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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B34/00—Computer-aided surgery; Manipulators or robots specially adapted for use in surgery
  • A61B34/20—Surgical navigation systems; Devices for tracking or guiding surgical instruments, e.g. for frameless stereotaxis
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B5/00—Measuring for diagnostic purposes; Identification of persons
  • A61B5/06—Devices, other than using radiation, for detecting or locating foreign bodies ; Determining position of diagnostic devices within or on the body of the patient
  • A61B5/065—Determining position of the probe employing exclusively positioning means located on or in the probe, e.g. using position sensors arranged on the probe
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B5/00—Measuring for diagnostic purposes; Identification of persons
  • A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
  • A61B5/6846—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be brought in contact with an internal body part, i.e. invasive
  • A61B5/6847—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be brought in contact with an internal body part, i.e. invasive mounted on an invasive device
  • A61B5/6852—Catheters
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B5/00—Measuring for diagnostic purposes; Identification of persons
  • A61B5/72—Signal processing specially adapted for physiological signals or for diagnostic purposes
  • A61B5/7221—Determining signal validity, reliability or quality
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M25/00—Catheters; Hollow probes
  • A61M25/01—Introducing, guiding, advancing, emplacing or holding catheters
• • 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
• • 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
• • 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
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • 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
  • G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
• • 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
  • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
  • G03F7/2024—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure of the already developed image
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F17/00—Digital computing or data processing equipment or methods, specially adapted for specific functions
  • G06F17/10—Complex mathematical operations
  • G06F17/18—Complex mathematical operations for evaluating statistical data, e.g. average values, frequency distributions, probability functions, regression analysis
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B2505/00—Evaluating, monitoring or diagnosing in the context of a particular type of medical care
  • A61B2505/03—Intensive care
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
  • A61B2505/00—Evaluating, monitoring or diagnosing in the context of a particular type of medical care
  • A61B2505/05—Surgical care
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M25/00—Catheters; Hollow probes
  • A61M25/01—Introducing, guiding, advancing, emplacing or holding catheters
  • A61M25/0105—Steering means as part of the catheter or advancing means; Markers for positioning
  • A61M2025/0166—Sensors, electrodes or the like for guiding the catheter to a target zone, e.g. image guided or magnetically guided
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M2205/00—General characteristics of the apparatus
  • A61M2205/13—General characteristics of the apparatus with means for the detection of operative contact with patient, e.g. lip sensor
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M2205/00—General characteristics of the apparatus
  • A61M2205/18—General characteristics of the apparatus with alarm
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M2205/00—General characteristics of the apparatus
  • A61M2205/50—General characteristics of the apparatus with microprocessors or computers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M2210/00—Anatomical parts of the body
  • A61M2210/12—Blood circulatory system
  • A61M2210/125—Heart
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M2230/00—Measuring parameters of the user
  • A61M2230/005—Parameter used as control input for the apparatus
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M2230/00—Measuring parameters of the user
  • A61M2230/04—Heartbeat characteristics, e.g. ECG, blood pressure modulation
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates to novel methanofullerene derivatives, negative-type photoresist compositions prepared therefrom and methods of using mem.
• the invention further relates to 2-step resist processes which allow for improvements in contrast, resolution and/or line edge roughness.
• the invention also relates to dual resist processes including fullerenes and/or chemically amplified materials.
• the derivatives, their photoresist compositions and/or the methods are ideal for fine pattern processing using, for example, ultraviolet radiation, extreme ultraviolet radiation, beyond extreme ultraviolet radiation, X-rays and charged particle rays.
• the manufacturing process of various kinds of electronic or semiconductor devices involves a fine patterning of a resist layer on the surface of a substrate material such as a semiconductor silicon wafer.
• This fine patterning process has traditionally been conducted by the photolithographic method in which the substrate surface is uniformly coated with a positive or negative tone photoresist composition to form a thin layer of the photoresist composition and selectively irradiating with actinic rays (such as ultraviolet light) through a photomask followed by a development treatment to selectively dissolve away the photoresist layer in the areas exposed or unexposed, respectively, to the actinic rays leaving a patterned resist layer on the substrate surface.
• actinic rays such as ultraviolet light
• the thus obtained patterned resist layer is utilized as a mask in the subsequent treatment on the substrate surface such as etching.
• the fabrication of structures with dimensions of the order of nanometers is an area of considerable interest since it enables the realization of electronic and optical devices which exploit novel phenomena such as quantum confinement effects and also allows greater component packing density.
• the resist layer is required to have an ever increasing fineness which can by accomplished only by using actinic rays having a shorter wavelength man the conventional ultraviolet light. Accordingly, it is now the case that, in place of the conventional ultraviolet light, electron beams (e-beams), excimer laser beams, EUV, BEUV and X-rays are used as the short wavelength actinic rays.
• the minimum size obtainable is primarily determined by the performance of the resist material and the wavelength of the actinic rays.
• Various materials have been proposed as suitable resist materials.
• a chemically amplified resist material is generally a multi- component formulation in which there is a main polymeric component, such as a novolac resin which contributes towards properties such as resistance of the material to etching and its mechanical stability and one or more additional components which impart desired properties to the resist and a sensitizer.
• the chemical amplification occurs through a catalytic process involving the sensitizer which results in a single irradiation event causing exposure of multiple resist molecules.
• the resist comprises a polymer and a photoacid generator (PAG) as sensitizer. The PAG releases a proton in the presence of radiation (light or e-beam).
• This proton then reacts with the polymer to cause it to lose a functional group.
• a second proton is generated which can then react with a further molecule.
• the speed of the reaction can be controlled, for example, by heating the resist film to drive the reaction. After heating, the reacted polymer molecules are free to react with remaining components of the
• polymeric resist material may be self cross-linking or a cross linking molecule may be included.
• Chemical amplification of polymeric-based resists is disclosed in U.S. Pat. Nos. 5,968,712, 5,529,885, 5,981,139 and 6,607,870.
• Figure 1 shows an SEM showing the resolution obtained from example 1.
• Figure 2 shows an SEM showing the resolution obtained from example 2.
• Figure 3 shows an SEM showing the resolution obtained from example 3.
• Figure 4 shows an SEM showing the resolution obtained from example 4.
• Figure 5 shows an SEM showing the resolution obtained from example 5.
• Figure 6 shows an SEM showing the resolution obtained from example 6.
• Figure 7 shows an SEM showing the resolution obtained from example 7.
• Figure 8 shows an SEM showing the resolution obtained from example 8.
• Figure 9 shows an SEM showing the resolution obtained from example 9.
• Figure 10 shows an SEM showing the resolution obtained from example 10.
• a methanofullerene comprising the general formula:
• C2x represents a fullerene with x at least 10, y is 1 - 6, n is 0 - 1, alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1 - 16 carbons with or without one or more heteroatoms substituted into the chain, aryl is a substituted or unsubstituted divalent phenyl group, heteroaromatic group, or fused aromatic or fused heteroaromatic group, and R is H or an acid labile group.
• An example of a disclosed methanofullerene comprises the general formula:
• the methanofullerene of the above embodiment includes divalent alkyl groups comprising a substituted or unsubstituted methylene, ethylene or 1,3-propylene group, and the divalent aryl group comprises a substituted or unsubstituted phenylene group.
• the methanofuHerene of all the above embodiments includes R as either H or an acid labile alkoxycarbonyl group.
• the methanofullerene of the above embodiments includes divalent alkyl group wherein the heteroatoms are one or more of oxygen, nitrogen, sulfur, or oxides of sulfur and/or the alkyl chains may be substituted with fluorine atoms.
• a negative-tone photoresist composition comprising at least one of any of the methanofullerenes of the above embodiments, at least one photo acid generator, at least one crosslinker, and at least one solvent, wherein the crosslinker crosslinks at least with the methanofullerene when processed.
• the negative-tone photoresist composition of the above embodiments wherein the at least one photoacid generator comprises an onium salt compound, a sulfone imide compound, a halogen-containing compound, a sulfone compound, a sulfonate ester compound, a quinone-diazide compound, or a diazomethane compound.
• the at least one photoacid generator comprises an onium salt compound, a sulfone imide compound, a halogen-containing compound, a sulfone compound, a sulfonate ester compound, a quinone-diazide compound, or a diazomethane compound.
• the negative-tone photoresist composition of any of the above embodiments is disclosed wherein the at least one crosslinker comprises an acid sensitive monomer or polymer.
• the negative-tone photoresist composition of any of the above embodiments wherein at least one methanofullerene comprising the general formula is also included:
• x is at least 10
• y is 1 - 6
• a is 1 - 10
• R is H or an acid labile group and the - CH2-CH2 - group may be substituted with fluorine atoms.
• An example of a disclosed methanofullerene comprises the general formula:
• the above methanofullerenes contain only partially blocked hydroxy groups.
• the R groups of the above structures are different and one of the R groups in the molecule is an H while the other R group in the molecule is an acid labile group, as described above. To obtain these molecules, the acid labile group is only partially hydrolyzed.
• the amount of H groups in these hybrid methanofullerenes ranges between about 1% and about 90%.
• a process for using any of the above mentioned negative-tone compositions including the steps of obtaining a substrate, applying any one of the photoresist compositions of the above embodiments to a desired wet thickness, optionally heating the coated substrate to remove a majority of the solvent to obtain a desired thickness, imagewise exposing the coating to actinic radiation, removing the unexposed areas of the coating, and optionally heating the remaining coating.
• the process of the above embodiment including a further step of either heating the imagewise exposed coating prior to removing the unexposed areas of the coating or exposing the coating to infrared exposure.
• the process of the above embodiment is disclosed wherein the unexposed areas are removed by treating with an organic solvent
• the process of the above embodiment is disclosed wherein the actinic radiation is ultraviolet, extreme ultraviolet, beyond extreme ultraviolet, charged particle beam or electron beam.
• the fullerene may be substituted with more than one type of methanofullerene.
• negative working photosensitive compositions which contain crosslinkable materials which are protected by acid labile protecting groups.
• compositions and method for two-step photoresist processes using negative working photosensitive compositions that contain crosslinkable materials which are protected by acid labile protecting groups.
• crosslinkable materials include monomers, oligomers and polymers, wherein acid generated from the acid generator removes the acid-labile group from the polymer, oligomer or monomer in a first step, followed by crosslinking the crosslinkable polymer, oligomer or monomer alone or with additional crosslinking systems included in the composition in a second step.
• compositions and methods for two-step photoresist processes where acid generated from the acid generator removes the acid-labile group from the polymer, oligomer or monomer, and protected fullerene, if present, in a first step, followed by crosslinking with itself or a deprotected polymer, oligomer or monomer, if present, and with additional crosslinking systems, if present, in the composition in a second step.
• in another embodiment is a dual photoresist process using the above compositions wherein the resist is exposed and the exposed areas are removed using a suitable developer. The remaining material is again exposed and heated and the unexposed areas are removed using a suitable developer.
• the alkyl group can be a branched or unbranched divalent alky] chain of 1 - 16 carbons with or without heteroatoms substituted into the chain, such as, for example, - CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, butylene isomers, and the higher analogs up to and including hexadecylene, as well as their isomers.
• branched alkyl groups mat contain heteroatoms in the ring, such as, for example -(CH 2 CH2NR")v- wherein R" can be a branched or unbranched divalent alkyl chain of 1 - 16 carbons with or without heteroatoms substituted into the R" chain.
• Aryl is a substituted or unsubstituted divalent aromatic group, such aromatic groups include, for example the phenylenes ( -C6H4-), the fused divalent aromatic group, such as, for example, the naphthylenes (-C 10 H 6 -) , the anthacenylenes (-C 14 H 8 -) and the like, as well as the heteroaromatic groups, such as, for example, the nitrogen
• heterocycles pyridines, quinolines, pyrroles, indoles, pyrazoles, the triazines, and other nitrogen-containing aromatic heterocycles well known in the arts, as well as the oxygen heterocycles: furans, oxazoles and oilier oxygen-containing aromatic heterocycles, as well the sulfur containing aromatic heterocycles, such as, for example, thiophenes.
• R may be H or D or an acid labile group, including, for example, substituted methyl groups, 1-substituted ethyl groups, 1-substituted alkyl groups, silyl groups, germyl groups, alkoxycarbonyl group, acyl groups and cyclic acid-dissociable groups.
• the substituted methyl groups include, for example, the methoxymethyl group, methylthiomethyl group, ethoxy methyl group, ethylthiomethyl group, methoxyethoxy methyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl group, methylthiophenacyl group, a- methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenyl methyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxy benzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxy carbonylmethyl group, N-propoxy
• the 1-substituted ethyl groups include, for example. 1-methoxyethyl group, 1 -methyl thioethyl group, 1,1-dimethoxyethyl group, 1- ethoxy ethyl group, 1-ethylthioethyl group, 1,1-diethoxy ethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1- benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1 -diphenyl ethyl group, 1-methoxycarbonylethyl group, 1 -ethoxy carbonylethyl group, 1 -N-propoxy carbon
• the 1-substituted alkyl group include the isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group and 1,1-dimethylbutyl group.
• the silyl acid labile groups include, for example, the trimethyl silyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group,
• the germyl groups include, for example, the trimethyl germyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, isopropyldimethylgermyl group, methyldiisopropylgermyl group, triisopropylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenyl germyl group and triphenylgermyl group.
• the alkoxycarbonyl acid labile groups include the raethoxycarbonyl group, ethoxy carbonyl group, isopropoxy carbonyl group and t-butoxycarbonyl group.
• the acyl acid labile groups include, for example, the acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oxaryl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoyl group, sebacoyl group, acrylyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fura
• Cyclic acid groups include, for example, the cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexanyl group, 4-methoxycyclohexyl group,
• memanofullerene contains a benzyl alcohol which will crosslink with the crosslinking systems when processed. Additionally, in a further embodiment, when the benzyl alcohol is protected with the acid labile groups of the current disclosure, a reactive benzyl alcohol will be obtained when deprotected and, as above, will crosslink with the crosslinking systems when processed.
• the fullerenes may also be substituted with other groups that introduce certain desired characteristics to the fullerene such as, for example, solubility in certain solvents or compatibility with certain components of the formulation.
• the fullerenes can be prepared by any of a number of methods, such as, for example, the procedure as shown in the examples below.
• the photo acid generators (PAGs) suitable for the negative-tone photoresist of the current disclosure include onium salt compounds, sulfone imide compounds, halogen- containing compounds, sulfone compounds, ester sulfonate compounds, quinone diazide compounds, and diazomethane compounds. Specific examples of these acid generators are indicated below.
• onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts and pyridinium salts.
• Specific examples of onium salt compounds include diphenyl(4-phenylthiophenyl)sulphonium hexafluoroantimonate, 4,4'-bis[diphenylsulfoniolphenylsulphide bis hexafluoroantimonate and combinations there of, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulf onium
• triphenylsulfonium pyrenesulfonate triphenylsulfonium dodecylbenzenesulfonate
• triphenylsulfonium p-toluene sulfonate triphenylsulfonium benzenesulfonate
• triphenylsulfonium 10-camphor-sulfonate triphenylsulfonium octanesulfonate
• triphenylsulfonium 2-trifluoromethyl benzenesulfonate triphenylsulfonium
• benzenesulfonate tri(4-hydiOxyphenyl)sulfoniuml0-camphor-sulfonate, tri(4- hydroxyphenyl)sulfonium octanesulfonate, tri(4-hydroxyphenyl)sulfonium 2- trifluoromemylbenzenesulfonate, tri(4-hydroxyphenyl)sulfonium hexafluoroantimonate, tri(4-hydroxyphenyl)sulfonium napthalenesulfonate, diphenyliodonium
• diphenyliodonium pyrenesulfonate diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium p-toluene sulfonate, diphenyliodonium benzenesulfonate,
• dodecylbenzenesulfonate bis(4-t-butylphenyl)iodonium p-toluene sulfonate, bis(4-t- buty]phenyl)iodonium benzenesulfonate, bis(4-t-butylphenyl)iodonium 10-camphor- sulfonate, bis(4-t-butylphenyl)iodonium octanesulfonate, bis(4-t-butylphenyl)iodonium 2-trifluoromeAylbenzenesulfonate, 4-hydroxy- 1-naphthyl tetrahydrothiophenium trifluoromethanesulfonate and 4,7-dihydroxy-l-naphthyl tetrahydrothiophenium trffluoromethanesulfonate.
• a sulfone imide compound examples include N- (trifluoromemylsulfonyloxy)succmimide, N-(trifluoromemylsulfonyloxy)phmalimide, N- (Mfluoromemylsulfonyloxy)diphenylmaleimide, N-
• halogen-containing compounds include, for example, haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of halogen-containing compounds include
• (poly)trichloromethyl-s-triadine derivatives such as phenyl-bis(trichloromethyl)-s- triadine, 4-memoxyphenyl-bis(trichloromemyl)-s-triadine and 1-naphthyl- bis(trichlorometibyl)-s-triadine, and 1 , l-bis(4-chlorophenyl)-2,2,2-trichloiOethane.
• sulfone compounds include, for example, ⁇ -ketosulfone and ⁇ - sulfonylsulfone, and the a-diazo compounds thereof.
• Specific examples of the sulfone compounds include phenacyl phenylsulfone, mesitylphenacyl sulfone,
• sulfonate ester compounds include alkylsulfonate esters, haloalkyl sulfonate esters, aryl sulfonate esters sand imino sulfonates.
• Specific examples of sulfonate ester compounds include benzoin tosylate, pyrogallol
• quinine diazide compounds include compounds containing a 1,2- quinone diazide sulfonyl group such as the 1,2-benzoquinone diazide-4-sulfonyl group, 1,2-naphthoquinone diazide-4-sulfonyl group, 1,2-naphtho quinine diazide-5-sulfonyl group and 1,2-naphthoquinone diazide-6-sulfonyl group.
• quinone diazide compounds include 1,2-quinone diazidesulfonate esters of (poly)
• hydroxyphenylaryl ketones such as 2,3,4-trihydroxybenzophenone, 2,4,6- trihydroxybenzophenone, 2,3,4,4' -tetrahydroxybenzophenone, 2,2' ,3,4- tetrahydroxybenzophenone, 3 ' -methoxy-2,3 ,4,4' -tetrahydroxybenzophenone, 2,2' ,4,4' - tetrahydroxybenzophenone, 2,2'3,4,4'-pentahydroxybenzophenone, 2,2'3,4,6'- pentahydroxybenzophenone, 2,3 ,3 ' 4,4' ,5 ' -hexahydroxybenzophenone, 2,3 ' 4,4' ,5 ' ,6- hexahydroxybenzophenone; 1,2-quinone diazide sulfonate esters of bis [ (poly) hydroxyphenyl]alkanes such as bis(4-hydroxyphenyl) methane, bis(2,4-d
• diazomethane compounds include
• compositions of the current disclosure may contain one or more of the above mentioned photoacid generators.
• Crosslinking systems suitable for the current disclosure constitute compounds able to crosslink with the methanofullerene during the process such mat when the methanofullerene is substituted with a phenol or similar group, such as, for example, an alkyl -OH group, or when the methanofullerene is deprotected to provide for a phenol or similar group, the crosslinking system will react with the -OH group situated on the phenol or similar group.
• the acid mat is generated by exposure to the actinic radiation not only reacts with the acid-labile group of the methanofullerene but aids in the reaction of the crosslinking system with itself and with the methanofullerene.
• crosslinking systems include compounds comprising at least one type of substituted group that possess a crosslinking reactivity with the phenol or similar group of the methanofullerene.
• mis crosslinking systems include the glycidyl ether group, glycidyl ester group, glycidyl amino group, methoxymethyl group, ethoxy methyl group, benzyloxymethyl group, dimemylamino methyl group, diemylamino methyl group, dimethylol amino methyl group, diethylol amino methyl group, morpholino methyl group, acetoxymethyl group, benzyloxy methyl group, formyl group, acetyl group, vinyl group and isopropenyl group.
• crosslinking systems having the aforementioned crosslinking substituted group include, for example, bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compound, resol resin-based epoxy compounds, poly (hydroxystyrene)-based epoxy compounds, methylol group-containing melamine compounds, methylol group- containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing phenol compounds, carboxymethyl group-containing melamine resins, carboxy methyl group-containing benzoguanamine resins, carboxymethyl group-containing urea resins, carboxymethyl group-containing phenol resins, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguan
• methoxymethyl group-containing glycol-uril compounds methoxymethyl group-containing glycol-uril compounds, methoxymethyl group- containing urea compounds and acetoxymethyl group-containing phenol compounds .
• the methoxymethyl group-containing melamine compounds are commercially available as, for example, CYMEL300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui Cyanamid)
• the methoxymethyl group-containing glycol-uril compounds are commercially available as, for example, CYMEL117 4 (manufactured by Mitsui Cyanamid)
• the methoxymethyl group-containing urea compounds are commercially available as, for example, MX290 (manufactured by Sanwa Chemicals).
• suitable solvents for the current disclosure include ethers, esters, etheresters, ketones and ketoneesters and, more specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetate esters, hydroxyacetate esters, lactate esters, ethylene glycol monoalkylether acetates, propylene glycol monoalkylether acetates, alkoxyacetate esters, (non-)cyclic ketones, acetoacetate esters, pyruvate esters and propionate esters.
• solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyletheracetate, propylene glycol
• the aforementioned solvents may be used independently or as a mixture of two or more types.
• at least one type of high boiling point solvent such as benzylethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isoholon, caproic acid, capric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate and phenylcellosolve acetate may be added to the aforementioned solvent.
• additives may be added to the photoresist formulations to provide certain desirable characteristic of the photoresist such as, for example, acid diffusion control agents to retard acid from migrating into unexposed areas of the coating, surfactants to improve coating of substrates, adhesion promoters to improve adhesion of the coating to the substrate and sensitizers to improve the photosensitivity of the photoresist coating during photoexposure, and antifoaming agents and air release agents, as well as other materials well know in the coatings industry.
• acid diffusion control agents to retard acid from migrating into unexposed areas of the coating
• surfactants to improve coating of substrates
• adhesion promoters to improve adhesion of the coating to the substrate
• sensitizers to improve the photosensitivity of the photoresist coating during photoexposure
• antifoaming agents and air release agents as well as other materials well know in the coatings industry.
• methanofullerenes include:
• R can include a carboxylic acid derivative which together with the -(CH2CH2-0) a provides for a carboxylic ester structure.
• the - (CH2CH2-O) group may be substituted with fluorine atoms.
• A can be from about 1 to about 10.
• compositions of the current disclosure are included in ranges as follows based on weight/weight: methanofullerenes from about 1% to about 65%, crosslinking systems from about 10% to about 80%, photoacid generator from about 0.5% to about 50%.
• the percent solids of the composition may range from about 0.001% - about 25%.
• the above methanofullerenes contain only partially blocked hydroxy groups.
• the R groups of the above structures are different and one of the R groups in the molecule is an H while the other R group in the molecule is an acid labile group, as described above. To obtain these molecules, the acid labile group is only partially hydrolyzed.
• the amount of H groups in these hybrid methanofullerenes ranges between about 1% and about 90%.
• the photoresist compositions can be coated onto substrate such as a silicon wafer or a wafer coated with silicon dioxide, aluminium, aluminum oxide, copper, nickel, any of a number of semiconductor materials or nitrides or other substrates well known the semiconductor industry, or a substrate having thereon an organic film, such as, for example, a bottom layer anti-reflective film or the like.
• the photoresist compositions are applied by such processes as spin coating, curtain coating, slot coating, dip coating, roller coating, blade coating and the like. After coating, the solvent is removed to a level wherein the coating can be properly exposed. In some cases a residual of 5% solvent may remain in the coating while in other cases less than 1% is required.
• UV ultraviolet rays
• EUV extreme ultraviolet
• BEUV extreme ultraviolet
• X-ray synchrotron radiation
• Ion beam lithography and charged particle rays such as electron beams may also be used.
• the exposed coated substrate may optionally be post exposure baked to enhance the reaction of the photoacid generator, such as, for example, heating from about 30 to about 200°C for about 10 to about 600 seconds. This may be accomplished by hot plate heating, convection heating, infrared heating and the like.
• the heating may also be performed by a laser heating processes such as, for example, a CO2 laser pulse heating for about 2 to about 5 milliseconds. Both heating processes may be combined in tandem.
• a flood exposure process may be applied after the pattern exposure to aid in further cure. Results have indicated that flood exposure reduces or eliminates pattern collapse after development of the negative-tone resists as well as reduction in line edge roughness. For example, a 532 nm continuous wave laser exposes the previously exposed resist for 1 - 2 sec followed by wet development. The flood process may or may not be followed by a heating step.
• the unexposed areas are next moved using a developer.
• developers include organic solvents as well as aqueous solution such as aqueous alkali solution.
• aqueous solution such as aqueous alkali solution.
• aqueous alkali development solution examples include, for example, at least one type of alkaline compound such alkali metal hydroxides, ammonia water, alkylamines, alkanolamines, heterocyclicamines, tetraalkyl ammonium hydroxides, cholines, andl ,8- diazabicyclo[5.4.0]-7-undecan,l,5-diazabicyclo[4.3.0]-5-nonene at a concentration of about 1 to about 10 % by weight, such as, for example, about 2 to about 5 % by weight.
• Water-soluble organic solvents such as methanol and ethanol and surfactants may also be added in suitable amounts to the alkaline aqueous solution, depending on the desired development characteristics and process parameters.
• the heating process may be, for example, from about 30 to about 600°C for about 10 to about 120 seconds and may be accomplished by hot plate heating, convection heating, infrared heating and the like.
• Negative working photosensitive compositions of the current disclosure contain crosslinkable material which are protected by acid labile protecting groups.
• crosslinkable materials include monomer, oligomer and polymers.
• polymers include, for example, phenolic resins, cresol-formaldehyde resins, carboxylic acid containing resins, and hydroxy group containing resins. The reactive portions of these resins are protected by the acid labile protecting groups mat are listed above.
• the compositions contain photoacid generators, as listed above, the protected crosslinkable materials and other materials, such as crosslinking systems, which crosslink with the crosslinkable materials when the reactive portions of the crosslinkable materials are deprotected.
• compositions which are generally present in photosensitive coatings, such as, for example, wetting agents, leveling agents, colorants, photosensitizing agents, and the like.
• photosensitive coatings such as, for example, wetting agents, leveling agents, colorants, photosensitizing agents, and the like.
• the components of the composition are admixed in a solvent and coated onto a substrate and dried to a suitable dryness.
• the coating is exposed to actinic radiation to convert a portion of the photoacid generator to acid and the acid reacts to deprotect the protected crosslinkable materials.
• the crosslinkable materials by themselves or with the aid of the photogenerated acid, crosslinks with itself or crosslinking systems, if present in the composition.
• the unexposed areas can now be removed with a developer leaving behind an image.
• poly(4-tert-butoxycarbonyloxystyrene) is a polymer protected by an acid-labile group, such as those described above, which becomes a material capable of crosslinking when acid from an acid generator is generated, either by photolytic or thermal means, and the polymer is deprotected to give poly(4- hydroxystyrene) PHOST.
• Oilier crosslinking systems such as those mentioned above, for example, hexamethoxymethylmelamine (HMMM) crosslinker systems, poly[(o-cresyl glycidyl ether)-co-formaldehyde] and the like, may be included which can then crosslink with the deprotected polymers, oligomers or monomers, such as the PHOST already mentioned.
• HMMM hexamethoxymethylmelamine
• poly[(o-cresyl glycidyl ether)-co-formaldehyde] and the like may be included which can then crosslink with the deprotected polymers, oligomers or monomers, such as the PHOST already mentioned.
• the acid is generated, deprotects the protected polymer, either at ambient temperature or with a thermal assistance step, the now deprotected polymer either crosslinks with itself or with an included crosslinking system, again at ambient temperature or with a thermal assist step.
• the acid mat is generated may also assist the crosslinking of the deprotected polymer, oligomer and/or monomer with the crosslinking system.
• the area in which no acid has been purposely generated thus contains little or no crosslinked materials and can be dissolved away with an appropriate developer such as those described above.
• This photoresist process can be termed a "2-step"; the first step being removal of the protecting group by acid which has been generated, and the second step being crosslinking of the deprotected polymer with itself and/or with an included crosslinking system to give a composition mat is substantially resistant to a developer material. While not being held to theory, it is believed that the crosslinking systems may start to crosslink with themselves once the PAG creates an acid, thus starting the curing process.
• Acid generated in undesirable areas may be captured by the protected materials.
• including acid labile materials in the resist compositions act as “acid scavengers” and aid in preventing undesired, developer resistant materials.
• Typical "acid scavengers” are nitrogen based materials which can reduce the amount of useful acid in the desired exposure regions thus reducing photospeed.
• the current system utilized the unique behaviour of the protected materials to act as acid scavengers; the same materials act as acid scavenging as it does for photocuring.
• the acid scavenging mechanism is a non-competing reaction.
• a coated and dried resist composition of the current disclosure is pattern- wise exposed to actinic radiation, such as UV, DUV, EUV, e-Beam and the like.
• actinic radiation such as UV, DUV, EUV, e-Beam and the like.
• the acid which is generated deprotects the material protected by an acid-labile group which men can become soluble in a developer.
• the acid-labile group protects a phenolic material, such as PHOST
• the deprotected material can be soluble in aqueous base developers, either alone or with additional ingredients, such as, for example, surfactants, emulsifying materials or a solvent added to aid in development.
• additional ingredients such as, for example, surfactants, emulsifying materials or a solvent added to aid in development.
• the resulting image, or pattern, which has not been exposed may now be again pattern- wise exposed to actinic radiation such as, for example, UV, DUV, EUV, e-Beam and the like.
• actinic radiation such as, for example, UV, DUV, EUV, e-Beam and the like.
• the image or pattern is now heated to cause crosslinking.
• the unexposed areas are now removed with a suitable developer to leave behind an image.
• the areas mat were not exposed to actinic radiation are removed resulting in a negative image.
• Methanofullerene I [3-(4-/-butoxycarbonyi)phenyl-l -propyl malonate]-methano- [60]fullerene.
• Methanofullerene ⁇ (3-phenoI-l -propyl malonate)-methano-[60]fullerene.
• PGME propylene glycol monomethyl ether
• methanofullerene 1 Into 100 mL of propylene glycol monomethyl ether (PGME) was added 0.25 g of methanofullerene 1 , 0.50 g of poly[(o-cresyl glycidyl ether)-co-formaldehyde] and 0.25 g of triphenylsulfonium hexafluoroantimonate and stirred for 1 hr at room temperature.
• the composition was applied to a silicon wafer and spin coated at 500 rpm for 5 sec followed by 2000 rpm for 60 sec. The coated wafer was men heated on a hot plate at 75° C for 5 min to give a film of approximately 25 nm.
• Example 1 was repeated but 150 mL of PGME was used to reduce the solids content.
• the resulting film thickness was 18 nm and the exposure was 21.2 mJ/cm 2 .
• Figure 2 shows the resulting 18 nm lines and spaces for example 2.
• Example 1 was repeated using methanofullerene II in place of methanofullerene I. A 48 mJ/cm 2 exposure dosage was used. Figure 3 shows the resulting 25 nm lines and spaces forr example 3.
• Example 1 was repeated using an E-beam exposure in place of 13 - 14 nm exposure.
• Area dose testing established a sensitivity of 90 ⁇ C/cm2 . at 30 keV.
• For high resolution patterning a line dose of 575 pC/cm was applied at a nominal half-pitch of 50 nm, given lines of ⁇ 20 nm with ⁇ 30 nm spaces.
• Figure 4 shows the resulting lines and spaces for example 4.
• Example 3 was repeated using an E-beam exposure of 90 ⁇ C/cm2 at 30 keV in place of 13 - 14 nm exposure.
• a line dose of 575 pC/cm was applied at a nominal half-pitch of 50 nm, given lines of ⁇ 20 nm with ⁇ 30 nm spaces
• Figure 5 shows the resulting lines and spaces for the example 5.
• Example 6 The formulation of Example 1 was repeated using 0.125 g of methanofullerene I and 0.125 g of a memanofullerene having tetraethylene glycol esters capped with acetic acid to provide acetate esters.
• the composition was applied to a silicon wafer and spin coated at 500 rpm for 5 sec followed by 2000 rpm for 60 sec.
• the coated wafer was men heated on a hot plate at 75° C for 5 min to give a film of approximately 25 nm.
• the wafer was imagewise exposed to 40 ⁇ C/cm2 of E-beam radiation and post exposure baked at 90° C for 3 min.
• PGME propylene glycol monomethyl ether
• the wafer was imagewise exposed to 30keV E-beam and post exposure baked at 90° C for 2 min.
• the unexposed areas were removed by puddle development in a 50:50 blend of monochlorobenzene and isopropyl alcohol for 20 sec followed by an isopropyl alcohol rinse.
• a line dose of 118 pC/cm was applied, given an isolated line of ⁇ 20 nm.
• Figure 7 shows the resulting line for example 7.
• Example 7 was repeated using 0.5% polyhydroxystyrene which was 95.5% protected with t-BOC in place of the polyhydroxystyrene.
• a line dose of 118 pC/cm was applied, giving an isolated line of ⁇ 22 nm.
• Figure 8 shows the resulting line for example 8.
• Composition Example 9 :
• Example 9 was repeated using 0.25% polyhydroxystyrene which was 95.5% protected with t-BOC in place of the polyhydroxystyrene.
• a line dose of 117 pC/cm was applied at a nominal half -pitch of 25 nm, giving lines of ⁇ 20 nm with ⁇ 30 nm spaces.
• Figure 10 shows the resulting lines and spaces for the example 10.
• triphenylsulfonium hexafluoroantimonate and stirred for 1 hr at room temperature.
• the composition was applied to a silicon wafer and spin coated at 4000 rpm for 1 min and heated on a hot plate at 75° C for 5 min to give a film of approximately 25-30 nm.
• the wafer was imagewise exposed using a 20keV E-beam and post exposure baked at 160° C for 2 min. The unexposed areas were removed by puddle development in a 50:50 blend of monochlorobenzene and isopropyl alcohol for 20 sec followed by an isopropyl alcohol rinse.
• a line dose of 9.6 ⁇ C/cm2 was applied at a nominal half-pitch of 30 nm, given lines of 15.9 nm.
• Example 11 was repeated using an EUV exposure of 13.5 nm wavelength.
• the samples were post exposure heated at 90°C for 3 min followed by development as in example 11.
• Exposure doses of sub- 10 mJ/cm 2 provided for pitch resolution of 44 and 36 nm with excellent line quality.
• hexafluoroantimonate and stirred for 1 hr at room temperature.
• the composition was applied to a silicon wafer and spin coated at 4000 rpm for 1 min and heated on a hot plate at 75° C for 5 min to give a film of approximately 30 nm.
• the wafer was imagewise exposed to 30keV E-beam and post exposure baked at 140° C for 2 min.
• the unexposed areas were removed by puddle development in a 50:50 blend of monochlorobenzene and isopropyl alcohol for 20 sec followed by an isopropyl alcohol rinse.
• a line dose of 7.8pC/cm was applied at a nominal half-pitch of 25 nm, given lines of ⁇ 20 nm with ⁇ 30 nm spaces.

Landscapes

• Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Surgery (AREA)
• Public Health (AREA)
• Biomedical Technology (AREA)
• Heart & Thoracic Surgery (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Veterinary Medicine (AREA)
• Medical Informatics (AREA)
• Molecular Biology (AREA)
• Biophysics (AREA)
• Pathology (AREA)
• Data Mining & Analysis (AREA)
• Signal Processing (AREA)
• Mathematical Analysis (AREA)
• Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
• Psychiatry (AREA)
• Computational Mathematics (AREA)
• Theoretical Computer Science (AREA)
• Human Computer Interaction (AREA)
• Robotics (AREA)
• Mathematical Optimization (AREA)
• Physiology (AREA)
• Computer Vision & Pattern Recognition (AREA)
• Pure & Applied Mathematics (AREA)
• Artificial Intelligence (AREA)
• Mathematical Physics (AREA)
• Evolutionary Biology (AREA)
• Operations Research (AREA)
• General Engineering & Computer Science (AREA)
• Databases & Information Systems (AREA)
• Pulmonology (AREA)
• Anesthesiology (AREA)
• Hematology (AREA)
• Algebra (AREA)

Priority Applications (3)

Applications Claiming Priority (3)

Publications (2)

Family

ID=60201754

Family Applications (1)

Country Status (5)

Families Citing this family (7)

Family Cites Families (11)

• 2014
  • 2014-10-16 US US14/516,472 patent/US9383646B2/en active Active
• 2015
  • 2015-12-15 CN CN201580002527.0A patent/CN107087426A/zh active Pending
  • 2015-12-15 JP JP2016534124A patent/JP2017534070A/ja active Pending
  • 2015-12-15 KR KR1020167015368A patent/KR20170118587A/ko not_active Withdrawn
  • 2015-12-15 WO PCT/US2015/065691 patent/WO2016086236A2/en not_active Ceased

Also Published As

Similar Documents

Legal Events