WO1989007787A1 - Procede de preparation d'un substrat comportant des motifs - Google Patents

Procede de preparation d'un substrat comportant des motifs Download PDF

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Publication number
WO1989007787A1
WO1989007787A1 PCT/JP1989/000152 JP8900152W WO8907787A1 WO 1989007787 A1 WO1989007787 A1 WO 1989007787A1 JP 8900152 W JP8900152 W JP 8900152W WO 8907787 A1 WO8907787 A1 WO 8907787A1
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WO
WIPO (PCT)
Prior art keywords
vinyl
resist layer
substrate
molecular weight
mask
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1989/000152
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English (en)
Japanese (ja)
Inventor
Masataka Murahara
Takeshi Shimomura
Tohru Takahashi
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Terumo Corp
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Terumo Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Terumo Corp filed Critical Terumo Corp
Publication of WO1989007787A1 publication Critical patent/WO1989007787A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to a method for manufacturing a substrate on which a pattern is formed. More specifically, the present invention particularly relates to a method for manufacturing a substrate capable of providing a high-resolution pattern having a line width of 1 micron or less.
  • the substrate surface is often covered with a resist material, a mask is placed thereon, and light is irradiated from above. After exposure to light, the masking is removed, and the photosensitive or non-photosensitive portions of the resist material are removed (developed as necessary), and the portions without the resist material are removed.
  • An application of photographic technology called photoetching, in which a substrate is etched with a solvent, is used. In the fabrication of semiconductor devices, similar techniques are used for forming electrode holes, removing insoluble metal deposited after electrode deposition, and forming gates.
  • a mercury lamp xenon lamp such as a high-pressure mercury lamp of 356 nm has been used, and a long exposure of 5 to 10 minutes has been performed.
  • a mercury lamp xenon lamp such as a high-pressure mercury lamp of 356 nm has been used, and a long exposure of 5 to 10 minutes has been performed.
  • the reaction products of the resist material formed by the chemical or physical reaction may not be adequately removed due to the excimer laser irradiation, or ketones, anolecols, toluene, xylene , Benzene
  • a developing solution such as cyclohexane or methyl acetate or a hydrofluoric acid aqueous solution
  • the resist material itself is subject to Ko erosion, making it difficult to control the development, making the process shorter and easier.
  • an object of the present invention is to provide a novel method for manufacturing a substrate on which a pattern is formed.
  • a short wavelength beam of 300 nm or less is irradiated at a dose of 2 J / oi or less through a mask on a substrate having a resist layer formed on the surface. This is achieved by a method of manufacturing the formed substrate.
  • the present invention is also a method of manufacturing a substrate on which a pattern having a thickness of a resist layer ⁇ 1 ° to 1 ⁇ m is formed.
  • Fig. 1 is a graph showing the molecular weight change of the resist due to KrF laser irradiation.
  • Fig. 2 is a graph showing the change in molecular weight due to the difference in the irradiation energy of a single KrF laser.
  • Fig. 3 is a graph showing the development characteristics of the resist layer.
  • Figure 4 shows the results of Fourier transform infrared spectroscopy of the resist layer. It is a graph which shows a result.
  • a substrate on which a pattern according to the present invention is formed is provided with a short-wavelength beam of 30 O nm or less through a mask on a substrate having a resist layer formed on its surface. It is manufactured by irradiating with an irradiation amount of 2 J Zci! Or less, and then developing the resist layer.
  • the resist material used in the present invention needs to have good transmittance and irradiation energy absorption with respect to a short-wave beam of 300 nm or less.
  • viscosity average molecular weight 4. 3 3 X 1 0 5 or more (limiting viscosity ?? is 1 X 1 0 2 or more), the favored properly 1. 08 xl 0 6 ⁇ 5 . 56 X 1 0 7 (intrinsic viscosity of 2 X 1 0 2 ⁇ 4 X 1 0 3) and is Arukirume Tak Li rate copolymer than made things good or arbitrary.
  • the intrinsic viscosity is a value at 30 ° C (in benzene).
  • Alkyl methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec There are alkyl methacrylates having 1 to 4 carbon atoms, such as monobutyl methacrylate and tert-butyl methacrylate, which may be used alone or in combination of two or more. Yes, but preferably contains at least methyl methacrylate, and 3 ⁇ 4 is also preferably methyl methacrylate.
  • a comonomer in the copolymer As a comonomer in the copolymer, another ⁇ , / 3-ethylenic monomer having a color-forming group that shows the absorption peak of the copolymer as a resist material in the ultraviolet wavelength region are mentioned.
  • a photosensitizing effect is caused by a comonomer incorporated in the copolymer-IS union, so that the perceived light absorption characteristics are affected by external factors such as temperature. It is extremely stable without being affected, and shows high etching efficiency.
  • a comonomer having a coloring group showing the absorption beak in the ultraviolet wavelength region there is a vinyl monomer having an aromatic ring or a heteroaromatic ring as the coloring group.
  • a radical polymerization initiator is present in a gaseous phase containing monomer vapor, and plasma is irradiated into the gaseous phase, and the generated polymerization initiation active species are coagulated into monomers.
  • a plasma-initiated polymerization method with a radical polymerization initiator Japanese Patent Application Publication No. 183,303, Showa 61. And it can be prepared in good yield.
  • the polymerization method it is not always necessary to have all kinds of monomers constituting the copolymer present in the gas phase. May be only one kind.
  • alcohol is present in the coagulation phase in which post-polymerization is performed, the polymerization time is shortened and the yield is good (Japanese Patent Application Publication No. 86,0086 / 1987). No. 4)
  • any radical polymerization initiator may be used as long as it is used in general radical polymerization of monomers.
  • Low temperature such as azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylthiophene) and 2,2'-azobis (2,4-dimethylvaleronitrile) Active radical polymerization initiator, and t-butylcumyl peroxide, diisopropylpropylbenzene dropoxide, di-t-butylethyl 3- oxide, p-menthenodidronooxy 2,5-Dimethyl-2,5-di- (t-butyl-butoxy) hexine-3,
  • azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylthiophene) and 2,2'-azobis (2,4-dimethylvaleronitrile) Active radical polymerization initiator, and t-butylcumyl peroxide, diisopropylpropylbenzene dropoxide, di-t-butylethyl 3- oxide, p-menthenodidrono
  • the low-temperature active radical polymerization initiator has a decomposition temperature of not more than 50 ° C for obtaining a half-life of 10 hours, while the high-temperature active radical initiator has a decomposition temperature of 50 ° C or less.
  • Decomposition temperature for obtaining a 10-hour half-life is 60 to 220. It is about C.
  • the amount of the radical polymerization initiator to be added to the monomer depends on the degree of polymerization of the copolymer to be obtained and the types of the monomer and the radical polymerization initiator, and cannot be determined unconditionally. . However, if the radical polymerization initiator is added more than necessary, the radical polymerization initiator does not disappear during the polymerization of the polymer but remains in the resulting copolymer. I don't like it because it would be bad.
  • non-equilibrium plasma particularly low-temperature plasma by glow discharge, is preferable.
  • the electrodes used include an external or internal parallel plate electrode or a coil-shaped electrode, and preferably an external parallel plate electrode.
  • the gas of the plasma generating source may be any gas such as hydrogen, methane, nitrogen, argon, ethylene, or the monomer gas itself.
  • plasma irradiation to the gas phase is performed at a temperature at which monomer vapor can exist in the depressurized gas phase, generally at a temperature around room temperature, and the irradiation time is not particularly limited. However, even a short time is enough to generate polymerization active species, usually about several seconds to several minutes.
  • the post-polymerization in the coagulation phase is carried out at about room temperature, although it depends on the type of radical polymerization initiator used and the like. That is, if the post-polymerization is carried out under extremely high temperature conditions, the reaction proceeds thermopolymerically, and a copolymer having a low degree of polymerization may be generated.
  • the polymerization may not proceed well.
  • a low-temperature active radical polymerization initiator is used as the radical polymerization initiator, the post-polymerization in the coagulation phase is not performed by the conventional brass.
  • the plasma initiated polymerization method the polymerization proceeded sufficiently even in a low temperature range where the progress of the post-polymerization is difficult, for example, 0 to 120 ° C.
  • the degree of polymerization of the polymer obtained in the plasma-initiated polymerization method is adjusted by generating a stoichiometric amount of the polymerization active species when obtaining the polymerization active species by plasma irradiation.
  • alcohols used in the case of being added to the reaction system as described above include methanol, ethanol, ⁇ -propanol, isopropanol, ⁇ -butanol, sec-butanol, and tert-butanol. , N-amyl alcohol, isoamino alcohol, hexanol, peptanol, octanol, propyl alcohol, nonyl alcohol, decyl alcohol, and other alcohols having about 1 to 10 carbon atoms.
  • ⁇ Especially preferred are lower alcohols, especially methanol. These alcohols may or may not be present in the gas phase during plasma irradiation.
  • the copolymer is dissolved in an organic solvent such as methylisobutylketone, acetate, benzene, chloroform, ethyl acetate, and the like, and a resist layer is formed by applying the solution to the surface of the substrate.
  • the dry film thickness of the resist layer is from 100 A to 1 micron, preferably from 400 A to 2,000 A. In other words, if it exceeds 1 micron, it becomes difficult for the laser beam to pass through the resist ⁇ and only the surface of the resist layer This is because high-resolution patterns cannot be obtained, and when it is less than 100 A, the effect of layer coating is reduced due to the unevenness of the substrate.
  • Substrates used include silicon, glass, metal oxides, ceramics, alumina, IrOx, PdOx, etc.
  • a resist layer formed on the substrate is irradiated with a short-wavelength beam of 300 nm or less through a mask.
  • a short-wavelength beam preferably has a short-wavelength region of 300 ⁇ m or less in order to form a polymer pattern after the development processing, and more preferably 150 to 290 ⁇ m.
  • the short wavelength range is preferred.
  • the energy of the short-wavelength beam to be irradiated is preferably 2 J Zei or less, and more preferably 50 to: L, 000 m J C !. That is, if the thickness is less than 50 mJ Zci, it is difficult to obtain a high resolution of the pattern. On the other hand, if it exceeds 2 J, abrasion occurs.
  • Masks include a full-size mask and a reticle mask. Preferably, it is a reticle mask.
  • the beam exposure includes (a) close contact (proxy) exposure, (b) 1: 1 projection exposure, and (c) reduced projection exposure.
  • a full-size mask is used for contact exposure and 1: 1 projection exposure, and a reticle mask is used for reduction projection exposure.
  • reduction projection exposure a mask for one chip with a size larger than the target pattern (usually 5 to 10 times) is used, and the reduction optical system is used to repeatedly reduce the pattern by the number of chips on the wafer. Transcribe. This enlarged mask is called a reticle mask or simply a reticle.
  • the reticle can be mounted on a pattern for several chips.
  • the method of forming a pattern according to the present invention comprises the steps of: (1) irradiating a short-wavelength beam (for example, a KrF excimer laser beam) of 300 nm or less with an energy of 2 J / dl or less, particularly 1 J / cif or less.
  • a short-wavelength beam for example, a KrF excimer laser beam
  • the resist layer can be reduced in molecular weight by an order of 10 3 in terms of number average molecular weight.
  • the laser beam irradiation energy is 1 JZ cif or more, light transmission to the resist layer occurs.
  • the laser beam reaches the vicinity of the boundary between the resist layer and the substrate, and the usefulness as a positive type resist can be exhibited. Since the molecular weight can be reduced to the vicinity, the low molecular weight portion is easily peeled off by laser beam irradiation during postbaking or development processing, and a high-resolution pattern is formed on the substrate.
  • the image processing is a processing for selectively removing products reacted by beam irradiation.
  • the resist layer developing method is to selectively decompose the copolymer present in the exposed portion of the substrate, especially the formed resist layer, by exposing the copolymer to a decomposition reaction or a low-molecular-weight reaction, and then selectively using a developer. This is a method of dissolving and removing, so that a pattern is formed on the unexposed portion.
  • the system was degassed below 1 0_ 3 T orr a feeding oxygen in the well system and redissolved. After repeating this operation three times, the cock was closed and plasma was generated in the gasket when a part of the monomers in the polymerization tube began to be dissolved. Plasma treatment was performed at 50 W for 60 seconds using a high frequency generator at 13.56 MHz.
  • the experiment of molecular weight distribution change at this time was performed by using gel permeation chromatography (manufactured by JASCO Corporation; T1U1-0TAR VI) and using G7000HXL and GMH6 manufactured by Kanekaso Co., Ltd. as columns. The measurement was performed using the attached column apparatus. Table 1 shows the results. FIG. 1 shows the respective molecular weight distribution curves. Since the resist layer is a thin film, the degree of change in molecular weight was determined based on the number average molecular weight.
  • Mn is the viscosity average molecular 3 ⁇ 4 of 1. 1 6 X 1 0 6 is 4. a 57 x 1 0 6.
  • the number-average molecular weight (Mn) is from 116,000 to 89,9, even if the wafer is baked without laser irradiation.
  • the irradiation dose of the KrF excimer laser was changed to 60, 100, 200, and 100 mJ Zcif.
  • the number average molecular weight was 6 . 6 2 X 1 0 5, and 4. 4 9 1 0 5, 1. 5 6 x 1 0 5 and 6. 5 7 x 1 0 3, was significantly lower molecular weight.
  • the total energy of rF laser irradiation is 1 J / cif, and the number of irradiations is 20 (irradiation energy 50 mJ cif), 10 times (irradiation energy 100 m J / ci, 5 times (irradiation energy per one time: 200 m J ZeiD)
  • the change in molecular weight distribution was measured, and the results in Table 2 and FIG. 2 were obtained.
  • a 1% by weight solution of the obtained copolymer in methyl isobutyl ketone was applied to a silicon wafer at 2,000 rpm using Spirco Ichiichi (Mikasa Corporation). After forming a thin film with a thickness of 1, 000 A, pre-baking is performed (at 110 for 30 minutes), and 1 J / cif with KrF excimer laser (249 nm). (5 irradiations; 200 mJ Xcif per irradiation). The time of one irradiation was 10 nanoseconds.
  • FIG. 3 shows the result.
  • Comparative Examples 1 and 2 3 ⁇ 4 swells due to the ⁇ image solution, and the ⁇ thickness changes by 50 to 8 A A.
  • a short-wavelength beam of 300 nm or less is irradiated at a dose of 2 J Zcif or less through a mask, particularly a reticle mask, onto a plate having a resist layer formed on its surface. Therefore, an extremely high resolution can be obtained. Therefore, a pattern with a line width of 1 micron or less can be formed on the substrate, which is extremely useful as a substrate for devices such as IC and LSI.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing Optical Record Carriers (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Procédé de préparation d'un substrat comportant des motifs à haute résolution formés par irradiation d'un substrat recouvert d'une réserve à travers un masque à l'aide d'un faisceau présentant une longueur d'onde inférieure à 300 nm à une concentration inférieure à 2 J/cm2.
PCT/JP1989/000152 1988-02-17 1989-02-15 Procede de preparation d'un substrat comportant des motifs Ceased WO1989007787A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP63/34872 1988-02-17
JP63034872A JPH0772798B2 (ja) 1988-02-17 1988-02-17 基板上のパターン形成方法

Publications (1)

Publication Number Publication Date
WO1989007787A1 true WO1989007787A1 (fr) 1989-08-24

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PCT/JP1989/000152 Ceased WO1989007787A1 (fr) 1988-02-17 1989-02-15 Procede de preparation d'un substrat comportant des motifs

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JP (1) JPH0772798B2 (fr)
AU (1) AU3063589A (fr)
WO (1) WO1989007787A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5734550A (en) * 1980-08-11 1982-02-24 Fujitsu Ltd Formation of pattern
JPS58189627A (ja) * 1982-04-30 1983-11-05 Japan Synthetic Rubber Co Ltd 感光材料
JPS5992532A (ja) * 1982-11-18 1984-05-28 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション ポジテイブ型レジストの製造方法
JPS61209442A (ja) * 1985-03-13 1986-09-17 Matsushita Electronics Corp パタ−ン形成方法
JPS61223837A (ja) * 1985-03-28 1986-10-04 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション リソグラフイ−レジスト

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5734550A (en) * 1980-08-11 1982-02-24 Fujitsu Ltd Formation of pattern
JPS58189627A (ja) * 1982-04-30 1983-11-05 Japan Synthetic Rubber Co Ltd 感光材料
JPS5992532A (ja) * 1982-11-18 1984-05-28 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション ポジテイブ型レジストの製造方法
JPS61209442A (ja) * 1985-03-13 1986-09-17 Matsushita Electronics Corp パタ−ン形成方法
JPS61223837A (ja) * 1985-03-28 1986-10-04 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション リソグラフイ−レジスト

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Semiconductor, Integrated circuit Gijutsu, THE 32ND SYMPOSIUM KOEN RONBUN-SHU, pages 49 to 55, (June 1987), NAKASE MAKOTO et al., (Excimer laser lithography Gijutsu). *

Also Published As

Publication number Publication date
JPH01211255A (ja) 1989-08-24
AU3063589A (en) 1989-09-06
JPH0772798B2 (ja) 1995-08-02

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