JPS6245973B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an image forming method that allows correction of exposed areas. For example, in the manufacture of semiconductors, photoresists are generally used, and because of their excellent resolution, positive resists containing o-quinonediazide compounds as a main component are often used. Many photomasks to which this photoresist is applied have a metal such as chromium deposited on a glass plate in the form of an image. These photomasks are usually divided into three types according to their usage: one is a "working" one for printing silicon wafers, and the other is a "master" used as an original image to reproduce the working photomask. Thirdly, it is a "reticle" for creating a master mask by printing a 1/10 scale projection. In this way, multiple masks or silicon wafers are printed from one original image, starting from a reticle and ending with printing onto a silicon wafer. Therefore, if a reticle or master mask with pinholes is mistakenly printed as an original image, a large number of defective working masks or silicon chips will be produced. At this time, rather than creating a new original image, masks with pinholes are often corrected. As a general correction method, the entire surface of the photoresist ε is coated with a spinner on an existing mask with pinholes, only the pinhole area is exposed using a pattern correction device, and then the pinhole area is removed after development. A method is used to correct defects by vapor depositing chromium. However, this conventional method has the disadvantage that many complicated steps such as resist coating, drying, exposure, development, chromium deposition, and resist removal must be repeated for correction. Therefore, the master mask with pinholes is used as an original image without modification, and after being burned into a working mask, prior to development, a simple process is applied only to the portions of the original image that correspond to the pinholes. It would be very convenient if we could prevent it from being duplicated. The same holds true when printing a master using a reticle with pinholes, and when printing a silicon chip using a working mask with pinholes. Furthermore, when producing a photomask, the pattern arrangement may be changed or patterns may be added due to design changes. Therefore, it would be very convenient to be able to easily add drawing lines to a photomask that has already been image-exposed. However, with conventional positive working resists, as it is well known, the non-image areas become soluble in the developing solution due to image exposure, so a simple process is applied to the exposed non-image areas to create new image lines. It was not possible to add . As mentioned above, in pattern formation using conventional positive photoresist, repairing a photomask with pinholes involves a very complicated process, and furthermore, It was not possible to add a drawing line to a non-drawing area. In order to eliminate the above-mentioned drawbacks, the present inventors designed a system in which, by performing a simple process on the desired exposed area after image exposure, only that area becomes insoluble in the developer. We came to the conclusion that it is possible in principle if we can do this. For example, Japanese Patent Application Laid-open Nos. 127615-1982 and 108002-1980 describe a method of making a photosensitive material that has been exposed to light and becomes soluble in a developer solution by heat treatment. , examples of printing plate materials are described. In each of the above-mentioned specifications, for example, after image exposure,
A method is disclosed in which the exposed portion is heated in an air constant temperature bath for about 10 minutes at 100° C. to make it insoluble in an alkaline developer, and then the entire surface is exposed and developed to reverse the process from positive working to negative working. However, with the method described in the above specification, it is substantially difficult to heat only a part of a fine pattern such as a pattern for producing an integrated circuit. Therefore, the present inventors investigated various methods for changing the fine parts of the exposed photosensitive material from a state soluble in a developer to an insoluble state. For example, the photosensitive layer described in the above specification was After that, only the desired part of the exposed area was irradiated with laser light and immediately developed. It was discovered that the light irradiated part was not dissolved, and the present invention was achieved. An object of the present invention is to provide a method for removing pinholes that occur when exposing a positive working resist using a photomask with pinholes. Another object of the present invention is to provide a method for printing additional lines on a positive working resist that has been image exposed. The present invention uses an o-quinonediazide compound as a main component on a support, and by irradiating the o-quinonediazide compound with a laser beam after irradiation with actinic rays,
In an image forming material provided with a photosensitive resin layer containing as a second component a compound capable of reducing the dissolution rate of the laser beam irradiated area in a developing solution to be lower than the dissolution rate of the laser beam non-irradiated area, an o- This is an image forming method capable of correcting an original image using laser light, which is characterized by exposing a quinonediazide compound to actinic rays, irradiating a desired portion of the exposed portions with laser light, and then developing the image. Supports used in the present invention include planar materials and other shapes that do not undergo significant dimensional changes. Examples of planar materials include glass, silicon oxide, ceramics, paper, metals such as aluminum, zinc, magnesium, copper, iron, chromium,
Alloys mainly composed of nickel, silver, gold, platinum, palladium, aluminum, alloys mainly composed of zinc, alloys mainly composed of magnesium, copper-zinc alloys, iron-nickel-chromium alloys, alloys mainly composed of copper alloys and metal compounds such as aluminum oxide, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ),
Polymers such as regenerated cellulose, cellulose nitride, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polystyrene, polyethylene terephthalate, polyethylene isophthalate, polycarbohydrates of bisphenol A Polyethylene, polypropylene, nylon (6-nylon, 6,6-nylon, 6,10-nylon, etc.), polyvinyl chloride-vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride- Examples include vinylidene chloride copolymer, polyacrylonitrile, polymethyl acrylate, and polymethyl methacrylate. In addition, two thin plates of the above-mentioned material are
3 or more firmly laminated materials, such as cermets, iron-aluminum laminates, iron-copper-aluminum laminates, iron-chromium-copper laminates, paper coated with polyethylene on the surface, and paper coated with cellulose triacetate on the surface. paper, an aluminum plate whose surface is anodized to form an aluminum oxide layer, a chromium plate whose surface is formed with a chromium oxide layer by a known method, a glass plate whose surface is coated with a tin oxide layer, oxidized A silicon oxide plate with a layer of indium on its surface can also be used as a support. Furthermore, as the opaque support, silicon, which is used for example in semiconductor manufacturing, is also suitably used.
In this case, the silicon may or may not have a thin silicon oxide layer on its surface. Furthermore, silicon may be doped with a different element such as phosphorus or boron in advance. Furthermore, in the present invention, glass (quartz glass, soda lime glass, potash lime glass, barium glass,
A support having a mask layer provided on a plate (such as borosilicate glass or phosphate-aluminum oxide glass) is preferably used. The mask layer is provided by depositing a mask material onto the transparent support by means such as vacuum evaporation, sputtering, ion plating, chemical plating, or the like. Mask materials include metal oxides such as silicon dioxide, chromic oxide, ferric oxide, magnetic iron oxide (iron oxide), cuprous oxide, cupric oxide, chromium, aluminum, and silver. , metals such as titanium, cobalt, tungsten, tellurium, nickel, nickel-chromium alloys, semimetals such as silicon, germanium, and combinations thereof (e.g. Cr-
Cr ₂ O ₃ , Co―Co ₂ O ₃ , Si―SiO ₂ , Si―Ge, etc.), As
There are chalcogen glasses such as -S-Ge, As-Se-Ge, and Ge-S. Although the thickness of the mask layer cannot be clearly defined as it varies depending on the application, it is generally in the range of 0.04 μm to 1.5 μm, preferably in the range of 0.05 μm to 0.3 μm. If it is too thin, the absorption of ultraviolet rays will be low, and if it is too thick, it will be difficult to etch, resulting in the problem of side etching. metal or metal oxide,
Metalloids, chalcogen glasses, etc. have much greater mechanical strength than photographic emulsion layers, and therefore provide scratch resistance to the final photomask. These supports are selected from transparent or opaque depending on the purpose of the photosensitive image forming material. When it is transparent, it is not only colorless and transparent, but also "J.
As described in "SMPTE" magazine, Vol. 67, p. 296 (1958), dyes or pigments can be added to make the material colored and transparent. In the case of opaque supports, in addition to those that are inherently opaque such as paper and metal, there are also those that are transparent materials with pigments such as dyes and titanium oxide added, and those that are surface-treated using the method described in Japanese Patent Publication No. 19068-1972. It is also possible to use paper, plastic film, etc., which have been made completely light-shielding by adding plastic film, carbon black, etc. It is also possible to use a support whose surface has been provided with fine depressions by graining, electrolytic etching, anodic oxidation, chemical etching, etc., and a support whose surface has been pretreated by corona discharge, ultraviolet irradiation, flame treatment, etc. . Furthermore, it is also possible to use a plastic support in which reinforcing agents such as glass fibers, carbon fibers, boron fibers, various metal fibers, and metal whiskers are mixed to increase the strength. The support may be provided with other coating layers, an antihalation layer, an ultraviolet absorbing layer, or a visible light absorbing layer on its surface, if necessary, to facilitate bonding. Next, the photosensitive layer will be explained. The photosensitive layer is made of a photosensitive resin composition containing an o-quinonediazide compound as a main component. In the photosensitive resin composition, in addition to the o-quinonediazide compound (A), the dissolution rate of the laser beam irradiated portion of (A) in the developer after exposure to actinic rays is compared with the dissolution rate of the laser beam non-irradiated portion. A second component that can be reduced in size and optionally a binder is included. Here, as the second component, amines, nitrogen-containing cyclic compounds other than amines, aromatic hydrocarbons having hydroxyl groups, aromatic carbonyl compounds, and various dyes are used. Furthermore, two or more of these second components can be used in combination. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases its solubility in an alkaline solution by irradiation with actinic light, and compounds with various structures are known, for example, J. “Light―” by KOSAR
Sensitive Systems” (John Wiley & Sons,
Inc., published in 1965). Particularly suitable are sulfonic acid esters of various hydroxyl compounds and o-benzoquinonediazide or o-naphthoquinonediazide. A typical example is 2,2'-dihydroxy-diphenyl-
Bis-[naphthoquinone-1,2-diazide-5-
sulfonic acid ester], 2,2',4,4'-tetrahydroxydiphenyl-tetra[naphthoquinone-
1,2-diazido-5-sulfonic acid ester],
2,3,4-trioxybenzophenone-bis-
[Naphthoquinone-1,2-diazide-5-sulfonic acid ester], etc.
Polyhydroxyphenyl and naphthoquinone-1,2-diazide-5- obtained by condensation polymerization of acetone and pyrogallol described in Publication No. 28403
Sulfonic acid esters can be used advantageously. As the amine of the second component, in addition to aliphatic primary amines such as monostearylamine, aromatic primary amines such as aniline, secondary amines or tertiary amines can be used. Examples include dialkylamines, trialkylamines, secondary or tertiary amines having a hydroxyl group (hereinafter referred to as hydroxyalkylamines), dialkylamino aromatic hydrocarbons, and cyclic polyamines. Specific examples of dialkylamines include:
Examples include diamylamine, diheptylamine, and didecylamine. Specific examples of trialkylamine include tributylamine, triamylamine, trihexylamine, and triisoamylamine. Specific examples of hydroxyalkylamines include diethanolamine, N-methylethanolamine, N-methyldiethanolamine, dipropanolamine, and triethanolamine. Specific examples of dialkylamino aromatic hydrocarbons include diethylaniline and dipropylaniline. A specific example of the cyclic polyamine is hexamethylenetetramine. The second component used in the present invention further includes a cyclic 5 represented by the following general formula () or ().
There are ring-membered compounds, specifically the compounds shown in Table 1 are shown as examples.

【formula】

[Formula] (However, in the formula, X is =S, =O, =Se,

[Formula]=N-Rc, an organic atomic group, Ra, Rb, Rc, Y are organic atomic groups not containing a carboxylic acid group, and Z represents N or C. )

【table】

【table】

【table】

【table】

【table】

[Table] In addition to the heterocyclic compounds represented by the above general formulas () and (), examples of the second component used in the present invention include nitrogen-containing heterocyclic compounds such as pyridine, triazine, quinoline, imidazole, indoline, oxazoline, and thiazoline. Compounds with cyclic groups are also effective. Among these compounds having a nitrogen-containing heterocyclic group, spiropyran compounds represented by the following general formula () are particularly preferably used. The second essential component of the photosensitive layer is a compound represented by the general formula below. In the formula, X represents S, O, Se, Te, C(CH ₃ ) ₂ , Y and Z each represent C or N,
R ₁ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₃ , R ₄ , and R ₅ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, a nitro group, amino group, halogen atom, nitrile group, formyl group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, or R ₂ and R ₃ and R ₄ and R ₅ are bonded at one end to form a cyclic Eggplant represents C=C-C=C-. Many compounds represented by the above general formula () are known, and these compounds are described in, for example, "Photochromism" by Glenn H. Brawn (Wiley-Interscience, Inc.).
New York, 1971), pages 45 to 294. Representative compounds include the following. Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 7 Compound 8 Compound 9 compound 10 compound 11 compound 12 compound 13 compound 14 compound 15 compound 16 compound 17 compound 18 compound 19 compound 20 compound 21 compound 22 compound 23 compound 24 compound 25 compound 26 compound 27 compound 28 compound 29 compound 30 compound 31 compound 32 compound 33 compound 34 compound 35 compound 36 compound 37 As the aromatic hydrocarbon having a hydroxyl group, an aromatic hydrocarbon having one or more hydroxyl groups that can be esterified or etherified can be used.
Examples of the aromatic hydrocarbon having a hydroxyl group include a resin having a benzene ring having a hydroxyl group and a hydroxybenzene compound. Specific examples of the resin having a benzene ring having a hydroxyl group include phenol formaldehyde novolac resin and cresol formaldehyde novolac resin. Specific examples of hydroxybenzene compounds include pyrogallol, phloroglucinol, and 2,2-bis(4-hydroxyphenyl)propane. Specific examples of 1-hydroxyethyl-2-alkylimidazolines include compounds in which the alkyl group has 7 to 17 carbon atoms, and mixtures thereof. Examples of the carbonyl group-containing compound used as the second component of the present invention include acyloin such as benzoin, toluoin, anisoin, and furoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin sec-butyl ether, and toluoin methyl ether. Acilloin derivative, benzophenone, phenyltolyl ketone, 2-chlorobenzophenone, 2-chloroacetophenone, benzyl,
Aryl ketones such as 2,2'-dimethylbenzene and Michler's ketone, fluorenone, phenyl β-
Aromatic ketones in which an oxo oxygen atom is bonded to a carbon atom forming a ring such as naphthyl ketone, anthrone, benzanthrone, 10,10′-pianthrone, anthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2- Methylanthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 1-bromoanthraquinone, 2-chloroanthraquinone, phenanthraquinone, 1-methylphenanthraquinone,
Examples include condensed quinones such as 4-ethylphenanthraquinone, 2-chlorophenanthraquinone, 3-bromophenanthraquinone, 2,7-di-t-butylphenanthraquinone, and benzanthraquinone. can. A very wide range of compounds are useful as dyes for use as the second component of the present invention. Specifically, Direct Fast Yellow R (C.
I.29025) (CI is "Color Index" 3rd edition (The
Society of Dyers and Colourists, Bradford
England and the American Association of
Textile Chemists and Colorists，Research
Color by Triangle Park, USA, published in 1971)
Represents the Index Constitution Number. ), Direct Fast Yellow GC (CI29000), Sumilite Supra Yellow BC conc (CI19555), Chrysamine G (CI22010), Direct Fast Yellow 5GL (CI25300), Benzocaprol Yellow
GRL (CI29020), Direct Fast Orange S (CI29150), Neoza Panlet GE (C.
I.12715), Pomegranate GE (C.
I.12716), Palifastbratsk #3804 (C.
I.12195), diazo dyes such as Alizarin Yellow R (CI14030), Oil Red #330 (C.
I.60505), Oil Violet #730 (C.
I.60725), Oil Violet #732 (C.
I.61705), Oleosol Blue G (CI61525),
Anthraquinone dyes such as Sumiplast Green G (CI61565), Japanese Thren Yellow GCN (CI67300), Japanese Thren Violet D/P (CI68700), Acid Violet 5B (C.
I.42640), Patent Pure Blue VX (C.
I.42045), Patent Blue AF (CI42080), Lacto-Brilliant Blue FCF (CI42090), Brilliant Acid Blue R (CI42645), Soracyanine 6B conc (CI42660), Orient Soluble Blue OBB (CI42780), Sumitomo Brilliant Blue 5G (CI42120), Acid Brilliant Milling Green B (CI42100), Eisen Auramine O-125 (CI41000), Paramagenta Base (CI42500), Eisen Methyl Violet
BB Special (CI42535), Eisen Crystal Violet Power (CI42555), Magenta (CI42510), Eisenbasic Cyanine 6GH
(CI42025), pyrimocyanin BX conc (C.
I.42140), Crampons Victoria Piure Blue BOH
(CI42595), Rose Aniline (CI622), Eisen Victoria Blue BH (CI44045), Eisen Diamond Green GH (CI42040), Malachite Green (CI42000), Mitsuichrome Brilliant Red RX (CI43565), Phenol Red (α-hydroxy- γ of α,α-bis(4-hydroxyphenyl)-o-toluenesulfonic acid
-Sulton), Eisenrhodamin BH (C.
I.45170), Rhodamine 6GCP (CI45160), Sumimicromin Brilliant Red B (CI45305), Rose Bengal (CI45440), Eosin Y (C.
I.45380), fluorescein (CI45350), carbonium dyes such as acridine orange (CI46005), Sakuranin OK70 (CI50240), Eisenkati Long Gray BLH (CI11825), Eisenbasic Piure Blue 5GH (CI51005), Methylene Blue FZ (CI52015) ), new methylene blue
NS conc (CI52030), basic blue GO
Quinoneimine dyes such as (CI52025), methine dyes such as Astrazone Pink FG (CI48015),
Examples include copper phthalocyanine dyes such as Oil Blue #15 (CI74350). Regarding dyes other than these, as auxochromes,
Dyes having an amino group, an alkyl-substituted amino group, or a hydroxyl group can be used. Of the second components mentioned above, compounds other than dyes are of course effective alone, but in order to increase laser sensitivity, it is recommended to add one kind of second component other than dyes to a dye with high laser light absorption efficiency. It is particularly effective to use the above combinations. The amount of the second component to be used is about 0.005 parts by weight to about 10 parts by weight, preferably about 0.01 parts by weight to about 10 parts by weight in the case of aromatic hydrocarbons having a hydroxyl group or citric acid per 1 part by weight of the o-quinonediazide compound. 3
When compounds other than these are used, the amount ranges from about 0.005 parts by weight to about 1 part by weight, preferably from about 0.01 parts by weight to about 0.3 parts by weight. In addition to the above-mentioned components, various additives can be added to the photosensitive resin composition used in the method of the present invention. For example, pigments such as phthalocyan blue can be added to improve image clarity.
In addition, to increase image strength or as a binder, resins that can be mixed uniformly with the above components, such as styrene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, etc.
Acrylic acid copolymers, methacrylic acid-methyl methacrylate copolymers, etc. can also be added. Since these techniques are well known to those skilled in the art, further detailed explanation will be omitted. The photosensitive resin composition having the above composition is
Applied on top of the support. The photosensitive resin composition can be made into a photosensitive resin composition solution using a solvent if necessary and applied onto the support. The solvent can be appropriately selected from known solvents that do not impair the photographic properties of the photosensitive resin composition. The method for applying the photosensitive resin composition or its solution onto the support can be appropriately selected from known methods. A typical application method is a coating method, which can be easily carried out by those skilled in the art according to known methods. The image recording material formed as described above is o
- Imagewise exposure of the quinonediazide compound to actinic light (usually light with a wavelength of about 290 nm to 500 nm) using a conventional method. Mercury lamp as a light source of active rays,
Xenon lamps, carbon arc lamps, tungsten lamps, fluorescent lamps, sunlight, etc. can be used. The photosensitive material imagewise exposed to the actinic rays of the o-quinonediazide compound is then scanned and exposed to a laser beam. It is obvious that a visible light laser is desirable as a laser for image recording used in the present invention, since lasers that emit infrared or ultraviolet light that are invisible to the human eye have problems in handling. Visible light lasers include helium and neon lasers,
Ion lasers such as argon and krypton, helium and cadmium lasers, etc. can be used. Among these lasers, argon ion lasers and helium neon lasers are particularly suitable since they provide beams with good stability. In addition to these, lasers other than those in the visible region, such as YAG laser light, can also be used. The image forming material processed in this way is then subjected to a development process. The developer used in the development process can be selected from many known developers conventionally used for developing photosensitive layers containing o-quinonediazide compounds. That is, it can be easily developed by immersion or washing with an alkaline solution. Preferred alkaline solutions include aqueous solutions containing inorganic compounds such as caustic soda, caustic potash, sodium silicate, potassium silicate, tribasic sodium phosphate, tribasic potassium phosphate, sodium carbonate, and potassium carbonate, or ethanolamine, diethanolamine, and triethanol. Examples include aqueous solutions containing organic bases such as amines and tetramethylammonium hydroxide, and in some cases organic solvents,
A surfactant or the like may also be included. The photosensitive material that has been subjected to development processing is used for many purposes. For example, if a grained aluminum substrate is used as a support, good printed matter can be obtained by applying it to a printing machine after development. Further, if a photosensitive layer containing a dye is provided on a transparent plastic film such as a polyester film, it can be used for printing proofing. Furthermore, the support for the developed photosensitive layer may be subjected to various processing depending on the purpose. For example, when using a chromium vapor deposited film provided on a glass substrate as a support, the chromium vapor deposited film is etched using a known etching solution containing ceric ions, etc., using the photosensitive layer remaining after development as an etching resist. The resist can then be removed and used as a hard mask. Furthermore, when a silicon substrate is used as a support, it can also be used in the etching process and lift-off process of the silicon oxide film layer. Furthermore, when using a copper foil substrate for a printed wiring board, it can be used as an etching resist or a plating resist after development. One of the special and preferred embodiments of the method of the present invention is a mode in which the development of the photosensitive resin composition layer and the etching of the mask layer are simultaneously carried out in one processing solution (hereinafter referred to as the one-bath development etching method). ). Examples of the mask layer that can implement this embodiment include a tellurium layer, a chalcogen glass layer, an aluminum layer, and a layer containing a mixture of aluminum and noble metals. At the same time that the composition layer is dissolved or swollen in an imagewise manner and removed (that is, developed), the alkaline processing liquid reaches the mask layer and the mask layer is similarly etched and removed in an imagewise manner. A preferred mask layer for performing a one-bath development etching method using an alkaline processing solution is a layer in which aluminum and noble metal are mixed. Examples of the alkaline processing solution that can be used in the one-bath development etching method (hereinafter referred to as one-bath development etching solution) include an aqueous solution containing an inorganic alkaline substance, a water-organic solvent mixture solution, or an organic solvent solution. can. Inorganic alkaline substances include alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium), alkaline earth metal hydroxides (e.g., magnesium hydroxide), hydroxide ammonium, alkali metal phosphites (e.g. disodium phosphite, dipotassium phosphite), alkali metal phosphates (e.g. trisodium phosphate, tripotassium phosphate), alkali metal metasilicate (e.g. sodium metasilicate, meta potassium silicate), alkali metal carbonates (e.g., dilithium carbonate, disodium carbonate,
dipotassium carbonate, dicesium carbonate). Among these inorganic alkaline substances, alkali metal hydroxides, alkali metal phosphites,
Alkali metal phosphates and alkali metal metasilicate salts are preferred, and among them, sodium salts are most preferred because of their low cost. Next, as organic solvents, alcohol, ketone,
fatty acid ester, hydroxyalkyl ether,
Fatty acid esters of hydroxyalkyl ethers can be mentioned. Specific examples of alcohol include methanol, ethanol, propanol, butanol, isopropyl alcohol, and furfuryl alcohol. Specific examples of ketones include acetone and methyl ethyl ketone. Specific examples of fatty acid esters include methyl formate, methyl acetate, and ethyl acetate. Specific examples of hydroxyalkyl ethers include methyl cellosolve (2-methoxyethanol), ethyl cellosolve (2-ethoxyethanol), and phenyl cellosolve (2-phenoxyethanol). Specific examples of fatty acid esters of hydroxyalkyl ethers include 2-methoxyethyl acetate, 2
- Ethoxyethyl acetate can be mentioned. Among these organic solvents, alcohols and hydroxyalkyl ethers are preferred. Moreover, these organic solvents can be used in combination of two or more types. A mixed medium of these organic solvents and water is a preferable solvent, and among these, a mixed solvent in which the amount of the organic solvent is about 10% or less of the water by volume is particularly preferable. The one-bath development etching solution is a solution in which an inorganic alkaline substance is dissolved in the above-mentioned solvent, and can contain an oxidizing agent, a stabilizer for the alkaline substance, and a surfactant, if necessary. Among these, a single-bath developing etching solution containing an oxidizing agent oxidizes and eliminates microbubbles of hydrogen gas generated during etching of the mask layer, and also oxidizes the metal constituting the mask layer. This is preferred because the etching speed can be increased. Examples of oxidizing agents include bromic acid or its metal salt, iodic acid or its metal salt, metaperiodic acid or its metal salt, orthoperiodic acid or its metal salt, which are described in JP-A-52-99101. Metal salts (examples of metals for each of the above include sodium or potassium), chlorite or its metal salts, chlorite or its metals as described in JP-A No. 50-2925 salts, perchloric acid or its metal salts (examples of metals for each of the above include sodium or potassium), other bromite or its sodium or potassium salts, cerium () compounds, sulfuric acid, nitric acid or nitrates Examples include sodium nitrate, potassium nitrate, and hydrogen peroxide. The amount of the inorganic alkaline substance that can be contained in the single-bath developing etching solution ranges from about 0.05% to about 8%, preferably from about 0.01% to about 5% by weight based on the total amount of the solution. be. The amount of oxidizing agent that can be contained in the single-bath developing etching solution ranges from about 0.05% to about 0.05% by weight based on the total amount of the solution.
It ranges up to 10%, preferably from about 0.1% to about 7%. The one-bath development etching solution contains potassium chloride, sodium borate, sodium hydrogen carbonate, which are described in JP-A-49-34323 as stabilizers for alkaline substances, or trisodium phosphate, which also acts as an alkaline substance. Approx. weight ratio of sodium metasilicate to alkaline substance
The content can range from 50% to about 200%. In addition, the one-bath development etching solution contains phosphoric acid, phosphorous acid, or a mixture thereof as an etching agent or an etching accelerator as described in JP-A-53-14002 and JP-A-53-49508. The content and the type and content of auxiliary agents added at the same time are disclosed in Japanese Patent Application Laid-open No. 1983-
14002 and JP-A-53-49508 can be followed. Furthermore, a known surfactant is added to the one-bath development etching solution in a weight ratio of about 0.005% to about 2%, preferably about 0.01%, based on the total amount of the solution.
% to about 0.3%. The PH of the monobath developing etching solution ranges from about 10 to about 14, preferably from about PH 10.5 to PH 13.5. The temperature of the solution during the single-bath development and etching process ranges from about 15°C to about 40°C, preferably from about 20°C to about 35°C. Specific processing methods for carrying out single-bath development and etching processing include dipping method,
Examples include a spray method, a method using an automatic developing device, or a similar mechanical device. In either case, the time required to complete the development and etching process ranges from about 5 seconds to about 60 seconds, preferably about
The components of the one-bath developer so that it takes from 10 seconds to about 40 seconds,
Select the concentration, PH, and temperature and carry out the test. In addition, in order to quickly and completely remove the portion of the mask layer that should be etched, a brush, sponge, cotton pad, etc. is used to remove the photosensitive resin composition layer of the photomask forming material during or after the development and etching process. and the mask layer can be lightly rubbed. Example 1 1 part by weight of 1,2-naphthoquinonediazide-5-sulfonic acid ester of polyhydroxyphenyl obtained by polycondensation of acetone and pyrogallol as described in Example 1 of Japanese Patent Publication No. 43-28403,
Phenol resin (manufactured by Sumitomo Durez Co., Ltd., product name)
PR-50904, 2 parts by weight of polymerization degree 3-10), 0.4 parts by weight of triethanolamine, methyl ethyl ketone
A photosensitive solution was prepared by dissolving the mixture in 20 parts by weight and 20 parts by weight of methylcellosolve acetate and passing through a filter having a pore size of 0.5 μm. In addition, a vacuum evaporated film with a thickness of 700 Å was prepared on a 2.5-inch square (1.6 mm thick) clean soda-lime glass substrate by co-depositing aluminum with 98.5 atoms and iron with 1.5 atoms. did. The above-mentioned photosensitive liquid was applied onto the vapor deposited film of this substrate using a spin coater so that the dry film thickness was 0.6 μm, and dried to produce two photosensitive plates, photosensitive plates a and b, respectively. did. Next, a chrome mask for resolution testing with a pinhole of 10 μm in diameter in the image area was prepared, and for photosensitive plate a, a 2KW ultra-high pressure mercury lamp (manufactured by Oak Co., Ltd.) was used.
A contact exposure (image exposure) was performed for 20 seconds at a position 55 cm from the camera. Next, an argon ion laser beam that emits visible light with a wavelength of 514.5 nm (beam diameter is 20 μm on the mask surface, energy is 500 nm) is placed in close contact with the laser beam.
Only the pinhole portion of the mask was exposed to light for 1 second at a power (mW). For sample b, this laser beam irradiation was not performed. These photosensitive plates were mixed with 4 parts by weight of sodium hydroxide,
A developer solution (31
℃), removed after 25 seconds, washed with water, and dried. For both photosensitive plates a and b, the photosensitive layer and vapor deposited layer in the exposed area during image exposure are eluted, and the photosensitive layer and vapor deposited layer in the non-exposed area remain on the support, resulting in a positive working photomask image corresponding to the original image. However, in case of b, the pinholes in the original image were duplicated, and pinholes were also generated on photosensitive plate b. On the other hand, with regard to a, the pinholes in the original image were not duplicated and had good performance as a photomask. Example 2 A photosensitive layer with a dry film thickness of 0.6 μm was prepared in the same manner as in Example 1 except that compounds c to g shown in Table 3 were used instead of triethanolamine in the photosensitive solution used in Example 1. A photosensitive plate was prepared and subjected to the same treatment as photosensitive plate a in Example 1. As with photosensitive plate a in Example 1, a good photomask without pinholes in the original image was fabricated. Example 3 A photosensitive plate h was prepared in exactly the same manner as the photosensitive plate in Example 1, except that rose aniline (CI622) was used instead of triethanolamine in the photosensitive solution used in Example 1. When the photosensitive plate a was subjected to the same treatment as in Example 1, a good photomask without pinholes was produced, similar to photosensitive plate a in Example 1. Example 4 Oil Blue #15 (C.
A photosensitive plate was prepared in exactly the same manner except that a photosensitive plate (I.74350) was used, and after image exposure was performed in the same manner as photosensitive plate a in Example 1, helium neon was applied to the areas corresponding to the pinholes in the original image. Laser light (beam diameter 20 μm, energy 10 mW) was irradiated for 2 seconds. Next, development was performed in the same manner as for photosensitive plate a, and a good photomask without pinholes was produced. Example 5 Chromium was deposited on the glass plate used in Example 1 to a thickness of 1000 Å by vacuum evaporation to produce a substrate. The photosensitive liquid prepared in Example 5 was applied onto the vapor deposited film of this substrate in the same manner as in Example 1 to produce a photosensitive plate i having a photosensitive layer with a thickness of 0.6 μm. For this i, after image exposure was carried out in the same manner as in Example 4, helium neon laser light was irradiated on the part of the original image corresponding to the pinhole, immersed in the developer used in Example 1 for 18 seconds, washed with water, and dried. As a result, the photosensitive layer in the exposed area during image exposure was eluted and removed, but the area irradiated with laser light was not eluted. Next, the photosensitive plate i was heated at 100℃ for 5 minutes in an air constant temperature bath, and after cooling, nitric acid (61% weight concentration)
ml, ceric ammonium nitrate 125g, water 800g
ml was mixed and dissolved in an etching solution for 1 minute at 25°C and washed with water. The relief of the photosensitive layer formed by the development process acted as an etching resist and a positive working photomask image was obtained. . The photomask image formed on the photosensitive plate i is a good image with almost no pinholes in the image area and no fogging in the non-image area, similar to the photomask image obtained in Example 1. 2.0μm
The line width was well resolved. The transmission optical density of the mask layer in the image area was 3.0. Further, when the photosensitive plate i was immersed in methyl ethyl ketone at 25° C. for 1 minute, the photosensitive layer remaining on the chromium layer was removed, and a positive working chromium vapor deposited film pattern was obtained. Example 6 In place of the triethanolamine used in Example 1, Eisenvig triapiure blue BOH
Photosensitive plate j was prepared in exactly the same manner as a except that (CI42595) was used. A good original image with no pinholes is brought into close contact with the image and exposed in the same manner as in Example 1, and then a helium neon laser beam (on the photosensitive surface) is applied to the non-image area (exposed area) of the original image. Beam diameter 20μm, energy 10m
W) was scanned and exposed for 1 cm at a speed of 1 cm/sec. When the photosensitive plate a in Example 1 was then developed using the same method, a photosensitive layer and a vapor deposited layer remained on the photosensitive plate corresponding to the image lines of the original image (positive working image), and The photosensitive layer and vapor deposited layer remain even in the area scanned by the laser beam,
A drawing line that was not in the original drawing was added and recorded.

Claims (1)

[Claims] 1 By irradiating a support with an o-quinonediazide compound as a main component and after irradiating an o-quinonediazide compound with actinic rays as a second component, the dissolution rate of the laser-irradiated portion in a developer can be determined by laser light. In an image forming material provided with a photosensitive resin layer containing a compound that can reduce the dissolution rate compared to the non-irradiated area, o-
An image forming method capable of correcting an original image using laser light, which comprises exposing a quinonediazide compound to actinic rays, irradiating a desired portion of the exposed portions with laser light, and then developing the image.