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WO2008057367A1 - Procédé d'élimination des époxy pour dispositifs microformés et électrodéposés - Google Patents

Procédé d'élimination des époxy pour dispositifs microformés et électrodéposés Download PDF

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Publication number
WO2008057367A1
WO2008057367A1 PCT/US2007/023041 US2007023041W WO2008057367A1 WO 2008057367 A1 WO2008057367 A1 WO 2008057367A1 US 2007023041 W US2007023041 W US 2007023041W WO 2008057367 A1 WO2008057367 A1 WO 2008057367A1
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Prior art keywords
weight
alkali
solution
permanganate
photoresist
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Inventor
Harris Miller
Donald W. Johnson
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Kayaku Advanced Materials Inc
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Microchem Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C99/00—Subject matter not provided for in other groups of this subclass
    • B81C99/0075—Manufacture of substrate-free structures
    • B81C99/0095—Aspects relating to the manufacture of substrate-free structures, not covered by groups B81C99/008 - B81C99/009
    • 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
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • 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

Definitions

  • the present invention is directed to the production of micromachines, microelectromechanical systems (MEMS) and more particularly to methods for producing high aspect-ratio plated microstructures and deep etched vias using an epoxy-based photoresist and removing the photoresist with a permanganate-based photoresist remover.
  • MEMS microelectromechanical systems
  • Epoxy-based photoresists in particular are capable of producing very high aspect-ratio, micron-sized features with near perfect sidewalls. Some commercial applications of these photoresist structures can be found in ink-jet nozzles, micro-fluidic channels and bulk acoustic wave filters for wireless transmission. Other MEMS devices use these same epoxy-based photoresists as a microform or micro-mold to produce a secondary metallic image by electrolytic or electroless plating techniques. Once the metal micro- structure has been formed, the epoxy photoresist is removed, leaving behind the final plated metallic structure.
  • Removing the epoxy mold without harming the plated metal structure can be difficult, because many of the properties that make cured epoxy resins resistant to chemical attack from the plating solution also make them resistant to their removal in photoresist stripping chemistry.
  • complete removal of the epoxy mold is critical for producing many MEMS devices, such as induction coils, harmonic micro-drives and fuel cell catalysts.
  • Advanced packaging and chip stacking techniques rely upon a method of perforating the completed wafer with microscopic holes, which pass completely through the substrate and are known as through-hole-wafer-vias.
  • the vias are commonly formed using a dry, isotropic etching technique known as deep reactive ion etching (DRIE).
  • DRIE deep reactive ion etching
  • the wafer vias are isotropic, because of a process (a.k.a. "Bosch") of alternating gases of sulfur hexafluoride and octafluorocyclobutane. Alternating these two gases successively deposits and removes polymer in the etched vias, which acts to passivate the etched sidewall, which produces extremely high aspect ratio etched structures under vacuum and a radio frequency (RF) generated plasma.
  • RF radio frequency
  • Such an epoxy resin known as BMR, is commercially available from Nippon Kayaku Co. Ltd. Japan. It is also possible to remove the photoresist using dry processing techniques, such as reactive ion etching (RIE). However, RIE etch rates for photoresist stripping rarely exceed 1 -2 ⁇ m per minute. This means that the dwell time for stripping photoresist from a single wafer can be almost two hours for a 100 ⁇ m coating of photoresist, whether the plasma is generated by RF or microwaves.
  • RIE reactive ion etching
  • the drill bit temperature exceeds the glass transition temperature (Tg) of the epoxy resin and spreads excess, unwanted epoxy into the drilled hole, making it difficult to plate the hole with electrolytic or electroless copper plating solutions.
  • Tg glass transition temperature
  • This thin layer of epoxy resin, which is "smeared” by the drill bit into the printed circuit board hole can be removed by treatment with a solution of alkali permanganate.
  • This process known as “desmear” removes the cross-linked epoxy resin by reacting it with an aqueous solution of alkali and permanganate to produce insoluble manganese dioxide and alkali soluble carboxylic acids (See Scheme. 1).
  • the manganese dioxide precipitate is then removed by converting it to aqueous, soluble manganese sulfate in a subsequent neutralizer solution.
  • the present invention is directed to a method of removing epoxy-based photoresist from a manufactured metallic microstructure, comprising the steps of (1) providing a form comprising an epoxy-based photoresist and a manufactured metallic microstructure; (2) optionally exposing the form to a solvent, aqueous alkali, or amine- based photoresist stripper; (3) exposing the form to an alkali permanganate oxidizing solution to remove the form from the manufactured metallic microstructure, the alkali permanganate oxidizing solution comprising from about 4% to about 9% permanganate by weight, based on the total weight of the alkali permanganate solution, and from about 3% to about 6% alkali by weight, based on the total weight of the alkali permanganate solution; and (4) exposing the manufactured metallic microstructure to a neutralizing solution comprising from about 5% to about 10% by weight of an acid and from about 1% to about 10% by weight of a reducing agent, all weight percents being based on the
  • the present invention is directed to a method of manufacturing a MEMS device, comprising the steps of: (1) providing a form comprising an epoxy-based photoresist and a manufactured MEMS device; (2) optionally exposing the form to a solvent, aqueous alkali, or amine-based photoresist stripper; (3) exposing the form to an alkali permanganate oxidizing solution to remove the form from the manufactured MEMS device, the alkali permanganate oxidizing solution comprising from about 4% to about 9% permanganate by weight, based on the total weight of the alkali permanganate solution, and from about 3% to about 6% alkali by weight, based on the total weight of the alkali permanganate solution; and (4) exposing the manufactured MEMS device to a neutralizing solution comprising from about 5% to about 10% by weight of an acid and from about 1% to about 10% by weight of a reducing agent, all weight percents being based on the total weight of the neutralizing solution.
  • the present invention is directed to a method of removing crosslinked epoxy novolak photoresist from a substrate, comprising the steps of: (1) providing a substrate comprising a form made from crosslinked epoxy novolak photoresist; (2) optionally exposing the substrate to a solvent, aqueous alkali, or amine-based photoresist stripper; (3) exposing the substrate to an alkali permanganate oxidizing solution to remove the crosslinked epoxy novolak photoresist from the substrate, the alkali permanganate oxidizing solution comprising from about 4% to about 9% permanganate by weight, based on the total weight of the alkali permanganate solution, and from about 3% to about 6% alkali by weight, based on the total weight of the alkali permanganate solution; and (4) exposing the substrate to a neutralizing solution comprising from about 5% to about 10% by weight of an acid and from about 1% to about 10% by weight of a reducing agent, all weight percents being
  • the present invention is directed to a method of removing crosslinked epoxy-based photoresist, comprising the steps of: (1) lithographically producing an etch mask on a substrate with an epoxy-based photoresist; (2) exposing the substrate to a DRIE plasma comprising alternating gases of sulfur hexafluoride and octafluorocyclobutane; (3) exposing the substrate to an alkali permanganate oxidizing solution to remove the crosslinked epoxy novolak photoresist from the substrate, the alkali permanganate oxidizing solution comprising from about 4% to about 9% permanganate by weight, based on the total weight of the alkali permanganate solution, and from about 3% to about 6% alkali by weight, based on the total weight of the alkali permanganate solution; and (4) exposing the substrate to a neutralizing solution comprising from about 5% to about 10% by weight of an acid and from about 1% to about 10% by weight of a reducing agent, all weight
  • This invention relates to a method for producing high aspect-ratio, micron-sized structures in epoxy-based photoresists, plating and forming micron-sized metal structures between, under and/or around the micro-formed epoxy photoresist and removing said epoxy photoresist without deforming the plated metal structures.
  • Such structures can be encountered in the fabrication of MEMS devices or in computer flip-chip packaging structures known as bumps.
  • the desmear printed circuit board process is rate controlled, which means that time, temperature, pH and permanganate concentration all must be tightly controlled to prevent too much epoxy from being removed and exposing the many glass fibers that support the epoxy polymer.
  • the desmear process for printed circuit boards is performed prior to electrolytic or electroless plating.
  • the method of using alkali permanganate to remove epoxy-based photoresists for MEMS applications and for micro-machined parts is said to go to completion because all of the resist is removed from the metal plated structure. Therefore, the epoxy-based photoresist removal process stops when all of the resist is reacted and it is therefore not necessary for critical timing of the process step. In the event that the removal process is incomplete and that some epoxy-based photoresist still remains, the process steps can be repeated without adverse chemical reactions. Since the entire epoxy mold is removed in the alkali permanganate solution, a robust process can be obtained by incorporating a small excess process time and without analytical controls of the permanganate solution. Also, because the MEMS device plating is completed before the epoxy-based photoresist is removed, there are no issues with contaminating the plating solution with permanganate residue.
  • the present invention is directed to a method of removing epoxy-based photoresist from a manufactured metallic microstructure or deep etched via, comprising the steps of (1) providing a form comprising an epoxy-based photoresist and a manufactured metallic microstructure; (2) optionally exposing the form to a solvent, aqueous alkali, or amine-based photoresist stripper; (3) exposing the form to an alkali permanganate oxidizing solution to remove the form from the manufactured metallic microstructure, the alkali permanganate oxidizing solution comprising from about 4% to about 9% permanganate by weight, based on the total weight of the alkali permanganate solution, and from about 3% to about 6% alkali by weight, based on the total weight of the alkali permanganate solution; and (4) exposing the manufactured metallic microstructure to a neutralizing solution comprising from about 5% to about 10% by weight of an acid and from about 1% to about 10% by weight of a reducing agent, all weight percents being
  • a form made from an epoxy-based photoresist and a manufactured metallic microstructure may be any microstructure commonly employed in microelectronics manufacturing, such as a micromachined part, a microelectromechanical systems (MEMS) device, a metal plated part, computer flip-chip packaging structures, metallic bumps, and the like.
  • MEMS microelectromechanical systems
  • the metal microstructure has a high aspect ratio, and more preferably an aspect ratio of greater than two, where the aspect ratio is defined as the ratio of the height to width of the structure.
  • the form may be made by any process or technique, such as lithography, electroplating, combinations of these techniques, and the like.
  • a preferred epoxy-based photoresist used in the method of the present invention is a carboxylated epoxy cresol novolak photoresist known as KMPR , commercially available from MicroChem Corp. U.S.A. and also by Kayaku MicroChem Corporation of Japan.
  • KMPR ® photoresist is capable of producing near vertical, high aspect-ratio micron-sized structures, which can be used for either electrolytic or electroless plating.
  • the KMPR ® photoresist plating form can be partially removed from the plated metallic structures by optionally pre-treating the form with a solvent, aqueous alkali, or amine based photoresist stripper solution.
  • solvents or amine based strippers include N-methyl pyrrolidone (NMP), dimethylsulfoxide (DMSO), sulfolane, dimethylforamide (DMF), dimethylacetamide (DMAC), diethylene glycol monobutyl ether or propylene carbonate, as well as combinations of these.
  • aqueous alkali include 20-45 wt% of aqueous sodium or potassium hydroxide.
  • this pre- treatment step occurs at a solution temperature of 6O 0 C - 8O 0 C.
  • Fully cross-linked KMPR ® resist can be completely removed from the ultra-high aspect ratio, micron-sized metal-plated structures using an alkali permanganate oxidizing solution.
  • the permanganate component of the alkali permanganate oxidizing solution is preferably selected from sodium or potassium permanganate.
  • the concentration of permanganate in the alkali permanganate oxidizing solution is not critical, but is preferably in the range of from about 4% by weight to about 9% by weight, based on the total weight of the alkali permanganate solution.
  • the alkali component of the alkali permanganate oxidizing solution is preferably selected from hydroxides such sodium hydroxide, potassium hydroxide, magnesium hydroxide, and the like. Other alkalis are known to those of skill in the art.
  • the concentration of alkali in the alkali permanganate oxidizing solution is also not critical, but is preferably in the range of from about 3% by weight to about 6% by weight, based on the total weight of the alkali permanganate solution. One useful concentration is approximately 5% by weight of permanganate and 5% by weight of alkali, based on the total weight of the alkali permanganate oxidizing solution.
  • Alkali permanganate solutions have also been shown to be capable of removing thick coatings of cross-linked SU-8 photoresist from bare silicon wafers. This occurs even after prolonged hard baking of the patterned resist to temperatures as high as 15O 0 C.
  • the alkali permanganate process allows SU-8 patterned wafers to be reworked or reprocessed. Therefore, the fabrication cost of imaging with SU-8 photoresist can be reduced and the commercial viability increased by the use of this process.
  • Residual epoxy resist and manganese dioxide are removed from the metal structures by neutralizing (reducing) the manganese dioxide in a neutralizer solution that comprises (1) an acid, such as sulfuric acid, sulfamic acid, methane sulfonic acid, and the like, and (2) a mild reducing agent such as hydroxylamine sulfate, hydroxylamine nitrate, hydroxylamine phosphate, and the like.
  • the concentration of acid is not critical, but is preferably in the range of from about 5% by weight to about 10% by weight, based on the total weight of the neutralizer solution.
  • the concentration of reducing agent is also not critical, but is preferably in the range of from about 1 % by weight to about 10% by weight, based on the total weight of the neutralizer solution.
  • the neutralizing solution process acts quickly and can be processed at 2O 0 C - 25 0 C.
  • a copper MEMS structure was created by vacuum sputtering a 150 mm diameter silicon wafer with an adhesion layer of 200A titanium followed by 5O ⁇ A of a copper metal seed layer.
  • a photoresist adhesion promoter containing hexamethyldisilazane (HMDS) was spin coated for 30 seconds at 3000 rpm and then baked for 2 minutes at 95 0 C.
  • a 50 ⁇ m coating of KMPR ® 1050 epoxy-based photoresist (generically known as a carboxylated epoxy ortho cresol novolak photoresist and commercially available from MicroChem Corp., Newton, MA) was spin-coated for 30 seconds at 3000 rpm on the copper coated silicon wafer and baked for 15 minutes at 100 0 C.
  • the edge bead was removed using a fine stream of a dioxolane mixture (commercially available from MicroChem Corp., Newton, MA, as EBR PG) directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm.
  • the coated wafer was then baked for 60 seconds at 65 0 C.
  • the coated wafer was then exposed using an EVG 620 aligner to 1100 mJ/cm of 350-436 ran filtered UV radiation. After exposure, the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide
  • the imaged microform wafer was complete, it was cleaned using oxygen plasma in a reactive ion etcher (RIE, available from March Plasma Systems, Concord, CA).
  • RIE reactive ion etcher
  • the wafers were plasma treated for 2 minutes with 100 W of DC power, 10 seem of oxygen at a pressure of about 50 mTorr.
  • the patterned and cleaned wafer was then plated using a solution of copper sulfate and sulfuric acid (commercially available from Technic, Inc., , Cranston, RI, as Copper U Bath RTU), for 70 minutes at room temperature and a current density of 100 mA.
  • the patterned photoresist microform was removed from the plated copper structures and the copper seed layer by immersing the wafers in a solution of NMP for 10 minutes at 7O 0 C followed by immersing the wafers in a solution of 5% w/w sodium permanganate (NaMnO 4 ) and 5% w/w sodium hydroxide (NaOH) for 10 minutes at 7O 0 C. Finally, the manganese dioxide was neutralized and the photoresist completely removed by immersing the wafers in a solution of 5% w/w hydroxylamine sulfate and 2% w/w of methane sulfonic acid for 2 minutes at room temperature.
  • a nickel MEMS structure was created by vacuum sputtering a 150 mm diameter silicon wafer with a seed layer of 500A nickel metal.
  • a photoresist adhesion promoter containing hexamethyldisilazane (HMDS) was spin coated for 30 seconds at 3000 rpm and then baked for 2 minutes at 95 0 C.
  • a 50 ⁇ m coating of KMPR ® 1050 epoxy-based photoresist was then spin-coated for 30 seconds at 3000 rpm on the nickel coated silicon wafer and baked for 15 minutes at 100 0 C.
  • the edge bead was removed using a fine stream of a dioxolane mixture directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm.
  • the coated wafer was then baked for 60 seconds at 65 0 C.
  • the coated wafer was then exposed using an EVG 620 aligner to 1100 mJ/cm 2 of 350-436 nm filtered UV radiation. After exposure, the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide, rinsed in deionized water and dried.
  • the wafer was cleaned using oxygen plasma in a reactive ion etcher (RIE).
  • RIE reactive ion etcher
  • the wafers were plasma treated for 2 minutes with 100 W of DC power, 10 seem of oxygen at a pressure of about 50 mTorr.
  • the patterned and cleaned wafer was then plated using a solution of nickel sulfamate, for 70 minutes at room temperature and a current density of 100 mA.
  • the patterned photoresist microform was removed from the plated nickel structures and nickel seed layer by immersing the wafers in a solution of NMP for 10 minutes at 7O 0 C followed by immersing the wafers in a solution of 5% w/w sodium permanganate (NaMnO 4 ) and 5% w/w sodium hydroxide (NaOH) for 10 minutes at 7O 0 C. Finally, the manganese dioxide was neutralized and the photoresist completely removed by immersing the wafers in a solution of 5% w/w hydroxylamine sulfate and 2% w/w of methane sulfonic acid for 2 minutes at room temperature.
  • a metal solder bump structure was created by vacuum sputtering a 150 mm diameter silicon wafer with an adhesion layer of 2O ⁇ A titanium followed by another 5O ⁇ A of a copper metal seed layer.
  • a photoresist adhesion promoter containing hexamethyldisilazane (HMDS) was spin coated for 30 seconds at 3000 rpm and then baked for 2 minutes at 95 0 C.
  • a 50 ⁇ m coating of KMPR ® 1050 epoxy-based photoresist was then spin-coated for 30 seconds at 3000 rpm on the copper coated silicon wafer and baked for 15 minutes at 100 0 C.
  • the edge bead was removed using a fine stream of a dioxolane mixture directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm.
  • the coated wafer was then baked for 60 seconds at 65 0 C.
  • the coated wafer was then exposed using an EVG 620 aligner to 1100 mJ/cm 2 of 350-436 nm filtered UV radiation. After exposure, the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide, rinsed in deionized water and dried. Once the imaged microform wafer was complete, the wafer was cleaned using an oxygen plasma in a reactive ion etcher (RIE). The wafers were plasma treated for 2 minutes with 100 W of DC power, 10 seem of oxygen at a pressure of about 50 mTorr.
  • RIE reactive ion etcher
  • the patterned and cleaned wafer was then plated using a solution of stannous sulfate, lead sulfate and sulfuric acid (commercially available from Technic, Inc. as Techni NuSolder JM-6000 LS), for 70 minutes at 45 0 C and a current density of 100 mA.
  • stannous sulfate, lead sulfate and sulfuric acid commercially available from Technic, Inc. as Techni NuSolder JM-6000 LS
  • the patterned photoresist microform was removed from the plated tin-lead structures and copper seed layer by immersing the wafers in a solution of NMP for 10 minutes at 7O 0 C followed by immersing the wafers in a solution of 5% w/w sodium permanganate (NaMnO 4 ) and 5% w/w sodium hydroxide (NaOH) for 10 minutes at 7O 0 C. Finally, the manganese dioxide was neutralized and the KMPR ® photoresist completely removed by immersing the wafers in a solution of 5% w/w hydroxylamine sulfate and 2% w/w of methane sulfonic acid for 2 minutes at room temperature.
  • Nickel air bridge and cantilever structures were created by vacuum sputtering a 150 mm diameter silicon wafer with a seed layer of 5O ⁇ A nickel metal and a zero layer alignment mark.
  • a photoresist adhesion promoter containing hexamethyldisilazane (HMDS) was spin coated for 30 seconds at 3000 rpm and then baked for 2 minutes at 95 0 C.
  • a 50 ⁇ m coating of KMPR ® 1050 epoxy-based photoresist was then spin-coated for 30 seconds at 3000 rpm on the nickel coated silicon wafer and baked for 15 minutes at 100 0 C.
  • the edge bead was removed using a fine stream of a dioxolane mixture directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm.
  • the coated wafer was then baked for 60 seconds at 65 0 C.
  • the KMPR ® coated wafer was then exposed to 650 mJ/cm 2 of 350-436 run filtered UV radiation with a photo-mask aligned to the zero layer using an EVG 620 aligner. After exposure, the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide, rinsed in deionized water and dried. The wafer was then cleaned using oxygen plasma in a reactive ion etcher (RIE).
  • RIE reactive ion etcher
  • the wafers were plasma treated for 2 minutes with 100 W of DC power, 10 seem of oxygen at a pressure of about 50 mTorr.
  • the patterned and cleaned wafer was then plated using a solution of nickel sulfamate for 70 minutes at room temperature and a current density of 100 mA. After plating, the wafer was rinsed in deionized water, dried and plasma treated for another 2 minutes with 100 W of DC power, 10 seem of oxygen at a pressure of about 50 mTorr.
  • a second layer of KMPR ® 1050 epoxy-based photoresist was coated directly on top of the patterned and plated first layer of KMPR ® 1050 by spin coating for 30 seconds at 3000 rpm and baking for 15 minutes at 100 0 C.
  • the edge bead was removed using a fine stream of a dioxolane mixture directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm.
  • the KMPR ® coated wafer was then baked for 60 seconds at 65 0 C.
  • the KMPR ® coated wafer was then exposed to 650 mJ/cm 2 of 350-436 nm UV radiation and aligned to the same zero layer with a different photo mask using an EVG 620 aligner. After exposure, the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide, rinsed and dried.
  • the wafer was then cleaned again using oxygen plasma for 2 minutes with 100 W of DC power, 10 seem of oxygen at a pressure of about 50 mTorr and plated again using a solution of nickel sulfamate, for 70 minutes at room temperature and a current density of 100 mA.
  • the wafer was rinsed in deionized water, Once the imaged microform wafer was complete, the patterned photoresist microform was removed from the plated nickel structures and nickel seed layer by immersing the wafers in a solution of NMP for 20 minutes at 7O 0 C followed by immersing the wafers in a solution of 5% w/w sodium permanganate (NaMnO 4 ) and 5% w/w sodium hydroxide (NaOH) for 20 minutes at 7O 0 C.
  • NMP 5% w/w sodium permanganate
  • NaOH sodium hydroxide
  • a gold metal bump structure was created by vacuum sputtering a 150 mm diameter silicon wafer with an adhesion layer of 2O ⁇ A titanium followed by another 500A of a gold metal seed layer.
  • a photoresist adhesion promoter containing hexamethyldisilizane (HMDS) was spin coated for 30 seconds at 3000 rpm and then baked for 2 minutes at 95 0 C.
  • a 50 ⁇ m coating of KMPR ® 1050 epoxy-based photoresist was then spin-coated for 30 seconds at 3000 rpm on the gold coated silicon wafer and baked for 15 minutes at 100 0 C.
  • the edge bead was removed using a fine stream of a dioxolane mixture directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm.
  • the KMPR ® coated wafer was then baked for 60 seconds at 65 0 C.
  • the KMPR ® coated wafer was then exposed using an EVG 620 aligner to 1100 mJ/cm 2 of 350-436 nm UV radiation. After exposure, the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide (commercially available from Rohm & Haas Electronic Materials Co. as CD-26), rinsed in deionized water and dried.
  • EVG 620 aligner 1100 mJ/cm 2 of 350-436 nm UV radiation.
  • the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide (commercially available from Rohm & Haas Electronic Materials Co. as CD-26), rinsed in deionized water and dried.
  • the wafer was cleaned using an oxygen plasma in a reactive ion etcher.
  • the wafers were plasma treated for 2 minutes with 100 W of DC power, 10 seem of oxygen at a pressure of about 50 mTorr.
  • the patterned and cleaned KMPR ® wafer was then plated using a non-cyanide solution of auric sulfate (commercially available from Technic, Inc. as TechniGold 25 ES), for 70 minutes at 45 0 C and a current density of 100 mA.
  • the patterned KMPR ® photoresist microform was removed from the plated gold structures and gold seed layer by immersing the wafers in a solution of NMP for 10 minutes at 7O 0 C followed by immersing the wafers in a solution of 5% w/w sodium permanganate (NaMnO 4 ) and 5% w/w sodium hydroxide (NaOH) for 10 minutes at 7O 0 C. Finally, the manganese dioxide was neutralized and the KMPR ® photoresist completely removed by immersing the wafers in a solution of 5% w/w hydroxylamine sulfate and 2% w/w of sulfuric acid for 2 minutes at room temperature.
  • a bare silicon wafer was stripped of cross-linked SU-8 photoresist (commercially available from MicroChem Corp.).
  • a 50 um coating of SU-8 was first prepared by spin- coating SU-8 2050 for 30 seconds at 3000 rpm on an untreated silicon wafer and baked for 15 minutes at 95 0 C. The edge bead was removed using a fine stream of a dioxolane mixture directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm. The SU-8 coated wafer was then baked for 60 seconds at 65 0 C.
  • the SU-8 coated wafer was then exposed using an EVG 620 aligner to 500 mJ/cm 2 of 350-436 nm filtered UV radiation. After exposure, the wafer was post-exposure baked for 3 minutes at 95 0 C and then developed in 1 -methoxy-2-propanol acetate (commercially available from MicroChem Corp. as SU-8 developer), rinsed with isopropanol and dried. Once the patterned SU-8 wafer was complete, the wafer was hard baked for 30 minutes at 15O 0 C.
  • the patterned SU-8 wafer was placed in a solution of NMP for 10 minutes at 7O 0 C followed by immersing the wafers in a solution of 5% w/w sodium permanganate
  • the present invention may also be implemented in removal of highly crosslinked epoxy-based photoresist, such as KMPR ® or SU-8 photoresist as described above, following exposure to fluorine plasma in a deep reactive ion etch (DRIE) processing.
  • DRIE deep reactive ion etch
  • one preferred embodiment of this aspect of the invention includes (1) lithographically producing an etch mask with an epoxy-based photoresist; (2) exposing the substrate to a DRIE plasma comprising alternating gases of sulfur hexafluoride and octafluorocyclobutane; (3) exposing the substrate to an alkaline oxidizing solution to remove the crosslinked SU-8 photoresist from the substrate; and (4) exposing the substrate to a reducing agent.
  • DRIE deep reactive ion etch
  • a 1000 ⁇ m deep through-hole- wafer-via was created using a 10 um coating of KMPR ® 1010 epoxy-based photoresist (commercially available from MicroChem Corp.), which was spin-coated for 30 seconds at 3000 rpm on a bare silicon wafer and baked for 10 minutes at 100 0 C.
  • the edge bead was removed using a fine stream of a dioxolane mixture directed at the edge of the wafer while spinning the wafer for 60 seconds at 600 rpm.
  • the KMPR ® coated wafer was then baked for 60 minutes at 65 0 C.
  • the KMPR ® coated wafer was then exposed using an EVG 620 aligner to 500 mJ/cm 2 of 350-436 nm filtered UV radiation.
  • the wafer was post-exposure baked for 3 minutes at 100 0 C and then developed in 0.26N tetramethyl ammonium hydroxide, rinsed in deionized water and dried. After drying, the wafer was hard baked for 30 minutes at 15O 0 C. After drying, the wafer was post-exposure baked for 3 minutes at 95 0 C and then developed in 1 -methoxy-2-propanol acetate, rinsed with isopropanol and dried. Once the patterned KMPR wafer was complete, the wafer was hard baked for 30 minutes at 15O 0 C.
  • the KMPR ® patterned and hard baked wafer was then etched in a Surface Technology Systems (manufactured by STS pic, Newport, UK) Multiplex ICP etcher for 8 hours using 600 W of coil power, 140 W of platen power, 140 seem of sulfur hexafluoride and 95 seem of octafluorocyclobutane at a pressure of 31 mTorr. This resulted in a 1000 ⁇ m deep silicon etch and which consumed only 16 um of KMPR ® photoresist.
  • the patterned KMPR ® photoresist etch mask was removed from the through-hole- wafer-via by immersing the wafers in a solution of NMP for 10 minutes at 7O 0 C followed by immersing the wafers in a solution of 5% w/w sodium permanganate (NaMnO 4 ) and 5% w/w sodium hydroxide (NaOH) for 10 minutes at 7O 0 C. Finally, the manganese dioxide was neutralized and the KMPR ® photoresist completely removed by immersing the wafers in a solution of 5% w/w hydroxylamine sulfate and 2% w/w of sulfuric acid for 2 minutes at room temperature.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

La présente invention concerne un procédé d'élimination de photorésist à base d'époxy à partir d'une microstructure métallique manufacturée ou d'un trou d'interconnexion profondément gravé, ledit procédé comprenant les étapes consistant à : (1) utiliser un élément comprenant un photorésist à base d'époxy et une microstructure métallique manufacturée ; (2) éventuellement exposer l'élément à un solvant, un alcali aqueux ou un décapant de photorésist à base d'amine ; (3) exposer l'élément à une solution oxydante à base de permanganate alcalin pour éliminer l'élément de la microstructure métallique manufacturée, la solution oxydante à base de permanganate alcalin comprenant d'environ 4 % à environ 9 % en poids de permanganate, par rapport au poids total de la solution de permanganate alcalin, et d'environ 3 % à environ 6 % en poids d'alcali, par rapport au poids total de la solution de permanganate alcalin ; et (4) exposer la microstructure métallique manufacturée à une solution neutralisante comprenant d'environ 5 % à environ 10 % en poids d'un acide et d'environ 1 % à environ 10 % en poids d'un agent réducteur, tous les pourcentages en poids étant fondés sur le poids total de la solution neutralisante.
PCT/US2007/023041 2006-11-01 2007-10-31 Procédé d'élimination des époxy pour dispositifs microformés et électrodéposés Ceased WO2008057367A1 (fr)

Applications Claiming Priority (4)

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US85587706P 2006-11-01 2006-11-01
US60/855,877 2006-11-01
US11/978,391 2007-10-29
US11/978,391 US20080142478A1 (en) 2006-11-01 2007-10-29 Epoxy removal process for microformed electroplated devices

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WO2008057367A1 true WO2008057367A1 (fr) 2008-05-15

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US12356710B2 (en) * 2020-08-13 2025-07-08 Taiwan Semiconductor Manufacturing Co., Ltd. Fin height and STI depth for performance improvement in semiconductor devices having high-mobility p-channel transistors

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