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    • 专利摘要:
    The present invention relates to a photosensitive material comprising an alkali-soluble resin portion and a diazo compound portion having at least one of an alicyclic skeleton and a condensed monocyclic skeleton. The diazo compound part may be contained in the side chain of alkali-soluble resin, and may be contained as a component separate from a resin part. According to the present invention, there is provided a photosensitive material which is excellent in environmental stability and has high transparency to short wavelength light such as an ArF excimer laser and an electron beam, and can form a fine resist pattern having high adhesion to a substrate by alkali development. do. In addition, by using the manufacturing method of the electronic component of the present invention using the resist pattern formed by such a method as an etching mask, it is possible to faithfully transfer a very fine pattern to a substrate or the like, and the photosensitive material of the present invention can be finely processed into a high density device. It is useful for photolithography techniques, such as these.
    公开号:KR19980024609A
    申请号:KR1019970047094
    申请日:1997-09-12
    公开日:1998-07-06
    发明作者:다께시 오끼노；고지 아사까와；나오미 시다；도루 우시로고우찌；마꼬또 나까세
    申请人:니시무로 다이조；가부시끼가이샤 도시바；
    IPC主号:
    专利说明:

    Photosensitive material, resist pattern forming method and electronic component manufacturing method
    BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photosensitive materials used for microfabrication in manufacturing processes of semiconductor devices, TFTs (thin film transistors), optical disks, and the like.
    Conventionally, the microfabrication technique using photolithography is employ | adopted in the manufacturing process of an electronic component including LSI. That is, first, a resist liquid is applied onto a substrate or the like to form a resist film. Subsequently, pattern light is exposed to the obtained resist film, followed by an alkali development process to form a resist pattern. Subsequently, by dry etching the surface of the substrate or the like where the resist pattern is exposed as an etching mask, fine lines or holes are formed, and the resist is finally washed and removed.
    Therefore, the resist used herein generally requires high dry etching resistance. From this point of view, resists containing aromatic compounds have been widely used until now, and in particular, many base materials have been developed using alkali-soluble noblock resins and the like.
    On the other hand, with the high density integration of LSI and the like, the microfabrication technique as described above extends to sub-half micron orders in recent years, and such miniaturization is expected to become more remarkable in the future. For this reason, shortening of the wavelength of the light source in photolithography is progressing, and the formation of the fine resist pattern by the 5 times high frequency light of ArF excimer laser beam of 193 nm wavelength and YAG laser of 218 nm wavelength is currently attempted.
    By the way, in the resist which used the novolak resin as a base resin until now, the light absorption in the benzene nucleus of a novolak resin tends to become large with respect to the short wavelength light mentioned above. Therefore, when forming a resist pattern, it is difficult to reach | attain light to the board | substrate side of a resist film at the time of exposure, As a result, it was difficult to form a favorable pattern of a pattern shape with high sensitivity and high precision.
    However, a pattern formation method called the PCM (portable portable mask) method is described in B.J. Lin, Proc, SPIE. 174, 114, 1979. This is a pattern method in which an upper resist pattern is formed and the lower layer is collectively exposed as a mask. As implemented by this PCM method, A.W. McCullough et al., Proc. SPIE. 631, 316, 1986. Here, PMGI (polydimethylglutarimide) is used as a lower layer material, and the pattern formed by the upper layer novolak-naphthoquinone diazide is collectively exposed as a mask, and pattern formation is carried out.
    The PCM method as described above has the advantage that scum, such as scum, which appears in the pattern transfer and formation of the pattern by etching, does not occur by transferring and forming the pattern in a process called underlayer exposure and development. After that, various PCM methods have been proposed. However, in the conventional PCM method, the lower layer photosensitive material is often smaller in dry etching resistance than the conventional phenol resin, and has not been practical.
    In the example of McCullo et al., A material used in lithography by a mercury lamp called novolak naphthoquinone diazide is used as the upper photosensitive material, and as the lower photosensitive material, KrF having a shorter wavelength than a mercury lamp called PMGI. Materials used in lithography by excimer laser light are employed. For this reason, the wavelength of exposure light for forming an upper layer pattern is long, and there is no advantage in forming an optically fine pattern. In addition, there is a problem that it is difficult to form a fine pattern due to a problem such as mixing between layers after actually stacking the photosensitive layer.
    As described above, resists using novolac resins as base resins have high dry etching resistance and alkali development, but have insufficient transparency to short wavelength light, and thus are five times higher than those of ArF excimer lasers and YAG lasers. There is a strong demand for the development of resists suitable for photolithography using light. In view of such a point, in recent years, a resist containing an alicyclic compound in relation to an aromatic compound has been attracting attention. For example, Japanese Patent Application Laid-Open No. 4-39665 discloses dry etching resistance and transparency to short wavelength light. As a good resist, what made the base resin the polymer which has an adamantane frame | skeleton is proposed. Moreover, the example which provided alkali solubility to a polymer by copolymerizing the compound which has an adamantane frame | skeleton with the acryl-type compound which has a carboxylic acid group, and the example which formed the resist pattern by alkali image is also shown.
    However, when a resist pattern is formed by an alkali development with respect to a resist containing an alicyclic compound, various problems arise because alkali solubility greatly differs between an alicyclic structure such as adamantane skeleton and a carboxylic acid group. . For example, dissolution and removal of a predetermined region of the resist film at the time of development lead to a decrease in resolution, while partial dissolution occurs in a region where the resist film is expected to remain, causing cracks and roughness of the surface.
    In addition, an alkaline solution may penetrate into the interface between the resist film and the substrate, and the resist pattern may peel off, and sufficient adhesiveness is not obtained. In addition, phase separation of the alicyclic structure and the carboxylic acid portion in the polymer tends to proceed easily, making it difficult to produce a uniform resist liquid, and insufficient applicability.
    Again, chemically amplified resists have been developed that utilize acid catalysis as highly sensitive resists, but these chemically amplified resists are easily affected by the time until exposure to PEB. In particular, the shape of the resist pattern obtained by the influence of the amine contained in the air deteriorates, and in some cases, peeling from the substrate occurs.
    As described above, in the conventional PCM method, a material used in lithography in which the upper photosensitive material has a longer wavelength than the lower photosensitive material is employed, and there is no advantage in forming an optically fine pattern.
    Accordingly, an object of the present invention is to provide a photosensitive material having excellent environmental stability, high transparency to short wavelength light, high adhesion to a substrate by alkali development, and a fine pattern with good resolution. It is done.
    In addition, the present invention can be carried out with light or electron beams having a short wavelength of 193 nm, has a high absorption wavelength band which may act as a mask in the exposure of the lower layer, and it is difficult to form a mixture between the lower layer film and the like. It aims at providing the practical pattern formation method by the PCM method which used the specific material which has all as an upper layer material.
    In addition, an object of the present invention is to provide a method for producing an electronic component that performs fine processing with high precision using the obtained pattern.
    1 is a cross-sectional view showing an example of a process of a method of forming a resist pattern of the present invention.
    2 is a cross-sectional view showing another example of the process of the method of forming a resist pattern of the present invention.
    3 is a cross-sectional view showing still another example of the process of the method of forming a resist pattern of the present invention.
    According to the present invention, there is provided a photosensitive material comprising an alkali-soluble resin portion and a diazo compound portion having at least one of an alicyclic skeleton and a condensed polycyclic skeleton.
    Moreover, according to this invention, the process of forming the film | membrane containing the photosensitive material containing the alkali-soluble resin part and diazo compound part which has at least one of an alicyclic skeleton and a condensed polycyclic skeleton on a board | substrate, and predetermined | prescribed of the said photosensitive material film The pattern formation method provided with the process of irradiating actinic radiation to an area | region, and performing the exposure, and the process of melt-dissolving and developing the exposed part or unexposed part of the said photosensitive material film | membrane after exposure with aqueous alkali solution are provided.
    Further, according to the present invention, a step of forming a lower layer photosensitive material film on a substrate, a step of forming an upper photosensitive material film including a substituted or unsubstituted polycyclic condensed aromatic ring, and irradiating first actinic radiation to a predetermined region of the upper photosensitive material film And exposing the exposed portion or unexposed portion of the upper layer photosensitive material film after exposure using an aqueous alkali solution, and developing the first layer using the upper photosensitive material film pattern obtained after the developing step as a mask. A resist pattern comprising a step of collectively irradiating a second actinic radiation having a wavelength longer than actinic radiation, and performing a developing treatment to selectively dissolve and remove the exposed portion to transfer the upper photosensitive material film pattern to the lower photosensitive material film. A method of forming the same is provided.
    Moreover, according to this invention, the process of forming a lower layer photosensitive material film on a board | substrate, the process of forming an upper photosensitive material film containing a substituted or unsubstituted benzene ring or polycyclic condensed aromatic, and an electron beam to a predetermined area | region of the said upper photosensitive material film is carried out. Irradiating and exposing, exposing and unexposing the exposed or unexposed portions of the upper layer photosensitive material film after exposure using an aqueous alkali solution, and developing the photosensitive material film pattern obtained after the developing step as a mask using a wavelength of 190 to There is provided a resist pattern forming method comprising a step of transferring the upper photosensitive material film pattern to the lower photosensitive material film by collectively irradiating 260 nm light, subjecting the developer to dissolving and removing the exposed portion.
    Furthermore, according to this invention, the process of forming the film | membrane containing the photosensitive material containing the alkali-soluble resin part and diazo compound part which has at least one of an alicyclic skeleton and a condensed polycyclic skeleton on a board | substrate, and predetermined | prescribed of the said photosensitive material film A step of irradiating with light to an area of light, a process of dissolving and removing the exposed portion of the photosensitive material film after the exposure with an alkaline developer, forming a patterned photosensitive material film, and etching the obtained photosensitive material film pattern A method of manufacturing an electronic component is provided, which includes a process of transferring a pattern onto a substrate for use as a substrate.
    Hereinafter, the present invention will be described in detail.
    In this invention, alkali-soluble resin which consists of copolymers, such as acrylic acid and methacrylic acid, can be used as alkali-soluble resin. More specifically, copolymers composed of menthyl methacrylate, methyl methacrylate and methacrylic acid; The copolymer which consists of vinyl naphthalene, menthyl acrylate, methyl acrylate, and methacrylic acid, etc. are mentioned.
    In the present invention, in addition to the advantage of having good transparency at 193 nm because the alkali-soluble resin has an alicyclic structure or a condensed polycyclic structure, high dry etching resistance can be imparted to the resulting resist pattern. As the alicyclic structure may be a cyclic compound or a cyclic cycloalkyl bicyclo compounds and their condensed rings, such as represented by the general formula C n H 2n (n is an integer greater than or equal to 3).
    Specifically, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, crosslinked hydrocarbons introduced therein, spiro ring such as spiroheptane, spirooctane, norbornyl ring, adamantyl ring, bornen ring, men Terpene rings such as tilde rings and mentan rings, tufen, savinen, tozone, karan, karen, refuge, norpinan, boran, phencan, tricyclene, cholesteric ring such as cholesteric ring, tanjuic acid, digitoids, camphor Examples of the ring, isoendocrine ring, sesquiterpene ring, santon ring, diterpene ring, triterpene ring, and steroid saponins are illustrated. Moreover, as an alicyclic skeleton, the compound which exists in nature and has a substituted or unsubstituted menthyl group is especially preferable from a viewpoint of being excellent in environmental stability.
    On the other hand, as what has a condensed polycyclic structure, there exist some shown below, for example. For example, indene, indane, benzoprdene, 1-indanonone, 2-indanonone, 1,3-indadione, ninhydrin, naphthalene, methylnaphthalene, ethylnaphthalene, dimethylnaphthalene, cardarene, vinylnaphthalene, 1 , 2-dihydronaphthalene, 1,4-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalenetetrarin, 1,2,3,4,5,6,7,8-octahydronaphthalene, cis Decalin, trans-decarin, fluoronaphthalene, chloronaphthalene, bromonaphthalene, iodonaphthalene, dichloronaphthalene, (chloromethyl) naphthalene, 1-naphthol, 2-naphthol, naphthalenediol, 1,2,3, 4-tetrahydro-1-naphthol, 1,2,3,4-tetrahydro-2-naphthol, 5,6,7,8-tetrahydro-1-naphthol, 5,6,7,8-tetrahydro- 2-naphthol, decahydro-1-naphthol, decahydro-2-naphthol, chloronaphthol, nitronaphthol, aminonaphthol, methoxynaphthalene, ethoxynaphthalene, naphthyl ether, naphthyl acetate, naphthoaldehyde, Phthalenedicarbaldehyde, hydroxynaphthoaldehyde, dinaphthylketone, 1 (2H) -naphthylene, α-tetrarone, β-tetraron, α-decaron, β-decaron, 1,2-naphthoquinone , 1,4-naphthoquinone, 2,6-naphthoquinone, 2-methyl-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, isonaphthazarine, naphthoic acid , 1-naphthol-4-carboxylic acid, naphthalic acid, naphthalic anhydride, 1-naphthyl acetic acid, thionaphthol, N, N-dimethylnaphthylamine, naphtonitrile, nitronaphthalene, pentalene, azene, hep Talylene, Fluorene, 9-phenylfluorene, Nitrofluorene, 9-Fluoleenol, Fluoleenone, Anthracene, Methylanthracene, Dimethylanthracene, 9,10-Dihydroanthracene, Anthenol, Anthranone, Hydroanthranone , Dihydroxyanthracene, anthraganol, 1 (4H) -anthracenone, anthrone, anthrarobin, curissarobin, oxanthrone, anthracenecarboxylic acid, anthramin, nitroanthracene, anthracenquinone, anthrose Quinone, methylanthraquinone, hydroxyanthraquinone, phenanthrene, phenanthrol, phenanthrene hydroquinone, phenanthhraquinone, biphenylene, s-indacene, as-indacene, phenene, tetracene, chrysene, 5, 6-Crysoquinone, pyrene, 1,6-pyrenequinone, triphenylene, benzo [α] anthracene, benzo [α] anthracene-7, 12-quinone, benzanthrone, acetotorylene, acefenanthorene, ace Phenanthrene, 17H-cyclopenta [α] -phenanthrene, fluoranthene, praiadene, pentacene, pentaphene, pysene, pyriene, dibenzo [aj] anthracene, benzo [α] pyrene, coronene, pyrantorene , Pyrantoron and the like.
    Moreover, the absorption band of these condensed polycyclic frame | skeleton generally shifts from the absorption band of a benzene nucleus, and does not have high absorption in a short wavelength area | region. For this reason, the photosensitive material which can form the resist pattern which has dry etching resistance is obtained by including these frame | skeleton in this alkali-soluble acrylic resin.
    Moreover, the photosensitive material of this invention can be used also for optical property evaluation, such as ArF excimer laser. Therefore, when the obtained resist pattern is not used as an etching mask, it is not necessary to contain an alicyclic skeleton, a naphthalene skeleton, and an anthracene skeleton in alkali-soluble resin.
    When the alkali-soluble resin in the present invention contains an alicyclic skeleton, radical polymerization of a polymerizable compound having such a polymer, for example, an alicyclic structure into which an acidic substituent is introduced and a polymerizable double bond in a molecule thereof, It can be easily obtained by polymerization by cationic polymerization, anionic polymerization, or the like, or by polymerization under a Ziegler Nater catalyst. Generally, the polymeric compound which has an alicyclic structure and a polymerizable double bond in a molecule | numerator can be made into a high molecular weight polymer by using the latter catalyst. However, in the present invention, a polymer having a low molecular weight does not have any problem as long as it forms a film, so that the polymer may be polymerized using a simple method such as radical polymerization, and may be used in a state where a low molecular weight compound and a high molecular compound are mixed.
    In this case, copolymerization with acrylic acid, maleic anhydride and ester substituents thereof, vinylphenol, vinyl naphthol, hydroxyethyl methacrylate, SO 2 and the like from the viewpoint of adjusting the alkali solubility of the polymer and improving the adhesion between the resist film and the substrate. desirable. Moreover, you may copolymerize the compound formed by protecting with the acid-decomposable group which has the dissolution inhibiting ability with respect to alkali solution with respect to the alkali-soluble group of these alkali-soluble compounds.
    However, considering the transparency of the resist to the short wavelength light, it is preferable to copolymerize the compound with a compound having no molecular skeleton having a large light absorption in the short wavelength region such as benzene nucleus, specifically, the absorbance of the polymer with respect to light having a wavelength of 193 nm. 4 or less is preferable per 1 micrometer, and 2 or less is more preferable. However, in the case of using the photosensitive material of the present invention as an upper layer resist in a substrate having an intermediate layer, the film thickness can be reduced, so that the above-described absorbance may be increased to about 8 per micrometer.
    However, the copolymerization ratio of alkali-soluble compounds, such as acrylic acid, is 1 to 50% in a copolymer, More preferably, it is 10 to 50% of range. If it is less than 1%, the alkali solubility of the polymer may be insufficient. On the contrary, if it exceeds 50%, there is a tendency that nonuniform dissolution occurs and it is difficult to form a resist pattern.
    In addition, the average molecular weight of the polymer as described above is preferably set in the range of 500 to 500,000, more preferably 5,000 to 15,000. If the average molecular weight of the polymer is less than 500, it is disadvantageous for forming a resist film having sufficient mechanical strength. Conversely, if the average molecular weight exceeds 500,000, it becomes difficult to form a resist pattern having good resolution.
    These compounds are usually a mixture containing a component having various molecular weights, but in the present invention, even a compound having a relatively low molecular weight is effective. For example, even if it exists in the weight of the molecular weight of 500-1,000 heavily, uniform dissolution can be suppressed. Further, in this case, even if a large number of monomers are present in the resin, there is little deterioration in the dissolution characteristics of the alkaline developer and the dry etching resistance of the obtained resist pattern.
    On the other hand, as a diazo compound which is another component of the photosensitive material of this invention, p-quinone diazides, such as the diazo compound represented by following formula (1), (beta) -naphthylamide of p-benzoquinone sulfonic acid, for example , P-iminoquinonediazides described in British Patent No. 723,382, organic solvent soluble condensation products of diazonium salts and formaldehyde described in British Patent No. 1,110,017, p-diazophenylamine salts and 4 Aromatic diazonium salts, such as co-condensation products of 4-bismethoxymethyldiphenylether with formaldehyde, and copolymerization products of other aromatic products with formaldehyde, and azides described in British Patent No. 745,886 Aromatic azide such as compounds, and the like.
    In Formula 1, R 1 and R 2 may be the same or different, each having a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted unsubstituted aryl group, substituted with 1 to 20 carbon atoms including Si or A group optionally selected from an unsubstituted alkyl group and a substituted or unsubstituted aryl group containing Si.
    Among the diazo compounds described above, as positive type photosensitive agents, o-quinone diazides such as o-naphthoquinone diazide sulfonic acid or aromatic esters or amides of o-naphthoquinone diazide carbonic acid are particularly environmental and heat resistant. It is preferably used in view of. Especially, the naphthoquinone diazia sulfonic acid ester of polyhydroxy benzophenone is more preferable, The 1,2-naphthoquinone diazide sulfonic acid ester of 2,3,4- trihydroxy benzophenol specifically, is preferable. Or 1,2-naphthoquinone diazide sulfonic acid esters of 2,3,4,4'-tetrahydroxybenzophenone, and the like are most preferred.
    Of the two kinds suitable as the above-described photosensitizers, the latter 1,2-naphthoquinone diazide sulfonic acid esters of 2,3,4,4'-tetrihydroxybenzophenone are preferable because they can improve the heat resistance of the resist. . In addition, it is preferable that the esterification rate of 2,3,4,4'-tetrahydroxy benzophenone by 1,2-naphthoquinone diazide sulfonic acid in these photosensitizers shall be 40 to 100% of the total number of hydroxyl groups in this compound. . This is because there exists a possibility that resolution may fall when esterification rate is less than 40%.
    For example, the number of introduced naphthoquinone diazides is 1.6-4 on average per molecule of 2,3,4,4'-tetrahydroxybenzophenone, and generally tetrahydrate having 1-4 introduced water. It is a mixture of oxybenzophenones.
    In the photosensitive material of the present invention, the blending amount of the diazo compound as described above is preferably 20 to 60% by weight, more preferably 30 to 50% by weight based on the alkali-soluble resin. This is because if less than 20%, the effect of blending the diazo compound cannot be sufficiently obtained, and if it exceeds 60% by weight, the transparency to the ArF excimer laser light, which is a characteristic of the alkali-soluble resin, may be impaired.
    In addition, a diazo compound may be introduce | transduced into the side chain of alkali-soluble resin, In this case, it is preferable that alkali-soluble resin has alicyclic skeleton for the reason mentioned above. Thus, even when a diazo compound is contained in alkali-soluble resin, the ratio is preferably 20 to 60% by weight, more preferably 30 to 50% by weight.
    The photosensitive material of this invention can be manufactured by dissolving alkali-soluble resin and diazo compound, or alkali-soluble resin which has a diazo compound in a side chain in a predetermined solvent.
    As a catalyst used here, For example, Ketone solvents, such as cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone; Cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve acetate; Ester solvent, such as ethyl acetate, butyl acetate, isoamyl acetate, (gamma)-butyrolactone; Glycol solvents such as propylene glycol monomethyl ether acetate; Nitrogen-containing solvents such as dimethyl sulfoxide, hexamethylphosphoric triamide, dimethylformamide, and N-methylpyrrolidone. Again, a mixed solvent in which dimethyl sulfoxide, dimethyl formaldehyde, N-methylpyrrolidinone, or the like is added thereto can be used to improve solubility. In addition, propionic acid derivatives such as methyl methyl propionate, lactic acid esters such as ethyl lactate, PGMEA (propylene glycol monoethyl acetate) and the like are also low toxicity and can be preferably used.
    In addition, in the present invention, such a solvent may be used alone or in combination of two or more kinds, and again isopropyl alcohol, ethyl alcohol, methyl alcohol, butyl alcohol, n-butyl alcohol, s-butyl alcohol, t- Aliphatic alcohols, such as butyl alcohol and isobutyl alcohol, and aromatic solvents, such as toluene and xylene, may be contained.
    The formation process of the pattern using the photosensitive material of this invention manufactured as mentioned above is demonstrated. First, a solution of the photosensitive material dissolved in the organic solvent as described above is applied to a predetermined substrate by a spin coating method, a dipping method, or the like, and then dried at 150 ° C. or lower, preferably 70 to 120 ° C. to form a resist film. .
    As the substrate here, for example, a silicon wafer, a silicon wafer having various insulating films, electrodes, wirings, etc. formed on the surface thereof, a franc mask, a group III-V compound semiconductor wafer such as GaAs, AlGaAs, chromium or chromium oxide deposition mask, for example. , An aluminum vapor deposition substrate, an IBPSG coat substrate, a PSG coat substrate, an SOG coat substrate, a carbon film spar substrate, or the like can be used.
    Again, an intermediate layer made of polysilane, polysilicon, or the like is formed on these substrates with a film thickness of about 0.5 to 5 µm, and then the photosensitive material of the present invention can be applied and used as an upper layer resist. In addition, although the film thickness of the resist film formed on a board | substrate after evaporation of a solvent changes with a use, it is preferable to exist in the range of 0.05-15 micrometers normally. If it deviates from this range, there exists a possibility that a sensitivity may fall remarkably or a resolution may fall.
    Subsequently, according to a desired pattern, the resist film formed on a board | substrate is irradiated with a chemical ray through a predetermined | prescribed mask, or a chemical film is directly exposed to the resist film surface, and a resist film is exposed. As described above, since the photosensitive material of the present invention has excellent transparency over a wide range of wavelengths including short wavelength light, i. Although deep UV light, such as excimer laser light such as light, KrF, ArF, and F 2 , and synchrotron orbital radiation (SOR), electron beam (EB), γ-ray, and ion beam, can be used, the photosensitive material of the present invention is ArF. The present invention is particularly effective for short wavelength light such as excimer laser light. In addition, you may bake about 100 degreeC about the resist film after exposure.
    Next, the resist film is developed by an immersion method, a spray method, or the like, and the resist film of the exposed portion or the unexposed portion is selectively dissolved and removed in an alkaline solution to form a desired pattern. At this time, specific examples of the alkaline solution include aqueous organic alkali solutions such as tetramethylammonium hydroxide aqueous solution and choline aqueous solution, and inorganic alkali aqueous solutions such as potassium hydroxide and sodium hydroxide, and solutions in which alcohols and surfactants are added thereto. . The concentration of the alkaline solution here is preferably 15% by weight or less from the viewpoint of making the difference in the dissolution rate between the exposed portion and the unexposed portion sufficiently.
    The substrate and the resist pattern after development may be rinsed with water or the like.
    The photosensitive material of this invention contains alkali-soluble resin and a diazo compound, and its transparency with respect to ArF excimer laser beam is favorable. For this reason, a resist pattern can be formed with high sensitivity and high precision.
    Therefore, the resist pattern formed using the photosensitive material of this invention which is excellent in transparency is extremely favorable in resolution, and also the adhesiveness of the obtained resist pattern and a board | substrate is also high, and peeling from a board | substrate does not generate | occur | produce at all. Therefore, for example, by dry etching using a resist pattern formed by using the photosensitive material of the present invention as an etching mask, it is possible to faithfully transfer ultrafine patterns of quarter microns or less such as an exposed substrate.
    In addition, when an alkali-soluble resin containing an alicyclic skeleton or a condensed polycyclic skeleton is blended as a component of the photosensitive material of the present invention, the other bond remains even when one carbon-carbon bond is cleaved in the obtained resist pattern. . For this reason, such a resist pattern has high dry etching resistance.
    In the pattern forming process using the photosensitive material of the present invention, any other steps other than those described above are added, and there is no problem, for example, the planarization layer forming step as the underlayer of the resist film, the adhesion between the resist film and the underlayer. A pretreatment step for improvement, a rinsing step of removing with water or the like after development of the resist film, and an ultraviolet re-irradiation step before dry etching can be appropriately performed.
    The pattern forming method of the present invention can be preferably applied to a multilayer resist process. This process is described below.
    When the pattern formation method of the present invention is applied to a multilayer process, for example, a layer exposed by ArF excimer laser light as the first actinic radiation and a light in the wavelength range of 200 to 260 nm as the second actinic radiation. An underlayer exposed by the light may be formed. Alternatively, the upper layer exposed by the low speed electron beam and the lower layer exposed by the light in the wavelength range of 190 to 260 nm may be formed.
    In the former, as the photosensitive material used for the upper layer, a photosensitive material containing a condensed polycyclic skeleton containing a naphthyl group having a high transparency at 193 nm and a high absorption at around 220 nm is preferable.
    In this case, it is preferable to use a resist such as a phenol resin represented by the formulas (2) to (5) having good transparency in the wavelength range of 200 to 260 nm and high dry etching resistance.
    On the other hand, as the photosensitive material used for the upper layer in the latter, it is preferable to have a substituted or unsubstituted polycyclic condensed aromatic ring or benzene ring having absorption in the wavelength range of 190 to 260 nm which can be exposed and developed with low speed electron beam with high sensitivity. In addition, as a photosensitive material used for an underlayer, the material exposed by the light of wavelength 190-260 nm, and having high dry etching tolerance is preferable. In the case where the upper layer has a polycyclic condensed aromatic ring having absorption at around 220 nm, the phenolic resin represented by the following formulas 2 to 5 is preferable as the lower layer, while the upper layer has a benzene ring having absorption at around 193 nm. It is preferable to make lower layer into acrylic resin which has an alicyclic skeleton.
    Here, as a polycyclic condensation aromatic ring, substituted or unsubstituted naphthalene, atlasene, etc. are mentioned in a condensed polycyclic skeleton. Moreover, a phenol resin, a novolak resin, etc. are mentioned as what has a benzene ring.


    In general, if there is sufficient dry etching resistance in the lower layer, the upper layer is not necessary, and as the upper layer, the upper layer may have an absorbance that can serve as a mask during exposure of the lower layer. The film thickness of the upper layer may also satisfy the above condition. Therefore, since the film thickness can be reduced and high sensitivity is not required, non-chemically amplified resists are preferably used in addition to chemically amplified resists.
    By the way, when forming the upper and lower photosensitive material layers, the mixing which solvents are mixed between layers often becomes a problem. When forming the layer, it is also one of the solutions to form a layer between the upper layer and the lower photosensitive material in which no mixing occurs in any of the upper and lower layers called the barrier coat. However, from the viewpoint of shortening the process and saving of material, it is preferable that such a barrier coat layer is not included.
    In the pattern formation method of this invention, since the material which does not produce mixing as mentioned above is used, the influence is extremely small. Moreover, in order to prevent mixing, a material which is hard to dissolve is generally used in the lower layer. For example, when exposing the upper layer with an ArF excimer laser, a resist for ArF excimer laser in a xylene solvent can be used for the lower layer resist for KrF excimer laser based on polyhydroxystyrene. In addition, when using the chemically amplified ArF excimer laser resist of a xylene solvent, as an acid generator, nonionic photo-acid generators, such as a naphthalidyl triprate, are used preferably. Moreover, the quinonediazide compound with high induction rate is used suitably as a photosensitizer and a photo-acid generator.
    In addition, as described in Japanese Patent Application No. Hei 8-221,230, the upper layer ArF excimer laser resist contains a light absorbing compound such as novolak or naphthol novolak to such an extent that transparency at 193 nm is not significantly reduced. You may have to. Thereby, it is possible to have high absorbance in the wavelength range of 210 to 260 nm. This novolak and naphthol novolak also act as a dissolution inhibitor.
    On the other hand, when exposing the upper layer with an electron beam, a low-speed electron beam of 10 keV or less is preferable from the viewpoint of resist sensitivity in pattern formation. As the electron beam resist material used in the present invention, one having a high absorbance at 193 nm made of a novolak or a polystyrene resin is preferably used.
    Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples.
    Synthesis Example 1
    Synthesis of Alkali-Soluble Acrylic Resin Having Alicyclic Structure in Side Chain
    33 mol%, 29 mol%, 38 mol% of menthyl methacrylate, methyl methacrylate, and methacrylic acid (6.0 g in total) were mixed with 20 g of tetrahydrofuran (THF). Subsequently, 0.73 g of azoisobutylnitrile (AIBN) was added to the obtained solution, and the mixture was heated and reacted at 60 ° C for 35 hours while stirring, and then the reaction solution was added dropwise to n-hexane. The precipitate was then filtered and dried to give a copolymer of about 10,000 weight average molecular weight (styrene equivalent).
    Synthesis Example 2
    Synthesis of Alkali-Soluble Acrylic Resin Having Alicyclic Structure and Diazo Compound in the Side Chain
    Equimolar hydroxyethyl methacrylate and 1,2-naphthoquinonediazide-4-sulfonic acid chloride were dissolved in dioxane to give a 10 wt% dioxane solution. Subsequently, while maintaining this solution at 20 ° C., triethylamine in an amount corresponding to 1.2 equivalents of 1,2-naphthoquinone diazide-4-sulfonic acid chloride was slowly added dropwise to the dioxane solution to precipitate the precipitate. Separated and added to a large amount of 0.2% oxalic acid solution. The precipitate was filtered off and then washed with ion exchanged water, followed by vacuum drying to obtain hydroxyethyl methacrylate naphthoquinone diazide sulfonic acid ester.
    Subsequently, 33 mol%, 29 mol%, 38 mol% of menthyl methacrylate, hydroxyethyl methacrylate naphthoquinone diazide sulfonic acid ester, and methacrylic acid (total 6.0 g) were respectively added to tetrahydrofuran (THF) 20 mixed to g. Subsequently, 0.73 g of azoisobutylnitrile (AIBN) was added to the obtained solution, and the mixture was heated and reacted at 60 ° C for 35 hours while stirring, and then the reaction solution was added dropwise to n-hexane. The precipitate was then filtered and dried to give a copolymer of about 10,000 weight average molecular weight (styrene equivalent).
    Synthesis Example 3
    Synthesis of Alkali-Soluble Acrylic Resin Having Condensed Polycyclic Structure in Side Chain
    30 mol%, 30 mol% and 40 mol% of vinylnaphthalene, methyl methacrylate and methacrylic acid (6.0 g in total) were respectively mixed with 20 g of tetrahydrofuran (THF). Subsequently, 0.60 g of azobisisobutyronitrile (AIBN) was added to the obtained solution, and the mixture was heated and reacted at 60 ° C for 35 hours while stirring, and then the reaction solution was added dropwise to n-hexane. Thereafter, the precipitate was filtered and dried to obtain a copolymer having a weight average molecular weight (styrene equivalent) of about 7,000.
    Synthesis Example 4
    Synthesis of Alkali-Soluble Acrylic Resin Having Alicyclic Structure and Condensed Polycyclic Structure in Side Chain
    15 mol%, 20 mol%, 30 mol%, 35 mol% of vinylnaphthalene, menthyl methacrylate, methyl methacrylate and methacrylic acid (6.0 g in total) were mixed with 20 g of tetrahydrofuran (THF). . Subsequently, 0.60 g of azoisobutyronitrile (AIBN) was added to the obtained solution, and the mixture was heated and reacted at 60 ° C for 35 hours while stirring, and then the reaction solution was added dropwise to n-hexane. Thereafter, the precipitate was filtered and dried to obtain a copolymer having a weight average molecular weight (styrene equivalent) of about 7,000.
    Synthesis Example 5
    Synthesis of Chemically Amplified Acrylic Resin Having Alicyclic Structure and Condensed Polycyclic Structure in the Side Chain
    26.2 mol%, 19.4 mol%, 21.6 mol%, 32.7 mol% of vinylnaphthalene, menthyl acrylate, tetrahydropyranyl methacrylate and methacrylic acid (total 9.43 g) were added to 20 g of tetrahydrofuran (THF). Mixed. Subsequently, 1.6 g of azoisobutyronitrile (AIBN) was added to the obtained solution, and the mixture was heated and reacted at 60 ° C. for 40 hours while stirring, and then the reaction solution was added dropwise to n-hexane. Thereafter, the precipitate was filtered and dried to obtain a copolymer having a weight average molecular weight (styrene equivalent) of about 6,000.
    Synthesis Example 6
    Dissolution Inhibitor: Synthesis of 1-adamantylcarbonyl-2,2'-di-tert-butoxycarbonylethane
    0.02 mol of malonic acid di-tert-butyl was dissolved in THF and slowly added at 0 ° C. in a solution in which 0.02 mol of sodium hydride was dispersed. After the generation of hydrogen was completed, the reaction system was brought to room temperature, and 0.02 mol of THF solution of adamantyl (bromomethyl) ketone was introduced. Then, it was made to react at room temperature for 5 hours. Subsequently, the reaction solution was poured into a large amount of ice water, and the reaction solution was ether extracted, and the oil layer was washed once with an aqueous oxalic acid solution and then twice with water. Finally, it was concentrated to dryness to give 1-adamantylcarbonyl-2,2'-di-tert-butoxycarbonylethane (AdTB).
    Synthesis Example 7
    Synthesis of Dissolution Inhibitors
    Naphthol was condensed with glyoxylic acid to give a novolak oligomer. 10 g of this novolak oligomer was dissolved in 50 ml of 3,4-dihydropyran and stirred for 48 hours in the presence of a catalytic amount of hydrochloric acid. Thereafter, a sodium hydroxide lump was added to this solution, the mixture was stirred for a while, the residue was separated by filtration, the oil layer was concentrated under reduced pressure and dried under ethyl acetate, and washed twice with 5% aqueous oxalic acid solution. It was then separated, dried over anhydrous sodium sulfate, and concentrated to dryness to yield pyranylated naphthol novolak (NV4THP).
    Synthesis Example 8
    Synthesis of Photoresist
    0.1 g of α-naphthol was dissolved in THF, and then 0.1 mol of 1,2-naphthoquinonediazide-4-sulfonylchloride was added to this THF solution. While stirring this mixed liquid at 0 degreeC, it was gradually added dropwise to 0.1 mol of triethylamine. The precipitated salt was separated by filtration, and the reaction solution was concentrated to dryness, and then recrystallized with ethanol-hexane to obtain a naphthoquinone diazide compound (NPNQ) of naphthol.
    (Example 1)
    To the polymer obtained in Synthesis Example 1, 40% by weight of naphthoquinone diazide as a diazo compound was added to give 8% by weight of a cyclohexanone solution. The solution was filtered with a membrane filter of 0.2 mu m, then coated by spin coating on a Si wafer, and prebaked at 100 DEG C for 90 seconds to form a resist film having a thickness of 0.2 mu m.
    The resist film was exposed by irradiating with ArF excimer laser light (NA = 0.55) having a wavelength of 193 nm, and then the resist film after exposure was exposed to a 2.38% alkaline aqueous solution of tetramethylammonium hydroxide (TMAH) as an alkali developer. Developed. As a result, a line-and-space pattern of 0.15 탆 could be developed with a DOSE amount of 130 mJ / cm 2 . Moreover, the adhesiveness with the board | substrate of the obtained pattern was also favorable, and peeling of the pattern was not observed at all.
    (Example 2)
    To the polymer obtained in Synthesis Example 1, 45% by weight of a diazo compound of meldmic acid was added to make 8% by weight of an ethyl lactate solution. The solution was filtered with a 0.2 μm membrane filter, then spin coated on a Si wafer, and prebaked at 120 ° C. for 90 seconds to form a 0.2 μm resist film.
    The resist film was exposed by irradiating with an ArF excimer laser light (NA = 0.55) having a wavelength of 193 nm, and then the resist film after exposure was developed with a 2.38% aqueous alkali solution of TMAH as an alkali developer. As a result, a line-and-space pattern of 0.15 탆 could be developed with a DOSE amount of 120 mJ / cm 2 . Moreover, the adhesiveness with the board | substrate of the obtained pattern was also favorable, and peeling of the pattern was not observed at all.
    (Example 3)
    To the polymer obtained in Synthesis Example 1, 40% by weight of naphthoquinone diazide as a diazo compound was added to give 8% by weight of a cyclohexanone solution. The solution was filtered through a 0.2 μm membrane filter, then spin coated onto a Si wafer and prebaked at 100 ° C. for 90 seconds to form a 0.5 μm resist film.
    The resist film was exposed with an electron beam, and then the resist film after exposure was developed with a 2.38% aqueous alkali solution of TMAH as an alkali developer. As a result, a 0.15 μm line and space pattern could be resolved with an acceleration voltage of 50 keV and an amount of DOSE of 30 μC / cm 2 . Moreover, adhesiveness with the board | substrate of the obtained pattern was also favorable, and peeling of the pattern was not observed at all.
    (Example 4)
    This embodiment will be described with reference to FIGS. 1A to 1F.
    First, 40 wt% of naphthoquinone diazide as a diazo compound was added to the polymer obtained in Synthesis Example 1 to prepare a resist solution of the present invention as an 8 wt% cyclohexanone solution.
    On the other hand, as shown to FIG. 1A, the novolak-type photoresist was apply | coated on Si wafer 11, and was hard-baked at 190 degreeC, and the base layer 12 of 0.8 micrometer in thickness was formed. Again, SOG (spin on glass) was applied on the base layer and baked at 200 ° C. to form an intermediate layer 13 having a thickness of 0.1 μm.
    The cyclohexanone solution described above was filtered through a 0.2 μm membrane filter, spin coated on a Si wafer equipped with an underlayer and an intermediate layer, and then prebaked at 100 ° C. for 90 seconds to obtain a film thickness as shown in FIG. 1B. An upper layer resist film 14 of 0.2 mu m was formed.
    The resist film 14 was irradiated with an ArF excimer laser light (NA = 0.55) having a wavelength of 193 nm to be exposed as shown in Fig. 1C, and then the resist film after exposure was subjected to an alkali of 2.38% of TMAH as an alkali developer. It was developed with an aqueous solution. As a result, the line and space pattern of 0.15 micrometer as shown in FIG. 1D was able to be developed by DOSE amount of 130 mJ / cm <2> . Moreover, adhesiveness with the board | substrate of the obtained pattern was also favorable, and peeling of the pattern was not observed at all.
    Subsequently, using the resist pattern 14a formed as described above as an etching mask, the SOG film 13 of the intermediate layer was etched by CF 4 RIE to pattern the SOG film 13a as shown in Fig. 1E. ) Was formed. Again, the lower novolak-based photoresist film 12 was etched by O 2 RIE using patterns 14a and 13a obtained as described above as etching masks. As a result, the resist pattern can be faithfully transferred, and a patterned novolak-based photoresist film 12a as shown in FIG. 1F is obtained.
    (Example 5)
    The polymer obtained in Synthesis Example 2 was taken as an 8 wt% cyclohexanone solution. The solution was filtered with a membrane filter of 0.2 mu m, then coated by spin coating on a Si wafer, and prebaked at 100 DEG C for 90 seconds to form a resist layer of 0.3 mu m.
    This resist film was exposed by irradiating an ArF excimer laser light (NA = 0.55) having a wavelength of 193 nm, and then the resist film after exposure was developed with a 2.38% aqueous alkali solution of TMAH as an alkali developer. As a result, a line-and-space pattern of 0.15 탆 could be developed with a DOSE amount of 100 mJ / cm 2 . Moreover, the adhesiveness with the board | substrate of the obtained pattern was also favorable, and peeling of the pattern was not observed at all.
    (Example 6)
    To the polymer obtained in Synthesis Example 3, 20% by weight of naphthoquinone diazide as a diazo compound was added to give 8% by weight of a cyclohexanone solution. This solution was filtered through a 0.2 μm membrane filter. The solution thus obtained was applied onto the Si wafer by spin coating and prebaked at 100 ° C. for 90 seconds to form a resist film having a film thickness of 0.17 μm.
    The resist film was exposed by irradiating with ArF excimer laser light (NA = 0.55), and then the resist film after exposure was developed with an alkaline developer. As a result, a line-and-space pattern of 0.17 mu m could be developed with a DOSE amount of 140 mJ / cm 2 . Moreover, the adhesiveness with the board | substrate of the obtained pattern was also favorable, and peeling of the pattern was not observed at all.
    (Example 7)
    To the polymer obtained in Synthesis Example 4, naphthoquinonediazide as a diazo compound was added 30% by weight, which was dissolved in a 3: 1 mixed solution of cyclohexanone / PGMEA to obtain an 8% by weight solution. This solution was filtered through a 0.2 μm membrane filter. In addition, the Si wafer was surface-treated previously using HMDS (hexamethyldisilazane). The solution was applied onto the Si wafer by spin coating and prebaked at 120 ° C. for 90 seconds to form a 0.2 μm resist film.
    The resist film was exposed by irradiating with ArF excimer laser light (NA = 0.55), and then the resist film after exposure was developed with an alkaline developer. As a result, a 0.15 µm line-and-space pattern could be developed with a DOSE amount of 135 mJ / cm 2 . Moreover, the adhesiveness with the board | substrate of the obtained pattern was also favorable, and peeling of the pattern was not observed at all.
    (Example 8)
    2A to 2C, the present embodiment will be described.
    First, as shown in FIG. 2A, a silicon oxide film 22 having a thickness of 0.8 mu m is formed on the Si wafer 21 by CVD (Chemical Vapor Deposition), and then about 0.7 thick made of Al-Si-Cu. An interlayer insulating film 24 made of a SiO 2 film by CVD and an underlayer wiring layer 23 having a thickness of 占 퐉 and an upper wiring film 25 of about 0.7 μm made of Al-Si-Cu were sequentially formed.
    On the other hand, 30 wt% of naphthoquinonediazide as a diazo compound was added to the polymer obtained in Synthesis Example 4, and this was dissolved in a 3: 1 mixture of cyclohexanone / PGMEA to obtain an 8 wt% solution. This solution was filtered through a 0.2 μm membrane filter. The solution thus obtained was applied by spin coating on a Si wafer and prebaked at 120 ° C. for 90 seconds to form a resist film 26 having a thickness of 0.3 μm on the upper wiring film 25.
    Subsequently, the ArF excimer laser light (NA = 0.55) was irradiated to the resist film 26 at a DOSE amount of 135 mJ / cm 2 , and the exposed resist film was developed with an alkali developer to form a resist pattern as shown in FIG. 2B. (26a) was formed. Again, using this resist pattern as a mask, the upper wiring film was etched by the RIE method using CCl 4 gas to form the upper wiring 25a.
    Thereafter, the resist pattern 26a was removed by carbonization in an O 2 plasma to obtain a two-layer wiring as shown in Fig. 2C.
    The upper wiring 25a was hardly influenced by the step difference caused by the lower wiring film and the like, and exhibited a design error of ± 0.05 µm with respect to the design dimension of 0.35 µm. In addition, when the upper wirings with a wiring spacing of 0.35 mu m and a line width of 0.35 mu m were formed, no defects such as disconnection and short circuit occurred at all.
    (Example 9)
    3A to 3E, the present embodiment will be described.
    First, onium salt (triphenylsulfonium triplate) as an acid generator was added to the polymer represented by the above-mentioned formula (2), and this was used as a PGMEA solution. This PGMEA solution was then filtered through a 0.2 μm membrane filter to obtain a solution for lower layer resist formation. Moreover, 40% of NPNQ as a photosensitizer was mixed with the polymer obtained by the synthesis example 4, and this was made into the xylene solution. This xylene solution was filtered through a 0.2 μm membrane filter to obtain a solution for forming upper resist.
    On the other hand, as shown in FIG. 3A, a 0.8-micrometer-thick silicon oxide film 32 was formed on the Si wafer 31 by CVD. On this, the lower layer resist forming resist solution prepared as described above was applied by spin coating, and prebaked at 120 ° C for 90 seconds to form a lower layer resist film 33 having a film thickness of 0.4 m.
    Again, on the lower layer resist 33, the upper layer resist forming resist solution prepared as described above was applied by spin coating, and prebaked at 120 ° C for 90 seconds to form the upper layer resist film 34 having a thickness of 0.2 m. Formed.
    The obtained upper resist film 34 was irradiated with an ArF excimer laser and developed with an alkaline developer, whereby a resist pattern 34a having a line width of 0.15 mu m as shown in Fig. 3B was obtained. Again, using this resist pattern 34a as a mask, an underlayer resist film 33 is exposed and developed using an interference filter that passes light in the vicinity of a wavelength of 220 nm, and developed underlayer resist pattern (as shown in Fig. 3C) ( 33a) was obtained.
    Using the thus obtained resist patterns 34a and 33a as a mask, the silicon oxide film 32 was etched by RIE using CCl 4 gas to obtain a silicon oxide pattern 32a as shown in Fig. 3D. After that, the resist pattern was carbonized and removed in an O 2 plasma to obtain a structure as shown in FIG. 3E.
    By the present Example, it turned out that the pattern of 0.15 micrometer of line widths can also be formed also in a silicon oxide film.
    (Example 10)
    First, naphthoquinone diazide (naphthoquinone diazide-4-sulfonic acid ester of 2,3,4,4'-tetrahydroxybenzophenone) was added to the polymer obtained in the synthesis example 1, and this was PGMEA- The cyclohexanone mixed solution was dissolved. This solution was then filtered through a 0.2 μm membrane filter to obtain a solution for lower layer resist formation. In addition, 3% of naphthalidyl triflate and 20% of NV4THP were added to the polymer obtained in Synthesis Example 5 to obtain an ethyl lactate solution. This solution was filtered through a 0.2 μm membrane filter to obtain a solution for forming upper resist.
    On the other hand, as shown in FIG. 3A, a silicon oxide film 32 having a thickness of 0.8 μm was formed on the Si wafer 31 by the CVD method. On this, the lower layer resist forming resist solution prepared as described above was applied by spin coating, and prebaked at 120 ° C for 90 seconds to form a lower layer resist film 33 having a film thickness of 0.4 m.
    Again, on the lower layer resist 33, the upper layer resist forming resist solution prepared as described above was applied by spin coating, prebaked at 120 DEG C for 90 seconds to form an upper layer resist film 34 having a film thickness of 0.2 mu m. Formed.
    The obtained upper resist film 34 was exposed with an electron beam of 15 keV and developed with an alkaline developer, and as a result, a resist pattern 34a having a line width of 0.13 mu m as shown in Fig. 3B was obtained. Using this resist pattern as a mask and irradiating with ArF excimer laser light, the lower resist film 33 was exposed and developed to obtain a lower resist pattern 33a as shown in Fig. 3C.
    Using the thus obtained resist patterns 34a and 33a as a mask, the silicon oxide film 32 was etched by RIE using CCl 4 gas to obtain a silicon oxide pattern 32a as shown in FIG. 3D. After that, the resist pattern was carbonized and removed in an O 2 plasma to obtain a structure as shown in FIG. 3E.
    By the present Example, it turned out that the pattern of 0.13 micrometer of line widths can also be formed also in a silicon oxide film.
    (Example 11)
    First, onium salt (triphenylsulfonium triplate) as an acid generator was added to the polymer represented by the above formula (2), and this was used as a PGMEA solution. This PGMEA solution was then filtered through a 0.2 μm membrane filter to obtain a solution for lower layer resist formation. In addition, AdTB obtained in Synthesis Example 6 was added as a dissolution inhibitor to the polymer obtained in Synthesis Example 5, and 3% of naphthalidyl triflate was further added to obtain a xylene solution. This solution was filtered through a 0.2 μm membrane filter to obtain a solution for forming upper resist.
    The lower layer resist film with a film thickness of 0.4 micrometer was formed on the Si wafer 31 using the solution for lower layer resist prepared as mentioned above. On this, the solution for forming an upper layer resist was applied by spin coating, and prebaked at 120 ° C. for 90 seconds to form an upper layer resist film having a thickness of 0.3 μm.
    The upper resist film thus obtained was irradiated with 30 mJ / cm 2 of ArF excimer laser, and baked at 110 ° C. for 1 minute. Subsequently, as a result of developing with a 0.238% TMAH alkaline developer, an upper resist pattern having a line width of 0.15 탆 was formed.
    Then, using the obtained upper resist pattern as a mask, it exposed to the lower resist using the interference filter which passes the light of wavelength 250nm vicinity, and baked at 140 degreeC for 1 minute. Finally, as a result of developing with a 2.38% aqueous TMAH solution, a pattern of 0.15 mu m could be transferred onto the substrate.
    (Example 12)
    First, onium salt (triphenylsulfonium triplate) as an acid generator was added to the polymer represented by the above formula (2), and this was used as a PGMEA solution. This PGMEA solution was then filtered through a 0.2 μm membrane filter to obtain a solution for lower layer resist formation. To the polymer obtained in Synthesis Example 5, 20% of NV4THP obtained in Synthesis Example 7 was added as a dissolution inhibitor, and 3% of naphthalidyltriplate 3% was further added to obtain a xylene solution. This solution was filtered through a 0.2 μm membrane filter to obtain a solution for forming upper resist.
    The lower layer resist film with a film thickness of 0.4 was formed on a Si wafer using the solution for lower layer resist prepared as described above. The upper layer resist forming solution was applied by spin coating, and prebaked at 120 ° C. for 90 minutes to form an upper layer resist film having a thickness of 0.2 μm.
    The upper resist film thus obtained was exposed to light by irradiating an ArF excimer laser with 35 mJ / cm 2 , and baked at 110 ° C. for 1 minute. Subsequently, as a result of developing with a 0.238% TMAH alkali developer, an upper resist pattern having a line width of 0.14 µm was able to be formed.
    Again, using the obtained upper resist pattern as a mask, it exposed to a lower resist at 5 mJ / cm <2> using the interference filter which passes the light of wavelength 230nm vicinity, and baked at 140 degreeC for 1 minute. Finally, as a result of developing with a 2.38% aqueous TMAH solution, 0.14 patterns could be transferred onto the substrate.
    From the results of the above Examples (1 to 8), it can be seen that the photosensitive material of the present invention having an alkali-soluble acrylic resin as the base polymer has high transparency to short wavelength light such as ArF excimer laser light. On the other hand, it was confirmed that conventional resists containing poly (hydroxystyrene) or novolak-based resins had an absorption of 30 or more per 1 μm at a wavelength of 193 nm and hardly pass the ArF excimer laser light.
    In addition, since the photosensitive material of the present invention is not a chemically amplified resist that uses a catalytic reaction with an acid, there is no possibility that problems caused by the chemically amplified resist may occur. That is, chemically amplified resists have a two-stage reaction between acid generation reaction during exposure and catalytic reaction during PEB, and thus, the effect of stability of catalytic acid on time, temperature, and atmosphere, in particular, the time from exposure to PEB If the interval is large and the interval is long, pattern formation may not be possible (time delay effect). Roschert et al., Proc, SPIC 1672, 22 (1992) and the like.
    Therefore, it is predicted that the photosensitive material of this invention has the outstanding environmental stability, without being influenced by time, temperature, etc.
    (Comparative Example)
    To the polymer obtained in Synthesis Example 1, triphenylsulfonium triplate as an acid generator was added to the polymer in an amount of 1% by weight to obtain a cyclohexanone solution, except that this solution was used in the same manner as in Example 1 above. The resist film was formed. This resist film was exposed by irradiating with ArF excimer laser light (NA = 0.55), which was immediately heated at 150 ° C. for 90 seconds after exposure, and further developed with a 2.38% aqueous alkali solution of TMAH as an alkaline developer. As a result, the line and base pattern of 0.25 micrometer was partially resolvable by the DOSE amount of 30 mJ / cm <2> . However, it was confirmed by an optical microscope that the adhesion between the resist pattern and the substrate was poor and uneven peeling occurred in the resist film.
    From the results of the above Examples (9 to 12), it was found that the formation and transfer of patterns can be performed by the PCM method using the photosensitive material of the present invention.
    As described above, according to the present invention, a fine resist pattern having excellent environmental stability, high transparency to short wavelength light such as an ArF excimer laser and an electron beam, and high adhesion to the substrate is formed by alkali development. A photosensitive material that can be provided is provided. Furthermore, by exposing the upper layer with an ArF excimer laser or an electron beam by the PCM method, and exposing the lower layer with a KrF excimer laser or an ArF excimer laser, a good pattern can be formed and transferred. In addition, by using the manufacturing method of the electronic component of the present invention using the resist pattern formed by such a method as an etching mask, it is possible to faithfully transfer a very fine pattern to a substrate or the like. The photosensitive material of the present invention is useful for photolithography techniques such as microfabrication of high density devices.
    权利要求:
    Claims (23)
    [1" claim-type="Currently amended] A photosensitive material comprising an alkali-soluble resin portion and a diazo compound portion having at least one of an alicyclic skeleton and a condensed polycyclic skeleton.
    [2" claim-type="Currently amended] The photosensitive material as claimed in claim 1, wherein the diazo compound is a naphthoquinone diazide compound.
    [3" claim-type="Currently amended] The photosensitive material of Claim 1 whose said alkali-soluble resin part contains an alicyclic skeleton and the said alicyclic skeleton is a compound which has a substituted or unsubstituted menthyl group.
    [4" claim-type="Currently amended] The photosensitive material as claimed in claim 1, wherein the alkali-soluble resin moiety comprises a condensed polycyclic skeleton, and the condensed polycyclic skeleton is a compound having a substituted or unsubstituted naphthyl group.
    [5" claim-type="Currently amended] The said alkali-soluble resin part is resin formed by copolymerizing the vinyl or acryl compound which has at least one of an alicyclic skeleton and a condensed polycyclic skeleton with another monomer, The said diazo compound part is a said alkali-soluble resin, Is a photosensitive material included as a separate component.
    [6" claim-type="Currently amended] The photosensitive material of Claim 5 whose compounding quantity of the said diazo compound is 20 to 60 weight% with respect to the said alkali-soluble resin.
    [7" claim-type="Currently amended] The photosensitive material as claimed in claim 5, wherein the diazo compound is a naphthoquinone diazide compound.
    [8" claim-type="Currently amended] The photosensitive material of Claim 5 whose said alkali-soluble resin contains an alicyclic skeleton and the said alicyclic skeleton is a compound which has a substituted or unsubstituted menthyl group.
    [9" claim-type="Currently amended] The photosensitive material according to claim 5, wherein the alkali-soluble resin includes a condensed polycyclic skeleton, and the condensed polycyclic skeleton is a compound having a substituted or unsubstituted naphthyl group.
    [10" claim-type="Currently amended] The said alkali-soluble resin part is resin formed by copolymerizing the vinyl or acrylic compound which has at least one of an alicyclic skeleton and a condensed polycyclic skeleton, and the vinyl or acrylic monomer which has a diazo compound in a side chain, The photosensitive material in which a diazo compound part is contained in the same component as an alkali-soluble resin part.
    [11" claim-type="Currently amended] The photosensitive material as claimed in claim 10, wherein the diazo compound is a naphthoquinone diazide compound.
    [12" claim-type="Currently amended] The photosensitive material of Claim 10 whose said alkali-soluble resin contains an alicyclic skeleton and the said alicyclic skeleton is a compound which has a substituted or unsubstituted menthyl group.
    [13" claim-type="Currently amended] The photosensitive material of Claim 10 whose said alkali-soluble resin contains a condensed polycyclic frame | skeleton, and the said condensed polycyclic frame | skeleton is a compound which has a substituted or unsubstituted naphthyl group.
    [14" claim-type="Currently amended] Forming a film on the substrate comprising a photosensitive material containing an alkali-soluble resin portion and a diazo compound portion having at least one of an alicyclic skeleton and a condensed polycyclic skeleton;
    Performing exposure by irradiating actinic radiation to a predetermined region of the photosensitive material film; and
    A pattern forming method comprising the step of dissolving and removing the exposed portion or unexposed portion of the photosensitive material film after the exposure with an aqueous alkali solution.
    [15" claim-type="Currently amended] 15. The lower photosensitive material according to claim 14, wherein the photosensitive material film is formed as a photosensitive material film of the uppermost layer of the laminated film formed by stacking two or more photosensitive material films, and becomes an underlayer on the substrate before the step of applying the photosensitive material film on the substrate. A process of forming a material film, and a resist pattern forming method comprising a process of transferring the obtained photosensitive material film pattern to the lower photosensitive material film after the developing step.
    [16" claim-type="Currently amended] Forming an underlayer photosensitive material film on the substrate,
    Forming an upper photosensitive material film containing a substituted or unsubstituted polycyclic condensed aromatic ring,
    Irradiating a predetermined region of the upper photosensitive material film with first actinic radiation to perform exposure;
    Dissolving and removing the exposed portion or unexposed portion of the upper layer photosensitive material film after the exposure with an aqueous alkali solution, and developing them; and
    After the developing step, the obtained upper layer photosensitive material film pattern is used as a mask to collectively irradiate the second actinic radiation having a wavelength longer than the first actinic radiation, and to perform the developing treatment to selectively dissolve and remove the exposed portion, thereby forming the upper layer. The resist pattern formation method provided with the process of transferring the photosensitive material film pattern to the said lower photosensitive material film.
    [17" claim-type="Currently amended] The method of claim 16, wherein the first actinic radiation is ArF excimer laser light and the second radiation is light having a wavelength of 200 to 260 nm.
    [18" claim-type="Currently amended] The resist pattern forming method according to claim 16, wherein the lower photosensitive material film comprises a phenolic resin.
    [19" claim-type="Currently amended] The resist pattern forming method according to claim 16, wherein the upper photosensitive material film contains a vinyl copolymer containing a substituted or unsubstituted polycyclic condensed aromatic ring.
    [20" claim-type="Currently amended] Forming an underlayer photosensitive material film on the substrate,
    Forming an upper photosensitive material film containing a substituted or unsubstituted benzene ring or a polycyclic condensed aromatic ring;
    Irradiating an electron beam to a predetermined region of the upper photosensitive material film to perform exposure;
    Dissolving and developing the exposed portion or unexposed portion of the upper photosensitive material film after the exposure with an aqueous alkali solution, and
    After the developing step, the obtained upper photosensitive material film pattern is collectively irradiated with light having a wavelength of 190 to 260 nm, and subjected to a developing treatment to selectively dissolve and remove the exposed portion, thereby removing the upper photosensitive material film pattern. A resist pattern formation method including the process of transferring to an underlayer photosensitive material film.
    [21" claim-type="Currently amended] The method of forming a resist pattern according to claim 20, wherein said lower photosensitive material film comprises an acrylic resin having an alicyclic skeleton.
    [22" claim-type="Currently amended] Forming a film on the substrate comprising a photosensitive material containing an alkali-soluble resin portion and a diazo compound portion having at least one of an alicyclic skeleton and a condensed polycyclic skeleton;
    Performing exposure by irradiating actinic radiation to a predetermined region of the photosensitive material film;
    A step of dissolving and developing the exposed portion or the unexposed portion of the photosensitive material film after the exposure with an alkaline developer to form a patterned photosensitive material film, and
    The manufacturing method of the electronic component provided with the process of transferring a pattern on a board | substrate using the obtained photosensitive material film pattern as an etching mask.
    [23" claim-type="Currently amended] 23. The lower photosensitive material according to claim 22, wherein said photosensitive material film is formed as a photosensitive material film of the uppermost layer of a laminated film formed by laminating two or more photosensitive material films, and becomes an underlayer on a substrate before the step of applying said photosensitive material film on a substrate. A process of forming a material film, and a process of transferring the obtained photosensitive material film pattern to a lower photosensitive material film after the step of developing the uppermost photosensitive material film with an aqueous alkali solution.
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    同族专利:
    公开号 | 公开日
    US6228552B1|2001-05-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-09-13|Priority to JP24378696
    1996-09-13|Priority to JP96-243786
    1997-09-12|Application filed by 니시무로 다이조, 가부시끼가이샤 도시바
    1998-07-06|Publication of KR19980024609A
    优先权:
    申请号 | 申请日 | 专利标题
    JP24378696|1996-09-13|
    JP96-243786|1996-09-13|
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