Classifications

• • 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
  • G03F7/38—Treatment before imagewise removal, e.g. prebaking
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0387—Polyamides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/123—Treatment by wave energy or particle radiation
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
• • 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
  • G03F7/20—Exposure; Apparatus therefor
• • 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
• • 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
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/65—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
  • H10P14/6516—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials
  • H10P14/6529—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials by exposure to a gas or vapour
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2505/00—Polyamides
  • B05D2505/50—Polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment
  • B05D3/029—After-treatment with microwaves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• Embodiments of the present disclosure pertain to apparatus and methods for materials processing using microwave energy, and more particularly, to methods for processing photosensitive polyimide (PSPI) films for electronic devices.
• PSPI photosensitive polyimide
• VFM Variable Frequency Microwaves
• the PAA PAE copolymer can be directly photo patterned like a conventional photoresist. As shown schematically in FIG. 1 , areas exposed to light through mask openings are crosslinked at the photoactive group "R" creating areas that are less soluble in developer solutions. The more soluble areas are removed by the developer leaving high resolution patterns.
• the "curing" of photosensitive polyimide films now involves (1 ) the imidization (or ring closure) reaction step, and (2) the release of the acrylate residue by-product of that imidization as shown schematically in FIG. 2. Removal of the acrylate residue is subsequently achieved at the same 375°C soak temperature.
• the chemistry of the acrylate residuals involves decomposition reactions at temperatures typically in excess of 350°C for extended times of at least an hour depending on the extent of residue removal required [see M. Zussman and R. Hubbard, "Rapid Cure of Polyimide Coatings for Packaging Applications", Proceedings of The 13 th Symposium on Polymers for Microelectronics, Wilmington, DE, (2008)].
• the convection process did not remove substantial amounts of the acrylate residue while the VFM process appeared to remove almost all of the residues.
• the remaining acrylate residue peak is shown in the Dynamic Mechanical Analysis (DMA) of the convection cured sample but not in the VFM cured sample.
• DMA Dynamic Mechanical Analysis
• TGA Thermal Gravimetric Analysis
• Non-limiting examples of one or more advantages that may be provided by at least some embodiments of the present disclosure include the following: providing a method for curing photosensitive polymers; providing a process that allows lower thermal budgets for energy savings in manufacturing; providing a process that allows previous or subsequent processing steps to be done at lower temperatures; providing a method for curing polymers while protecting any temperature sensitive components or materials; and providing a processing method for polymer films that reduces stress in materials that has a direct proportional relationship between stress and temperature.
• a method for curing photosensitive polyimide (PSPI) films includes: depositing a PSPI film on a selected substrate; and, curing the film by microwave heating at a selected temperature from about 200 to 275°C in a selected atmosphere containing an oxygen concentration from about 20 to 200,000 ppm.
• a method for curing photosensitive polyimide (PSPI) films includes: depositing a PSPI film on a selected substrate; photopatterning the PSPI film; developing the photopatterned PSPI film; and, curing the developed film by microwave heating at a selected temperature from about 200 to 275°C in a selected atmosphere containing an oxygen concentration from about 20 to 200,000 ppm.
• Figure 1 is a schematic diagram of the modification of polyamic acid by the addition of a methacrylate group to create a photosensitive polyamic ester.
• Figure 2 is a schematic diagram of the processing steps on a polyamic ester for imidization and acrylate removal.
• Figure 3 is a comparison of DMA data for oven-cured and microwave cured films, showing that MW curing effectively eliminates the residual polyacrylate.
• Figure 4 is a comparison of TGA data for cured photosensitive polyimide films, showing that the MW cured film has a 1 % weight loss at a much higher temperature than does the convection-cured sample.
• Figure 5 compares the results of imidization by convection versus MW cure of PSPI films on silicon wafers.
• Figure 6 compares the results of TMA showing that MW curing gives a higher T g than convection curing.
• Figure 7 shows the effect of oxygen partial pressure on MW curing of PSPI films.
• Figure 8 shows the effect of oxygen partial pressure on MW curing of PSPI films using a batch wafer VFM process.
• T g glass transition temperature
• p-TMA penetration mode Thermal Mechanical Analysis
• VFM processing of PSPI films on silicon wafers achieves substantially identical film properties with cure temperatures from about 230 to 270°C and times from about 60 to 180 minutes. Under those conditions, oxygen may be safely introduced without damaging the polyimide.
• VFM cured PSPI films have significantly higher T g than convection cured films after processing at comparable temperatures (250°C) over the entire range from about 50 to 350 minutes.
• VFM curing at 340°C at oxygen partial pressures from about 20 to 200,000 ppm leads to T g values from about 240 to 280°C as measured by DMA.
• the chamber pressure and oxygen concentration can be adjusted independently or together in order to maintain a desired level of oxygen activity equivalent to that of 20 to 200,000 ppm mixtures at ambient pressure.
• Any means of achieving oxygen activities in the aforementioned range are considered to be within the scope of the present disclosure.
• an effective oxygen concentration of 200,000 ppm may be maintained using air at 1 atmosphere, or pure oxygen at 0.2 atmosphere, or some other combination.
• VFM processing is advantageous because of the ease of creating a highly uniform power density throughout a large processing volume
• fixed-frequency MW curing may be used, for example if the component to be processed is small and/or a single-mode cavity is used to create a uniform energy density over a selected working volume.
• Applicants do not intend to limit themselves to any particular type of microwave system or microwave generator.
• the discussion herein of particular commercial film-forming materials deposited on silicon wafers is exemplary only and is not intended to limit the disclosure to the use of silicon as the substrate nor to limit the disclosure to any particular manufacturer's PSPI material or any particular manufacturer's photosensitive polymer.
• compositions may involve the modification of some sites of the polyamic acid (PAA) precursor resin with a photosensitive methacrylate alcohol to form a photosensitive polyamic ester (PAE) as shown in FIG. 1 .
• PAA polyamic acid
• PAE photosensitive polyamic ester
• R indicates any selected organic moiety attached at the indicated position.
• embodiments of the disclosure may be more generally applied to other photosensitive chemistries, for example, polybenzoxazoles (PBO), provided that the photosensitive moiety is at least partially removable during subsequent processing and does not form a permanent part of the polymer backbone.
• PBO polybenzoxazoles

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Plasma & Fusion (AREA)
• Engineering & Computer Science (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
• Formation Of Insulating Films (AREA)
• Materials For Photolithography (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

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