and finally with copious amounts of pure SCF, in a second washing step, to remove any residual methanol and/or precipitated chemical additives from the wafer surface.
• the SCF used for washing is SCCO 2 .
• the co-solvent/etchant/surfactant component of the SCCO 2 -based removal compositions of the present invention is readily formulated by simple mixing of ingredients, e.g., in a mixing vessel under gentle agitation.
• SCCO 2 -based removal compositions are applied to the wafer surface for contacting with the photoresist and/or BARC layers thereon, at suitable elevated pressures, e.g., in a pressurized contacting chamber to which the SCCO -based removal composition is supplied at suitable volumetric rate and amount to effect the desired contacting operation for removal of the organic BARC layer from the wafer surface.
• the sample wafers examined in this study were Si/SiO 2 patterned wafers having organic BARC layers and photoresist layers thereon.
• Various chemical additives, as described herein, were added to the SCCO 2 -based removal composition and photoresist and/or organic BARC layer removal efficiency evaluated.
• the temperature of the SCCO 2 -based removal composition was maintained at 70°C throughout the removal experiments. Following layer removal, the wafers were thoroughly rinsed with copious amounts of SCCO 2 / methanol/ eionized water and pure
• SCCO 2 in order to remove any residual solvent and/or precipitated chemical additives.
• Figure 1 is an scanning electron microscope (SEM) image of a cross-section of the control wafer showing the Si wafer surface having an 8 nm SiO 2 layer, a 70 nm organic BARC layer and a 700 nm deep ultraviolet (DUV) photoresist layer thereon.
• SEM scanning electron microscope
• Figure 4 is an optical image of the wafer of Figure 2 following processing using a SCCO 2 / fluoride-source/ fluorinated surfactant/co-solvent composition, showing that both the photoresist and the organic BARC layers have been removed from the

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