CA2001852A1 - Process and apparatus for the formation of negative resist pattern - Google Patents
Process and apparatus for the formation of negative resist patternInfo
- Publication number
- CA2001852A1 CA2001852A1 CA 2001852 CA2001852A CA2001852A1 CA 2001852 A1 CA2001852 A1 CA 2001852A1 CA 2001852 CA2001852 CA 2001852 CA 2001852 A CA2001852 A CA 2001852A CA 2001852 A1 CA2001852 A1 CA 2001852A1
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- CA
- Canada
- Prior art keywords
- resist
- water
- carboxyl
- sensitizer
- plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
ABSTRACT
A negative resist pattern is formed using a resist containing a diazoquinone sensitizer. An imagewise ex-posed area of a layer of the resist is subjected to heat treatment with a water-containing heating medium in the presence of a carboxyl-inactivating agent. The entire surface of the layer is exposed to radiation. The thus-exposed surface is then treated with an alkaline devel-oper solution. An apparatus suitable for use in the practice of the above process is also disclosed.
A negative resist pattern is formed using a resist containing a diazoquinone sensitizer. An imagewise ex-posed area of a layer of the resist is subjected to heat treatment with a water-containing heating medium in the presence of a carboxyl-inactivating agent. The entire surface of the layer is exposed to radiation. The thus-exposed surface is then treated with an alkaline devel-oper solution. An apparatus suitable for use in the practice of the above process is also disclosed.
Description
E35~
TITLE OF THE INVENTION:
PROCESS AND APPARATUS FOR THE
FORMATION OF NEGATIVE RESIST PATTERN
BACKGROUND OF THE INVENTION
1) Field of the Invention:
The present invention relates to a process for the formation of a negative resist pattern and also to an apparatus suitable for use in the practice of the pro~
cess. More specifically, the present invention is con-cerned with a process for forming a negative resist pat-tern with a resist containing a diazoquinone sensitizer and also with an image-reversal developing apparatus suitable for use in the practice of the process to per-form both reversal of a positive image and development of the reversed, namely, negative image.
TITLE OF THE INVENTION:
PROCESS AND APPARATUS FOR THE
FORMATION OF NEGATIVE RESIST PATTERN
BACKGROUND OF THE INVENTION
1) Field of the Invention:
The present invention relates to a process for the formation of a negative resist pattern and also to an apparatus suitable for use in the practice of the pro~
cess. More specifically, the present invention is con-cerned with a process for forming a negative resist pat-tern with a resist containing a diazoquinone sensitizer and also with an image-reversal developing apparatus suitable for use in the practice of the process to per-form both reversal of a positive image and development of the reversed, namely, negative image.
2) Description of the Related Art:
As has been well-known, a variety o~ resists is employed widely in the fabrication of semiconductor devices and the liXe to form desired patterns on sub-strates.
These resists include negative resists and posi-tive resists. When imagewise exposed to radiation such as light, electron beams or x-rays, the exposed portion is insolubilized to a developer solution, namely, a sol-vent, whereby a negative image is provided. On the .
other hand, a positive resist turns to soluble in such a developer solution at an exposed portion so that a posi-tive pattern is provided. Making use of their respec-tive properties, these resists have found significant utility.
Many of these conventional resists are however used exclusively for the fo~ation of either negative or positive resist pattarns. ~amely, it is impossible to selectively form either a negative pattern or a positive pattern by using the same resin commonly. Inconvenient-ly, negative resists and positive resists must thus be selectively used depending on whether intended are nega-tive resist patterns or positive resist patterns. Among these resists, positive resists are superior in resolu-tion and the sharpness of printing areas to negativeresists. There is hence an outstanding demand for the improvement of the resolution of negative resists.
On the other hand, resists capable of selectively forming either negative or positive pa~terns by changing treatment conditions in spite of the use of the same sensitizer (photosensitizer), namely, so-called image reversal resists have also been developed.
Among image reversal resists of the above sort, those using as a sensitizer an o-quinonediazide compound (diazoquinone compound; hereinafter called "diazoquinone sensitizer) are mentioned as typical examples.
z The xeversal of an image formed in a resist, which uses such a diazoquinone sensitizer, is considered to take place in accordance with the following mechanism.
A diazoquinone sensitizer has the characteristic property that upon exposure (first exposure) to radia-tion, diazo groups are decomposed and at the same time, carboxyl groups are formed. Accordingly, when a posi-tive resist containing such a diazoquinone sensitizer (for example, a resist useful for imagewise e~posure lo through a positive film to ~orm a printing plate bearing a positive pattern) is exposed imagewise to radiation through a positive film by a method known per se in the art, carboxyl groups are formed in the exposed area (i.e., the area corresponding to the image-free area of the positive film), whereby upon treatment with an alkaline developer solution, the exposed area is removed to allow the unexposed area to remain as a pattern, thereby o~taining a positive ima~e.
To o~tain a negative image on the other hand, it is necessary to make the resultant carbQxyl groups inac-tive or inert to an alkaline developer solution. To make the area, which is other than that subjected to the first exposure, soluble in an alkali developer solution, after inactivation of the carboxyl groups, full-face ex-posure (second exposure) is performed, followed by de-velopment with an alkaline developer solution. As a 2a~B5i~
result, an image reversed from the aPorementioned image, i.e., a negakive image is obtained.
A variety of processes has been proposed for the inactivation of carboxyl groups formed by first exposure in a resist which contains a diazoquinone sensitizer for example, including the process in which a second component capable of promoting inacti~ation or decarboxylation ofcar-boxyl groups is added in combination with a diazoquinone sensitizer and heat treatment is applied subsequent to first exposure. Specifically described, it has been proposed to use triethanolamine (see Japanese Patent Ap-plication Laid-Open No. 127615/1974), a second or tertiary amine ~see Japanese Patent Application Laid-Open No. 108002/1975), a 1-hydroxyethyl-2-alkylimida-zoline (see Japanese Patent Application Laid-Open No.
6528/1977), a quinone compound or aromatic ketone com-pound (see Japanese Patent Application Laid-Open No.
127615/1974), a basic carbonium dye (see Japanese Patent Application Laid-Open No. 9740/1981), etc. These con-ventional reversal processes however require to conduct,subsequent to first exposure, heat traatment in air, for example, in a constant-temperature air oven maintained around-150C for a relatively long period of time, say, 10 minutes or even longer. This lies as a serious ob-stacle for practice of these processes. Further, heat-ing in such a constant-temperature air oven locally z~
results in uneven heating. These conventional processes are therefore accompanied by another serious drawback that they cannot provide any pattern of desired quality where the intended pattern is a fine pattern.
S A still further process has also been proposed, in which a resist subjected to first exposure is treated with an acidic aqueous solution such as HCl or H2SO4 to decarboxylate carboxyl groups formed by the first ex-posure (Japanese Patent Application Laid-Open No. 3633/1976). This process however requires treatment conditions of a time period as long as 4-5 minutes at a temperature of about 90C and involves inevitable corro-sion of a treatment apparatus. This process is there-fore impractical too.
SU~MA~Y OF THE INVENTION
The present inventors have carried out an ex-tensive investigation with a view toward solving the above-described drawbacks of the conventional processes.
As a result, it has been found that in a process for forming a resist pattern with a diazoquinone sensitizer capable of forming both positive and negative resist patterns, the technical feature of applying hot-water treatment for an extremely short period of time makes it possible to render carboxyl groups, which are formed in the sensitizer upon first exposure, inactive or inert to an alkaline developer solution to be used in the next step, to promote carboxylation in the unexposed area, to accelerate the treatment with the alkaline developer solution in the next step and further to obtain an reversed pattern of excellent resolution. It has also been found that in association with the hot-water treat-ment, use of a water-insolub:Le or sparingly water-soluble imidazole compound as a second component capable of directly or catalytically reacting with photochemical reaction products derived from the diazoquinone sensitizer by the first exposure can afford a pattern of extremely good resolution.
An object of this invention is therefore to pro-vide, based on these findings, novel process for forming an reversed, especially, neg~tive resist pattern with a resist which uses a diazoquinone sensitizer of the image reversal type.
Another object of this invention is to provide an image-reversal developing apparatus suitable for use in the practice of the above process.
In one aspect of this invention, there is thus provided a process for forming a negative resist pattern with a resist containin~ a diazoquinone sensitizer, which comprises subjecting an imagewise exposed area of 2S a layer of the resist to heat treatment with a water-containing heating medium in the presence of a carboxyl-5i2 inactivating agent, exposing the entire surface of the layer to radiation, and then treating the thus-exposed surface with an alkaline developer solution.
In another aspect of this invention, there is also provided an image-reversal developing apparatus for forming a negative resist pattern from a presensitized and imagewise-exposed plate carrying thereon a sensitized resist layer containing a diazoquinone sensitizer, comprising:
10(i) a means for conveying the plate through the apparatus from an inlet to an outlet;
(ii) a means for treating with a water-containing heating medium the plate transferred by the conveyor means;
15(iii) a means for eliminating the water-containing heating medium still remaining on the plate;
(iv) a means for subjecting the plate to full-face exposure; and (v) a means for developing the plate with an alkaline developer solution, and said treatment means (ii), elimination means (iii), full-face exposure mans (iv) and developing means (v) being arranged successively along the conveyor means (i) from a side of the inlet toward a side of the out-let.
The heat treatment by the water-containing heating 35~
medium, said treatment being applied for the reversal of the pattern subsequent to the first exposure, has sig-nificantly improved the drawbacks of the conventional reversal processes. Namely, the conventional heat treatment required to obtain a negative resist pattern is conducted in air. To achieve sufficient reversal ef-fects, it requires not only a temperature as high as around 150C but also a treatment time as long as 10 minutes or even longer. Heat treatmant at such a high temperature for such a long time is however not practi-cal. There has hence been a strong demand for further lowering of the treatment temperature and further shortening of the treatment time. The heat treatment of this invention, which makes use of a water-containing heating medium, permits heating under air free condi-tions. This has made it possible to complete the rever-sal at a lower temperature in a shorter time period.
Further, according to the heat treatment of this invention which makes use of a water-containing heating medium, the unexposed area (the area not exposed to radiation upon the first exposure) is brought into con-tact with the water-containing heating medium, for exam-ple, warm water. This has led to the merit that the treatment with an alkaline developer solution in the next step can be accelerated, in other words, the pro-ductivity can be increased. This may probably be at-tributed to the conversion of a portion o~ the sensitizer in the unexposed area into the corresponding carboxylic acid under t~e influance of water and heat.
The above effects are not available when the heat treat-ment is conducted using a water-free liquid, for exam-ple, paraffin alone. The use of water is therefore es-sential in the present invention.
In addition, the heat treatment with the water-containing heating medium can realize a uniform heat treatment temperature, in otherwise, can avoid uneven temperatures, thereby making it possible to obtain a negative resist pattern having excellent resolution.
The heat treatment in air involves the drawback that a negative resist pattern partially flows out upon davel-opment in an alkaline developer solution. The heattreatment of this invention does not have this problem.
Since the present invention has made it possible to form both positive patterns and negative patterns by using the same type of resists, the same type of devel-oper solution and the sama type of apparatus, ~ommonly.Unlike the conventional techniques, it is no longer needed to choose the type of resist depending on whether an original is positive or negative.
Reversed, namely, negative resist patterns formed on substrates (for example, presansitized plates) in ac-cordance with the present invention are subjected, for example, to etching, resist removal and washing in a similar manner to the conventional processes and are then used for the fabrication of semiconductor devices and the like.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a simplified schematic illustration of an image-reversal developing apparatus useful in the practice of the process of this invention for the forma-tion of an reversed, namely, negative resist pattern.
DETAILED DESCRIPTION OF THE INVENTION
As a sensitizer for making up a resin useful inthe practice of this invention, one of o-quinonediazide compounds, namely, diazoquinone sensitizers commonly known as positive sensitizers. Typical examples of this sort include hydroxybenzophenone, novolak resins, and o~
benzo- and o-naphthoquinonediazide sulfonate esters.
Representative and more specific examples of the o-quinonediazide compounds referred to above include 2,2'-dihyroxydiphenyl-bis(naphthoquinone-1,2-diazido-5-sulfonate) esters, 2,2',4,4'-tetrahydroxydiphenyl-tetra(naphthoquinone-1,2-diazido-5-sulfonate) esters, 2,3,4-trioxybenzophenone-bis(naphthoquinone-1,2-diazido-5-sulfonate) esters. In addition to these naphtho-quinone-1,2-diazido-5-sul~onate esters, 4 sulfonate esters can also be used either singly or in combination with the S-sulfonate esters.
To reverse a resist, which contains a diazoquinone sensitizer as a positive sensitizer, into a negative resist after subjecting the Eirst-mentioned resist to first exposure, one or more of various second component compounds are used in combination with the diazoquinone sensitizer in this invention as described above.
Usable as second component compounds of this sort ara various amines, 1-hydroxy-2-alkylimidazolines, quinone compounds, aromatic ketone compounds, basic carbonium dyes, imidazoline compounds, and imidazole compounds (for example, C~HloN2, 2-ethyl-4-methylimidazole) as de-scribed above.
For the efficient reversal of a resist, which con-tains one or more of the dia~oquinone sensitizers de-scribed above, into a negative resist after subjecting the first-mentioned resist to first e~posure in this in~
vention, it is particularly preferred to use one or more of water-insoluble or sparingly water-soluble imidazole compounds in view of the heat treatment with a water-containing heating medium, for example, hot water to be applied upon formation of a negative pattern.
The above-described imidazole compounds useful in the practice of this invention are represented by the following formula:
135~
R~R ' N
R"
whrein R, R', R" and R"'are independently a hydrogen atom or a substituted or unsubstituted alkyl, aryl or aralkyl group.
Specific examples of the imidazole compounds in-clude 2-phenyl-4-methylimidazole, 2-phenylimidazols, 1-benzyl-2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, etc. They may be used either sing-ly or in combination.
As a binder or base resin making up the resist useful in the practice of this invention, one or more of resins available as resist resins on the market can be used. Illustrative of the base or binder resin include phenol-formaldehyde resins, novolak cresol-formaldehyde resins, styrene-maleic anhydride copolymers, methacrylic acid-methyl methacrylate copolymers, and the like. Al-though not intended to be limited, commercially-available resist resins include "AZ1350", "AZ1370", "AZ1350J", "AS1375" and "AZlll" (all, trade names; pro-ducts of Spray Company); a series of "OFPR" (all, trade name; products of Tokyo Ohka Kogyo Co., Ltd.); "Waycoat LSI Posi Resist" (trade name; product of Hant Chemical Inc.).
The m:ixing of the sensitizer (diazoquinone 5~
sensitizers) and the second component compound with the resist resin (binder) can be practiced in a manner known per se in the art, for example, by thoroughly stirring them into an intimate mixture with a stirrer or the like. Incidentally, it is also possible to use the sec-ond component compound in a form in~orporated in the water-containing heating medium upon conducting the heat treatment for reversal. In this case, the second com-ponent compound is not mixed in the resist resin in gen-eral Although no particular limitation is imposed onthe amounts of the above additives (i.e., the sensitizer and second component) to be added to the resist resin, they may each be added, generally, in an amount of at least 1 part by waight, preferably 1-20 parts by weight, notably 5-15 parts by weight per lO0 parts by weight of the resist resin. If the amount of each of the addi-tives is smaller than 1 part by waight, there is a tendency that the intended effects may not be exhibited ~ully. Such a small amount is therefore not preferred.
In contrast, any amounts in excess of 20 parts by weight may impair the sensitivity of the resist and are hence not preferred either.
In addition to the above additives, various other additives can also be incorporated in the present inven-tion. For example, imaging materials (a variety of Z
dyes) can be added to enhance the contrast between an exposed area and an unexposed area so that the detection of non-conforming products may be facilitated.
A description will next be made of a process of this invention for forming a resist pattern on one of various substrates such as Si, SiO2 and Al substrates by using a resist which contains the above-described diazo-~uinone sensitizer capable o;E forming both positive and negative resist patterns.
Fir~t of all, a substrate which has been subjectad - in advance to washing pretreatment by a usual method is coated uniformly with the resist useful in the practice of this invention by spinning, spraying, roll-coating, dipping or the like. The thus-coated film is then prebaked, for example, in an infrared, closed-loop hot-air or convection-type oven, thereby completely eliminating the solvent from the coating filmO Although prebaking conditions vary depending on the kinds of the solvent and resist resin employed, the prebaking is gen-erally conducted for ~bout 5-30 minutes at 50-1107C.
(i) Formation of positive pattern:
After the prebaking, the coating film is exposed to radiation through a reticle or mask which bears a desired pattern. When a positive image is desired, it is only necessary to develop the thus-exposed coating film with a conventional alkaline devaloper solution.
Exemplary alkaline developer solutions include solutions of caustic soda, caustic potassium, sodium silicate, potassium silicate, tribasic sodium phosphate, tribasic potassium phosphate, sodium carbonate, potas-sium carbonate and the like. It is also possible to usealkaline developer solutions of organic bases such as tetraalkylammonium hydroxides (e.g., tetramethyl ammonium hydroxide) and trimethyl(2-hydroxyethyl)ammonium hydroxide (choline).
When treated with the above-described alkaline de-veloper solution, the exposed and solubilized area is dissolved in the developer solution and the unexposed portion of the coating film remains on the substrate.
As in conventional processes, the remaining positive coating film is then subjected to post-baking under heat treatment conditions which are determined depending on the kind of ths resist resin employed, whereby the adhe-sion between the substrate and the resist film can be enhanced to form a positive resist pattern on the sub-strate.Formation of negative pattern:
When it is desired to form a negative pattern on a substrate on the other hand, first exposure is conducted through a leticle or mask of a desired pattern. Either concurrently with or subsequently with the first ex-posure, heat treatment is conducted with hot water or a water-containing hot liquid. Thereafter, the entire surface of the coating film is exposed (second ex-posure), followed by development in an alkaline devel-oper ~olution employed widely to date. By this develop-ment, the unexposed area of 1:he coating film of theresist has been solubilized so that the unexposed area is dissolved in the developer solution. As a result, the area of the coating film of the resist, said area having been subjected to the first exposure step, remains on the substrate, so that a negative resist pat-tern of high resolution can be obtained.
In the process of this invention for the formation of a resist pattern, especially, a negative resist pat-tern, the greatest feature resides in the heat treatment by a water-containing heating medium such as hot water or a water-containing liquid, which is performed sub-sequent to the first exposure as described above.
The heat treatment is conducted for 5-180 seconds at 30-100C, preferably for 5-60 seconds, notably 5-30 seconds at 50-95C. For example, the heat treatment can be completed in 4-5 seconds using hot water of 85C.
The heat treatment can be carried out, for example, by immersing the resist-bearing substrate, which has been subjected to first exposure, in hot water or the like or by spraying hot water or the like onto the resist-bearing substrate.
Z~ 5~
The heat treatment can also be conducted using hot steam. Us2 of hot steam i8 suitable for a continuous operation because the heat treatment can be carried out in a short time, for example, at a temperature in the S neighborhood of 100C.
As liquids which may be used in combination with water, those not etching or otherwise adversely affect-ing on the resist resin are preferred. Por example, paraffin can be used.
An apparatus suitable for use in the practice of the process of this invention for the formation of an reversed, namely, negative resist pattPrn will next be described with reference to the accompanying sole draw-ing.
As has been mentioned above, the present invention has made it possible to reverse an undeveloped, i.e., latent positive pattern, which has been formed in a presensitized plate having a layer of a resist contain-ing a diazoquinone sensitizer of the image reversal type, into a positive pattern.
At a working site of a photomechanical process, it is generally necessary to install at least two t~pes of presensitized plates, one for positive patterns and the other for negative patterns. This also applies equally to developing machines. This reguirement leads to prob-lems in the initial cost and installation space and also 2~ 3$~
to the problem of cumbersomeness in operation that ei-ther one of thess two types of presensitizad plates have to be chosen depending on the type of each pattern.
The provision of an apparatus suitable for use in the practice of the process of this invention for the formation of a negative pattlern makes it possible to use a single type of developer solution and a single type of presensitized plates for the formation of both positive and negative patterns irrespective of the type of an original pattern through which the presensitized plate is exposed to radiation and moreover to solve the prob-lems described above.
One example of the apparatus suitable for use in the formation of a negative pattern in accordance with the process of this invention is illustrated in FIG. 1.
It should however be borne in mind that this invention is not necessarily limited to or by the illustrated ap-paratus.
Numeral 1 indicates a conveyor means for a pre-sensitized positive plate P. The presensitized plate P
is conveyed rightwards as viewed in the figure while being successively held bet~een a number of carrier rol-lers la,lb disposed in pairs in a face-to-face rela-tionship.
Designated at numeral 2 is a means for spraying hot water onto the presensitized plate P. Through many nozzles 2b attached to a feed line 2a which is in turn connected to an unillustrated hot water source, hot water is sprayed onto the presensitized plate P which the presensitized plate P is conveyed by the carrier rollers la,lb.
An enclosure indicated at numeral 2c is provided to prevent splashing of hot water released through the nozzles 2b.
A dryer means is indicated at numeral 3, which is equipped with lamps 3a as heat sources. Hot water - sprayed by the hot water spraying means 2 and still remaining on the presensitized plate P is removed while tha presensitized plate P travels through the dryer means.
Another enclosure designatPd at numeral 3b is pro-vided to prevent release of heat given off from the heat source lamps 3a.
Designated at numeral 4 is an exposure means for the presensitized plate P. When the presensitized plate P which has travelled through the dryer means 3 reachas the exposure means 4, the presensitized plate P is ex-posed to light irradiated from exposure lamps 4a.
A further enclosure indicat~d at numeral 4b is provided to prevent release of light irradiated from the exposure lamps 4a.
Numeral 5 indicates an ordinary developing ma-chine. ~lthough not illustrated in the drawing, the de-veloping machine is equipped with mechanisms required for development.
When it is desired to use the presensitized posi-tive plate P a negative plate, the presensitized posi-tive plate P bearing a latent positive pattern is loaded at a plate inlet lc. The presensitized plate P is then conveyed to the hot water spray means 2.
Here, hot water is sprayed onto the positive pat-tern bearing surface of the presensitized positiveplate, so that the solubility of the positive pattern in an alkaline solution is lost.
The presensitized plate which has been imparted wi~h the above-described property for the pattern by the hot w~ter spray means t2) is conveyed to the dryer means, where any remaining hot water is removed by the dryer means 3, followed by further travelling to the ex-posure means 4. Incidentally, any hot water still remaining on the presensitized plate P may be simply wiped away in this invention instead of drying it up by the dryer means 3.
The pattern-bearing surface of the presensitized plate P is next subjected to full-face exposure, whereby the unexposed area is rendered soluble in an alkaline solution The presensitized plate P is next fed into the de-35~
veloping machine 5 by the conveyor means 1, so that the une~posed area rendsred soluble to the alkaline solution is removed. Namely, prescribed developing treatment is applied.
When it is desired to use the presensitized plate as a positive plate, it is only neces~ary to feed the presensitized plate directly into the developer 5 without feeding same through the spay means 2 to ex-posure means 4. Prescribed development is then carried out by the developing machine 5.
Namely, the positive pattern formed in the pre-sensitized plate P is converted to have the same func-tions as the an ordinary negative film, so that the presensitized plate P can be developed without any prob-lem by the developing machine 5 which uses a developer solution for positive patterns.
The present invention will hereina~ter be de-scribed in further detail by the following examples. It should however be borne in mind that this invention will not be limited to or by the following examples.
Example l:
Eive parts by weight of methylethylimidazoline were mixed with 100 parts by weight of "AZ1350" (trade name for a positive photoresist produced by Spray Compa-ny). ~ glass substrate for mask, which had a vacuum-evaporated chromium coating, was coated with the above-s~
prepared coating formulation at 3,000 rpm on a spinner.
The thus-applied resist coating film was then prebaked at about 95C for approximately 5 minutes. To form a pattern in the coating film, the prebaked coating film was subjected to first imagewise exposure for 60 seconds under 250 W high-prec;sure mercury vapor lamps, followed by treatment with hot water of about 95C for 15 seconds. By this heat treatment, the exposed area was rendered insoluble in alkaline developer solutions.
The film thus heat-treated was then subjected to full-face exposure (second exposure) for about 30 seconds un-der 250 W high-pressure mercury vapor lamps.
The resulting exposed resist film was developed for 1 minute using an alkaline æeveloper solution which contained as principal components sodium silicate and sodium phosphate. The area not subjected to the first exposure was dissolved in the devaloper solution, there-by providing a negative resist pattern. The resolution of the thus-obtained negative resist pattern was 1 ~m~
so that the resolution was substantially improved com-pared to conventional negative resist patterns.
Comparative Example 1:
The procedure of Example 1 was ~ollowed in exactly the same manner except that the heat treatment after the first exposure was conducted for 3 minutes in air of 95C. The area subjected to the first exposure was not 2~D~3~ 8 completely reversed into a negative pattern by the reversal treatment, so that the resultant pattern flowed out over the entire area thereof upon development. No good pattern was hence obtained.
Example 2:
The procedure cf Example 1 was followed in exactly the same manner except that 21 commercial presensitized plate of the positive type using a diazoquinone sensitizer (product of Frendlefer Company) was used and the heat treatment after the first exposure was con-ducted for 10 seconds at about 75C. A perfect negative resist pattern was obtained.
Comparative Example 2: ¦
The procedure of Example 2 was followed in exactly the same manner except that the heat treatment after the first exposure was conducted fox 3 minutes in air of 95C. The area subjected to the first exposure was not completely reversed into a negative pattern by the revarsal treatment, so that the resultant pattern flowed out over the entire area thereof upon development. No good pattern was hence obtained.
Example ~:
"FPS" (trade name for a presensitized plate of the positive type using a diazoquinone sensitizer and pro-duced by Fuji Photo Film Co., Ltd.) was subjected tofirst imagewise exposure for 60 seconds under 250 W
high-pressure mercury vapor lamps. Next, O.2 g of methylethylimidazoline was dissolved in 1 e of hot water whose temperature was 85~C. The presensitized plate which had been subjected to the first exposure was immersed for 1 minute in the aqueous solution. The plate was washed with water, dried, subjected to full-face exposure in a similar manner to Example 1, and then developed. As a result, the area not subjected to the first exposure was dissolved completely, thereby provid-. 10 ing a negative pattern of excellent resolution.
Example 4:
In 100 parts by weight of methylcellosolve, were dissolved 1 part by weight of 2-phenyl-4-methylimida-zole, 4 parts by weight of an o-naphthoquinonedia2ide/
phenol novolaX ester, 1 part by weight of phenol novolak.
and 0.2 part by weight of oil blue. A silicate-treated aluminum plate was spin-coated with the thus-prepared coating formulation on a wheeler to give a dry film thickness of 1 pm, followed by drying.
In the above manner, two co~ted aluminum plates were prepared. Each of these coated aluminum plates was subjected to imagewise exposure (first exposure) at 100 mj/cm2. One of the aluminum plates was then * Trade name s~
~ 25 -developed in a developer solution wnich contained sodium silicate as principal component. As a result, a perfect positive pattern was obtained.
on the other hand, the other aluminum plate was immersed in hot water of 95C after the fir~t exposure.
sy this step, the pattern was reversed into a negative pattern. It was thereafter subjected to full-face ex-posure at 100 mj/cm2. Similarly to the above procedure, the aluminum plate was developed for 1 minute in a de-veloper solution which contained sodium silicate as a principal component. As a resul~, a perfect negative pattern was obtained.
Example 5:
The procedure of Example 4 was followed in exactly the same manner except for the use of 2-phenylimidazole instead of 2-phenyl-4-methylimidaz~le. Perfect positive and negative resist patterns were obtained.
Example 6:
The procedure of Example 4 was followed in exactly the same manner except for the use of 1-benzyl-2-methyl-imidazole in place of 2-phenyl-4-methylimidazole. Per-fect positive and negative resist patterns were ob-tained.
Example 7:
The procedure of Example 4 was followed in exactly the same manner except for the use of an acidic aqueous , solution, whose pH had been adjusted to 1.0 (pH 1.0) by the addition of p-sulfonic acid, in tha heat treatment.
A perfect negative resist pattern was obtained.
comparative Example 3:
A presensitized plate was prepared in a similar manner to Example 4 except for the use of a sensitizer free of imidazole, namely, a conventional positive sensitizer for presensitized plates. The plate was treated in a similar manner to Example 7. It was how-ever unable to obtain superior properties in resolution and ink applicability to those available from presensi-tized plates obtained using the imidazole-containing sensitizer.
Example 8:
The procedure of Example 4 was followed in a similar manner except for the addition of 0.5 part of 4,4'-methylenebis(2-chloroaniline) as an additive bes-ides 1 part by weight of 2-phenyl-4-mthylimidazole. As a result, a perfect negative pattern of excellent resolution was obtained.
Comparative Example 4:
The procedure of Example 4 was followed in a similar manner except for the use of 4,4'-methylene-bis(2-chloroaniline) in lieu of 2-phenyl-4-methyl-imidazole. It was however unable to obtain superior properties in resolution and ink applicability to those .
. ,, ,~ , . ~ . . , s.~
available from the use of the imidazole-containing sensitizer.
Example 9:
(i) Preparation of sensitizer:
5- o-Naphthoquinonediazido-4-sulfonyl chloride and a cresol novolak resin ("Ready Top PSF-2807", trade name;
product of Gun-ei Chemical ]:ndustry Co., Ltd.) were reacted at 1:1 by weight to obtain a sensitizer-binder mixture as a yellow powder.
(ii) Preparation of Sensitizer formulation:
A 1 kg batch was prepared by adding methylcel-losolve to 70 g of the mixture prepared in the above procedure (i), 3.5 g of imidazole and 0.3 g o~ oil blue.
The batch was stirred at temperatures below 45C to dis-solve the solid components. The resultant mixture was filtered through a 0.5-~m filter to obtain a sensitizer formulation.
(iii) .
Sand-blasted and anodized aluminum plates were separately spin-coated with the sensitizer formulationj which had been prepared in the above procedure (ii), at 80 rpm on a wheeler, followed by drying for 5 minutes in a hot-air dryer of 100C.
(iv) The aluminum plates (iii) were divided into two - groups, namely, Group A and Group B. The aluminum * Trade namc ~3~ 5~
plates in both the groups were subjected to imagewise exposure at 100 mj/cm2 under ultraviolet lamps. The aluminum plates in Group A were directly developed at room temperature in a developer solution which was a 1 aqueous solution of sodium silicate. Sharp positive r~sist patterns were obtained in about 30 seconds.
Some of the imagewise exposed aluminum plates in Group B were immersed for about 5 seconds in hot water of 95C. Water droplets on their surfaces were gently wiped away with a cloth, and they were then subjected to full-face exposure at 100 mj/cm2 in a similar manner to the imagewise exposure. The aluminum plates were then developed at room temperature in the same developer solution as that employed for tha aluminum plates in Group A. Sharp negative resist patterns were obtained in about 30 seconds.
Further, the remaining aluminum plates in Group B
were divided further into two groups. They were treated for about 15 seconds with hot water of 80C and for about 100 seconds with warm water of 60C, respectively.
The thus-treated aluminum plates were subjected to similar full-face exposure and development. Each of the aluminum plates gave a sharp negative resist pattern.
As has been well-known, a variety o~ resists is employed widely in the fabrication of semiconductor devices and the liXe to form desired patterns on sub-strates.
These resists include negative resists and posi-tive resists. When imagewise exposed to radiation such as light, electron beams or x-rays, the exposed portion is insolubilized to a developer solution, namely, a sol-vent, whereby a negative image is provided. On the .
other hand, a positive resist turns to soluble in such a developer solution at an exposed portion so that a posi-tive pattern is provided. Making use of their respec-tive properties, these resists have found significant utility.
Many of these conventional resists are however used exclusively for the fo~ation of either negative or positive resist pattarns. ~amely, it is impossible to selectively form either a negative pattern or a positive pattern by using the same resin commonly. Inconvenient-ly, negative resists and positive resists must thus be selectively used depending on whether intended are nega-tive resist patterns or positive resist patterns. Among these resists, positive resists are superior in resolu-tion and the sharpness of printing areas to negativeresists. There is hence an outstanding demand for the improvement of the resolution of negative resists.
On the other hand, resists capable of selectively forming either negative or positive pa~terns by changing treatment conditions in spite of the use of the same sensitizer (photosensitizer), namely, so-called image reversal resists have also been developed.
Among image reversal resists of the above sort, those using as a sensitizer an o-quinonediazide compound (diazoquinone compound; hereinafter called "diazoquinone sensitizer) are mentioned as typical examples.
z The xeversal of an image formed in a resist, which uses such a diazoquinone sensitizer, is considered to take place in accordance with the following mechanism.
A diazoquinone sensitizer has the characteristic property that upon exposure (first exposure) to radia-tion, diazo groups are decomposed and at the same time, carboxyl groups are formed. Accordingly, when a posi-tive resist containing such a diazoquinone sensitizer (for example, a resist useful for imagewise e~posure lo through a positive film to ~orm a printing plate bearing a positive pattern) is exposed imagewise to radiation through a positive film by a method known per se in the art, carboxyl groups are formed in the exposed area (i.e., the area corresponding to the image-free area of the positive film), whereby upon treatment with an alkaline developer solution, the exposed area is removed to allow the unexposed area to remain as a pattern, thereby o~taining a positive ima~e.
To o~tain a negative image on the other hand, it is necessary to make the resultant carbQxyl groups inac-tive or inert to an alkaline developer solution. To make the area, which is other than that subjected to the first exposure, soluble in an alkali developer solution, after inactivation of the carboxyl groups, full-face ex-posure (second exposure) is performed, followed by de-velopment with an alkaline developer solution. As a 2a~B5i~
result, an image reversed from the aPorementioned image, i.e., a negakive image is obtained.
A variety of processes has been proposed for the inactivation of carboxyl groups formed by first exposure in a resist which contains a diazoquinone sensitizer for example, including the process in which a second component capable of promoting inacti~ation or decarboxylation ofcar-boxyl groups is added in combination with a diazoquinone sensitizer and heat treatment is applied subsequent to first exposure. Specifically described, it has been proposed to use triethanolamine (see Japanese Patent Ap-plication Laid-Open No. 127615/1974), a second or tertiary amine ~see Japanese Patent Application Laid-Open No. 108002/1975), a 1-hydroxyethyl-2-alkylimida-zoline (see Japanese Patent Application Laid-Open No.
6528/1977), a quinone compound or aromatic ketone com-pound (see Japanese Patent Application Laid-Open No.
127615/1974), a basic carbonium dye (see Japanese Patent Application Laid-Open No. 9740/1981), etc. These con-ventional reversal processes however require to conduct,subsequent to first exposure, heat traatment in air, for example, in a constant-temperature air oven maintained around-150C for a relatively long period of time, say, 10 minutes or even longer. This lies as a serious ob-stacle for practice of these processes. Further, heat-ing in such a constant-temperature air oven locally z~
results in uneven heating. These conventional processes are therefore accompanied by another serious drawback that they cannot provide any pattern of desired quality where the intended pattern is a fine pattern.
S A still further process has also been proposed, in which a resist subjected to first exposure is treated with an acidic aqueous solution such as HCl or H2SO4 to decarboxylate carboxyl groups formed by the first ex-posure (Japanese Patent Application Laid-Open No. 3633/1976). This process however requires treatment conditions of a time period as long as 4-5 minutes at a temperature of about 90C and involves inevitable corro-sion of a treatment apparatus. This process is there-fore impractical too.
SU~MA~Y OF THE INVENTION
The present inventors have carried out an ex-tensive investigation with a view toward solving the above-described drawbacks of the conventional processes.
As a result, it has been found that in a process for forming a resist pattern with a diazoquinone sensitizer capable of forming both positive and negative resist patterns, the technical feature of applying hot-water treatment for an extremely short period of time makes it possible to render carboxyl groups, which are formed in the sensitizer upon first exposure, inactive or inert to an alkaline developer solution to be used in the next step, to promote carboxylation in the unexposed area, to accelerate the treatment with the alkaline developer solution in the next step and further to obtain an reversed pattern of excellent resolution. It has also been found that in association with the hot-water treat-ment, use of a water-insolub:Le or sparingly water-soluble imidazole compound as a second component capable of directly or catalytically reacting with photochemical reaction products derived from the diazoquinone sensitizer by the first exposure can afford a pattern of extremely good resolution.
An object of this invention is therefore to pro-vide, based on these findings, novel process for forming an reversed, especially, neg~tive resist pattern with a resist which uses a diazoquinone sensitizer of the image reversal type.
Another object of this invention is to provide an image-reversal developing apparatus suitable for use in the practice of the above process.
In one aspect of this invention, there is thus provided a process for forming a negative resist pattern with a resist containin~ a diazoquinone sensitizer, which comprises subjecting an imagewise exposed area of 2S a layer of the resist to heat treatment with a water-containing heating medium in the presence of a carboxyl-5i2 inactivating agent, exposing the entire surface of the layer to radiation, and then treating the thus-exposed surface with an alkaline developer solution.
In another aspect of this invention, there is also provided an image-reversal developing apparatus for forming a negative resist pattern from a presensitized and imagewise-exposed plate carrying thereon a sensitized resist layer containing a diazoquinone sensitizer, comprising:
10(i) a means for conveying the plate through the apparatus from an inlet to an outlet;
(ii) a means for treating with a water-containing heating medium the plate transferred by the conveyor means;
15(iii) a means for eliminating the water-containing heating medium still remaining on the plate;
(iv) a means for subjecting the plate to full-face exposure; and (v) a means for developing the plate with an alkaline developer solution, and said treatment means (ii), elimination means (iii), full-face exposure mans (iv) and developing means (v) being arranged successively along the conveyor means (i) from a side of the inlet toward a side of the out-let.
The heat treatment by the water-containing heating 35~
medium, said treatment being applied for the reversal of the pattern subsequent to the first exposure, has sig-nificantly improved the drawbacks of the conventional reversal processes. Namely, the conventional heat treatment required to obtain a negative resist pattern is conducted in air. To achieve sufficient reversal ef-fects, it requires not only a temperature as high as around 150C but also a treatment time as long as 10 minutes or even longer. Heat treatmant at such a high temperature for such a long time is however not practi-cal. There has hence been a strong demand for further lowering of the treatment temperature and further shortening of the treatment time. The heat treatment of this invention, which makes use of a water-containing heating medium, permits heating under air free condi-tions. This has made it possible to complete the rever-sal at a lower temperature in a shorter time period.
Further, according to the heat treatment of this invention which makes use of a water-containing heating medium, the unexposed area (the area not exposed to radiation upon the first exposure) is brought into con-tact with the water-containing heating medium, for exam-ple, warm water. This has led to the merit that the treatment with an alkaline developer solution in the next step can be accelerated, in other words, the pro-ductivity can be increased. This may probably be at-tributed to the conversion of a portion o~ the sensitizer in the unexposed area into the corresponding carboxylic acid under t~e influance of water and heat.
The above effects are not available when the heat treat-ment is conducted using a water-free liquid, for exam-ple, paraffin alone. The use of water is therefore es-sential in the present invention.
In addition, the heat treatment with the water-containing heating medium can realize a uniform heat treatment temperature, in otherwise, can avoid uneven temperatures, thereby making it possible to obtain a negative resist pattern having excellent resolution.
The heat treatment in air involves the drawback that a negative resist pattern partially flows out upon davel-opment in an alkaline developer solution. The heattreatment of this invention does not have this problem.
Since the present invention has made it possible to form both positive patterns and negative patterns by using the same type of resists, the same type of devel-oper solution and the sama type of apparatus, ~ommonly.Unlike the conventional techniques, it is no longer needed to choose the type of resist depending on whether an original is positive or negative.
Reversed, namely, negative resist patterns formed on substrates (for example, presansitized plates) in ac-cordance with the present invention are subjected, for example, to etching, resist removal and washing in a similar manner to the conventional processes and are then used for the fabrication of semiconductor devices and the like.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a simplified schematic illustration of an image-reversal developing apparatus useful in the practice of the process of this invention for the forma-tion of an reversed, namely, negative resist pattern.
DETAILED DESCRIPTION OF THE INVENTION
As a sensitizer for making up a resin useful inthe practice of this invention, one of o-quinonediazide compounds, namely, diazoquinone sensitizers commonly known as positive sensitizers. Typical examples of this sort include hydroxybenzophenone, novolak resins, and o~
benzo- and o-naphthoquinonediazide sulfonate esters.
Representative and more specific examples of the o-quinonediazide compounds referred to above include 2,2'-dihyroxydiphenyl-bis(naphthoquinone-1,2-diazido-5-sulfonate) esters, 2,2',4,4'-tetrahydroxydiphenyl-tetra(naphthoquinone-1,2-diazido-5-sulfonate) esters, 2,3,4-trioxybenzophenone-bis(naphthoquinone-1,2-diazido-5-sulfonate) esters. In addition to these naphtho-quinone-1,2-diazido-5-sul~onate esters, 4 sulfonate esters can also be used either singly or in combination with the S-sulfonate esters.
To reverse a resist, which contains a diazoquinone sensitizer as a positive sensitizer, into a negative resist after subjecting the Eirst-mentioned resist to first exposure, one or more of various second component compounds are used in combination with the diazoquinone sensitizer in this invention as described above.
Usable as second component compounds of this sort ara various amines, 1-hydroxy-2-alkylimidazolines, quinone compounds, aromatic ketone compounds, basic carbonium dyes, imidazoline compounds, and imidazole compounds (for example, C~HloN2, 2-ethyl-4-methylimidazole) as de-scribed above.
For the efficient reversal of a resist, which con-tains one or more of the dia~oquinone sensitizers de-scribed above, into a negative resist after subjecting the first-mentioned resist to first e~posure in this in~
vention, it is particularly preferred to use one or more of water-insoluble or sparingly water-soluble imidazole compounds in view of the heat treatment with a water-containing heating medium, for example, hot water to be applied upon formation of a negative pattern.
The above-described imidazole compounds useful in the practice of this invention are represented by the following formula:
135~
R~R ' N
R"
whrein R, R', R" and R"'are independently a hydrogen atom or a substituted or unsubstituted alkyl, aryl or aralkyl group.
Specific examples of the imidazole compounds in-clude 2-phenyl-4-methylimidazole, 2-phenylimidazols, 1-benzyl-2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, etc. They may be used either sing-ly or in combination.
As a binder or base resin making up the resist useful in the practice of this invention, one or more of resins available as resist resins on the market can be used. Illustrative of the base or binder resin include phenol-formaldehyde resins, novolak cresol-formaldehyde resins, styrene-maleic anhydride copolymers, methacrylic acid-methyl methacrylate copolymers, and the like. Al-though not intended to be limited, commercially-available resist resins include "AZ1350", "AZ1370", "AZ1350J", "AS1375" and "AZlll" (all, trade names; pro-ducts of Spray Company); a series of "OFPR" (all, trade name; products of Tokyo Ohka Kogyo Co., Ltd.); "Waycoat LSI Posi Resist" (trade name; product of Hant Chemical Inc.).
The m:ixing of the sensitizer (diazoquinone 5~
sensitizers) and the second component compound with the resist resin (binder) can be practiced in a manner known per se in the art, for example, by thoroughly stirring them into an intimate mixture with a stirrer or the like. Incidentally, it is also possible to use the sec-ond component compound in a form in~orporated in the water-containing heating medium upon conducting the heat treatment for reversal. In this case, the second com-ponent compound is not mixed in the resist resin in gen-eral Although no particular limitation is imposed onthe amounts of the above additives (i.e., the sensitizer and second component) to be added to the resist resin, they may each be added, generally, in an amount of at least 1 part by waight, preferably 1-20 parts by weight, notably 5-15 parts by weight per lO0 parts by weight of the resist resin. If the amount of each of the addi-tives is smaller than 1 part by waight, there is a tendency that the intended effects may not be exhibited ~ully. Such a small amount is therefore not preferred.
In contrast, any amounts in excess of 20 parts by weight may impair the sensitivity of the resist and are hence not preferred either.
In addition to the above additives, various other additives can also be incorporated in the present inven-tion. For example, imaging materials (a variety of Z
dyes) can be added to enhance the contrast between an exposed area and an unexposed area so that the detection of non-conforming products may be facilitated.
A description will next be made of a process of this invention for forming a resist pattern on one of various substrates such as Si, SiO2 and Al substrates by using a resist which contains the above-described diazo-~uinone sensitizer capable o;E forming both positive and negative resist patterns.
Fir~t of all, a substrate which has been subjectad - in advance to washing pretreatment by a usual method is coated uniformly with the resist useful in the practice of this invention by spinning, spraying, roll-coating, dipping or the like. The thus-coated film is then prebaked, for example, in an infrared, closed-loop hot-air or convection-type oven, thereby completely eliminating the solvent from the coating filmO Although prebaking conditions vary depending on the kinds of the solvent and resist resin employed, the prebaking is gen-erally conducted for ~bout 5-30 minutes at 50-1107C.
(i) Formation of positive pattern:
After the prebaking, the coating film is exposed to radiation through a reticle or mask which bears a desired pattern. When a positive image is desired, it is only necessary to develop the thus-exposed coating film with a conventional alkaline devaloper solution.
Exemplary alkaline developer solutions include solutions of caustic soda, caustic potassium, sodium silicate, potassium silicate, tribasic sodium phosphate, tribasic potassium phosphate, sodium carbonate, potas-sium carbonate and the like. It is also possible to usealkaline developer solutions of organic bases such as tetraalkylammonium hydroxides (e.g., tetramethyl ammonium hydroxide) and trimethyl(2-hydroxyethyl)ammonium hydroxide (choline).
When treated with the above-described alkaline de-veloper solution, the exposed and solubilized area is dissolved in the developer solution and the unexposed portion of the coating film remains on the substrate.
As in conventional processes, the remaining positive coating film is then subjected to post-baking under heat treatment conditions which are determined depending on the kind of ths resist resin employed, whereby the adhe-sion between the substrate and the resist film can be enhanced to form a positive resist pattern on the sub-strate.Formation of negative pattern:
When it is desired to form a negative pattern on a substrate on the other hand, first exposure is conducted through a leticle or mask of a desired pattern. Either concurrently with or subsequently with the first ex-posure, heat treatment is conducted with hot water or a water-containing hot liquid. Thereafter, the entire surface of the coating film is exposed (second ex-posure), followed by development in an alkaline devel-oper ~olution employed widely to date. By this develop-ment, the unexposed area of 1:he coating film of theresist has been solubilized so that the unexposed area is dissolved in the developer solution. As a result, the area of the coating film of the resist, said area having been subjected to the first exposure step, remains on the substrate, so that a negative resist pat-tern of high resolution can be obtained.
In the process of this invention for the formation of a resist pattern, especially, a negative resist pat-tern, the greatest feature resides in the heat treatment by a water-containing heating medium such as hot water or a water-containing liquid, which is performed sub-sequent to the first exposure as described above.
The heat treatment is conducted for 5-180 seconds at 30-100C, preferably for 5-60 seconds, notably 5-30 seconds at 50-95C. For example, the heat treatment can be completed in 4-5 seconds using hot water of 85C.
The heat treatment can be carried out, for example, by immersing the resist-bearing substrate, which has been subjected to first exposure, in hot water or the like or by spraying hot water or the like onto the resist-bearing substrate.
Z~ 5~
The heat treatment can also be conducted using hot steam. Us2 of hot steam i8 suitable for a continuous operation because the heat treatment can be carried out in a short time, for example, at a temperature in the S neighborhood of 100C.
As liquids which may be used in combination with water, those not etching or otherwise adversely affect-ing on the resist resin are preferred. Por example, paraffin can be used.
An apparatus suitable for use in the practice of the process of this invention for the formation of an reversed, namely, negative resist pattPrn will next be described with reference to the accompanying sole draw-ing.
As has been mentioned above, the present invention has made it possible to reverse an undeveloped, i.e., latent positive pattern, which has been formed in a presensitized plate having a layer of a resist contain-ing a diazoquinone sensitizer of the image reversal type, into a positive pattern.
At a working site of a photomechanical process, it is generally necessary to install at least two t~pes of presensitized plates, one for positive patterns and the other for negative patterns. This also applies equally to developing machines. This reguirement leads to prob-lems in the initial cost and installation space and also 2~ 3$~
to the problem of cumbersomeness in operation that ei-ther one of thess two types of presensitizad plates have to be chosen depending on the type of each pattern.
The provision of an apparatus suitable for use in the practice of the process of this invention for the formation of a negative pattlern makes it possible to use a single type of developer solution and a single type of presensitized plates for the formation of both positive and negative patterns irrespective of the type of an original pattern through which the presensitized plate is exposed to radiation and moreover to solve the prob-lems described above.
One example of the apparatus suitable for use in the formation of a negative pattern in accordance with the process of this invention is illustrated in FIG. 1.
It should however be borne in mind that this invention is not necessarily limited to or by the illustrated ap-paratus.
Numeral 1 indicates a conveyor means for a pre-sensitized positive plate P. The presensitized plate P
is conveyed rightwards as viewed in the figure while being successively held bet~een a number of carrier rol-lers la,lb disposed in pairs in a face-to-face rela-tionship.
Designated at numeral 2 is a means for spraying hot water onto the presensitized plate P. Through many nozzles 2b attached to a feed line 2a which is in turn connected to an unillustrated hot water source, hot water is sprayed onto the presensitized plate P which the presensitized plate P is conveyed by the carrier rollers la,lb.
An enclosure indicated at numeral 2c is provided to prevent splashing of hot water released through the nozzles 2b.
A dryer means is indicated at numeral 3, which is equipped with lamps 3a as heat sources. Hot water - sprayed by the hot water spraying means 2 and still remaining on the presensitized plate P is removed while tha presensitized plate P travels through the dryer means.
Another enclosure designatPd at numeral 3b is pro-vided to prevent release of heat given off from the heat source lamps 3a.
Designated at numeral 4 is an exposure means for the presensitized plate P. When the presensitized plate P which has travelled through the dryer means 3 reachas the exposure means 4, the presensitized plate P is ex-posed to light irradiated from exposure lamps 4a.
A further enclosure indicat~d at numeral 4b is provided to prevent release of light irradiated from the exposure lamps 4a.
Numeral 5 indicates an ordinary developing ma-chine. ~lthough not illustrated in the drawing, the de-veloping machine is equipped with mechanisms required for development.
When it is desired to use the presensitized posi-tive plate P a negative plate, the presensitized posi-tive plate P bearing a latent positive pattern is loaded at a plate inlet lc. The presensitized plate P is then conveyed to the hot water spray means 2.
Here, hot water is sprayed onto the positive pat-tern bearing surface of the presensitized positiveplate, so that the solubility of the positive pattern in an alkaline solution is lost.
The presensitized plate which has been imparted wi~h the above-described property for the pattern by the hot w~ter spray means t2) is conveyed to the dryer means, where any remaining hot water is removed by the dryer means 3, followed by further travelling to the ex-posure means 4. Incidentally, any hot water still remaining on the presensitized plate P may be simply wiped away in this invention instead of drying it up by the dryer means 3.
The pattern-bearing surface of the presensitized plate P is next subjected to full-face exposure, whereby the unexposed area is rendered soluble in an alkaline solution The presensitized plate P is next fed into the de-35~
veloping machine 5 by the conveyor means 1, so that the une~posed area rendsred soluble to the alkaline solution is removed. Namely, prescribed developing treatment is applied.
When it is desired to use the presensitized plate as a positive plate, it is only neces~ary to feed the presensitized plate directly into the developer 5 without feeding same through the spay means 2 to ex-posure means 4. Prescribed development is then carried out by the developing machine 5.
Namely, the positive pattern formed in the pre-sensitized plate P is converted to have the same func-tions as the an ordinary negative film, so that the presensitized plate P can be developed without any prob-lem by the developing machine 5 which uses a developer solution for positive patterns.
The present invention will hereina~ter be de-scribed in further detail by the following examples. It should however be borne in mind that this invention will not be limited to or by the following examples.
Example l:
Eive parts by weight of methylethylimidazoline were mixed with 100 parts by weight of "AZ1350" (trade name for a positive photoresist produced by Spray Compa-ny). ~ glass substrate for mask, which had a vacuum-evaporated chromium coating, was coated with the above-s~
prepared coating formulation at 3,000 rpm on a spinner.
The thus-applied resist coating film was then prebaked at about 95C for approximately 5 minutes. To form a pattern in the coating film, the prebaked coating film was subjected to first imagewise exposure for 60 seconds under 250 W high-prec;sure mercury vapor lamps, followed by treatment with hot water of about 95C for 15 seconds. By this heat treatment, the exposed area was rendered insoluble in alkaline developer solutions.
The film thus heat-treated was then subjected to full-face exposure (second exposure) for about 30 seconds un-der 250 W high-pressure mercury vapor lamps.
The resulting exposed resist film was developed for 1 minute using an alkaline æeveloper solution which contained as principal components sodium silicate and sodium phosphate. The area not subjected to the first exposure was dissolved in the devaloper solution, there-by providing a negative resist pattern. The resolution of the thus-obtained negative resist pattern was 1 ~m~
so that the resolution was substantially improved com-pared to conventional negative resist patterns.
Comparative Example 1:
The procedure of Example 1 was ~ollowed in exactly the same manner except that the heat treatment after the first exposure was conducted for 3 minutes in air of 95C. The area subjected to the first exposure was not 2~D~3~ 8 completely reversed into a negative pattern by the reversal treatment, so that the resultant pattern flowed out over the entire area thereof upon development. No good pattern was hence obtained.
Example 2:
The procedure cf Example 1 was followed in exactly the same manner except that 21 commercial presensitized plate of the positive type using a diazoquinone sensitizer (product of Frendlefer Company) was used and the heat treatment after the first exposure was con-ducted for 10 seconds at about 75C. A perfect negative resist pattern was obtained.
Comparative Example 2: ¦
The procedure of Example 2 was followed in exactly the same manner except that the heat treatment after the first exposure was conducted fox 3 minutes in air of 95C. The area subjected to the first exposure was not completely reversed into a negative pattern by the revarsal treatment, so that the resultant pattern flowed out over the entire area thereof upon development. No good pattern was hence obtained.
Example ~:
"FPS" (trade name for a presensitized plate of the positive type using a diazoquinone sensitizer and pro-duced by Fuji Photo Film Co., Ltd.) was subjected tofirst imagewise exposure for 60 seconds under 250 W
high-pressure mercury vapor lamps. Next, O.2 g of methylethylimidazoline was dissolved in 1 e of hot water whose temperature was 85~C. The presensitized plate which had been subjected to the first exposure was immersed for 1 minute in the aqueous solution. The plate was washed with water, dried, subjected to full-face exposure in a similar manner to Example 1, and then developed. As a result, the area not subjected to the first exposure was dissolved completely, thereby provid-. 10 ing a negative pattern of excellent resolution.
Example 4:
In 100 parts by weight of methylcellosolve, were dissolved 1 part by weight of 2-phenyl-4-methylimida-zole, 4 parts by weight of an o-naphthoquinonedia2ide/
phenol novolaX ester, 1 part by weight of phenol novolak.
and 0.2 part by weight of oil blue. A silicate-treated aluminum plate was spin-coated with the thus-prepared coating formulation on a wheeler to give a dry film thickness of 1 pm, followed by drying.
In the above manner, two co~ted aluminum plates were prepared. Each of these coated aluminum plates was subjected to imagewise exposure (first exposure) at 100 mj/cm2. One of the aluminum plates was then * Trade name s~
~ 25 -developed in a developer solution wnich contained sodium silicate as principal component. As a result, a perfect positive pattern was obtained.
on the other hand, the other aluminum plate was immersed in hot water of 95C after the fir~t exposure.
sy this step, the pattern was reversed into a negative pattern. It was thereafter subjected to full-face ex-posure at 100 mj/cm2. Similarly to the above procedure, the aluminum plate was developed for 1 minute in a de-veloper solution which contained sodium silicate as a principal component. As a resul~, a perfect negative pattern was obtained.
Example 5:
The procedure of Example 4 was followed in exactly the same manner except for the use of 2-phenylimidazole instead of 2-phenyl-4-methylimidaz~le. Perfect positive and negative resist patterns were obtained.
Example 6:
The procedure of Example 4 was followed in exactly the same manner except for the use of 1-benzyl-2-methyl-imidazole in place of 2-phenyl-4-methylimidazole. Per-fect positive and negative resist patterns were ob-tained.
Example 7:
The procedure of Example 4 was followed in exactly the same manner except for the use of an acidic aqueous , solution, whose pH had been adjusted to 1.0 (pH 1.0) by the addition of p-sulfonic acid, in tha heat treatment.
A perfect negative resist pattern was obtained.
comparative Example 3:
A presensitized plate was prepared in a similar manner to Example 4 except for the use of a sensitizer free of imidazole, namely, a conventional positive sensitizer for presensitized plates. The plate was treated in a similar manner to Example 7. It was how-ever unable to obtain superior properties in resolution and ink applicability to those available from presensi-tized plates obtained using the imidazole-containing sensitizer.
Example 8:
The procedure of Example 4 was followed in a similar manner except for the addition of 0.5 part of 4,4'-methylenebis(2-chloroaniline) as an additive bes-ides 1 part by weight of 2-phenyl-4-mthylimidazole. As a result, a perfect negative pattern of excellent resolution was obtained.
Comparative Example 4:
The procedure of Example 4 was followed in a similar manner except for the use of 4,4'-methylene-bis(2-chloroaniline) in lieu of 2-phenyl-4-methyl-imidazole. It was however unable to obtain superior properties in resolution and ink applicability to those .
. ,, ,~ , . ~ . . , s.~
available from the use of the imidazole-containing sensitizer.
Example 9:
(i) Preparation of sensitizer:
5- o-Naphthoquinonediazido-4-sulfonyl chloride and a cresol novolak resin ("Ready Top PSF-2807", trade name;
product of Gun-ei Chemical ]:ndustry Co., Ltd.) were reacted at 1:1 by weight to obtain a sensitizer-binder mixture as a yellow powder.
(ii) Preparation of Sensitizer formulation:
A 1 kg batch was prepared by adding methylcel-losolve to 70 g of the mixture prepared in the above procedure (i), 3.5 g of imidazole and 0.3 g o~ oil blue.
The batch was stirred at temperatures below 45C to dis-solve the solid components. The resultant mixture was filtered through a 0.5-~m filter to obtain a sensitizer formulation.
(iii) .
Sand-blasted and anodized aluminum plates were separately spin-coated with the sensitizer formulationj which had been prepared in the above procedure (ii), at 80 rpm on a wheeler, followed by drying for 5 minutes in a hot-air dryer of 100C.
(iv) The aluminum plates (iii) were divided into two - groups, namely, Group A and Group B. The aluminum * Trade namc ~3~ 5~
plates in both the groups were subjected to imagewise exposure at 100 mj/cm2 under ultraviolet lamps. The aluminum plates in Group A were directly developed at room temperature in a developer solution which was a 1 aqueous solution of sodium silicate. Sharp positive r~sist patterns were obtained in about 30 seconds.
Some of the imagewise exposed aluminum plates in Group B were immersed for about 5 seconds in hot water of 95C. Water droplets on their surfaces were gently wiped away with a cloth, and they were then subjected to full-face exposure at 100 mj/cm2 in a similar manner to the imagewise exposure. The aluminum plates were then developed at room temperature in the same developer solution as that employed for tha aluminum plates in Group A. Sharp negative resist patterns were obtained in about 30 seconds.
Further, the remaining aluminum plates in Group B
were divided further into two groups. They were treated for about 15 seconds with hot water of 80C and for about 100 seconds with warm water of 60C, respectively.
The thus-treated aluminum plates were subjected to similar full-face exposure and development. Each of the aluminum plates gave a sharp negative resist pattern.
Claims (22)
1. A process for forming a negative resist pat-tern with a resist containing a diazoquinone sensitizer, which comprises subjecting an imagewise exposed area of a layer of the resist to heat: treatment with a water-containing heating medium in the presence of a carboxyl-inactivating agent, exposing the entire surface of the layer to radiation, and then treating the thus-exposed surface with an alkaline developer solution.
2. The process of claim 1, wherein the heating medium is selected from the group consisting of water-containing hot liquids and steam.
3. The process of claim 2, wherein the heat treatment is conducted at 50-95°C for 5-60 seconds.
4. The process of claim 3, wherein the heat treatment is conducted for 5-30 seconds.
5. The process of claim 1, wherein the carboxyl-inactivating agent is contained in the resist.
6. The process of claim 1, wherein the carboxyl-inactivating agent is contained in the water-containing heating medium.
7. The process of claim 1, wherein the carboxyl-inactivating agent is a decarboxylation agent.
8. The process of claim 1, wherein the carboxyl-inactivating agent is selected from the group consisting of amines, quinone compounds, aromatic ketones, basic carbonium dyes, imidazoline compounds and imidazole com-pounds.
9. The process of claim 8, wherein the carboxyl-inactivating agent is an imidazole compound represented by the following formula:
wherein R, R', R" and R"'are independently a hydrogen atom or a substituted or unsubstituted alkyl, aryl or aralkyl group.
wherein R, R', R" and R"'are independently a hydrogen atom or a substituted or unsubstituted alkyl, aryl or aralkyl group.
10. The process of claim 9, wherein the imidazole compound is water-insoluble or sparingly water-soluble.
11. The process of claim 9, wherein the imidazole compound is selected from the group consisting of 2-phenyl-4-methylimidazole~ 2-phenylimidazole, l-ben2yl-2-methylimidazole, 2-undecylimidazole, 2-pentadecyl-imidazole, and mixtures thereof.
12. The process of claim 1, wherein the diazo-quinone sensitizer is selected from the group consisting of 2,2'-dihyroxydiphenyl-bis(naphthoquinone-1,2-diazido-5-sulfonate) esters, 2,2',4,4'-tetrahydroxy-diphenyl-tetra(naphthoquinon~e-1,2-diazido-5-sulfonates) esters, 2,3,4-trioxybenzophenone-bis(naphthoquinone-1,2-diazido-5-sulfonate) esters, 2,2'-dihyroxydiphenyl-bis(naphthoquinone-1,2-diazido-4-sulfonate) esters, 2,2',4,4'-tetrahydroxydiphenyl-tetra(naphthoquinone-1,2-diazido-4-sulfonates) esters, 2,3,4 trioxybenzophenone-bis(naphthoquinone-1,2-diazido-4-sulfonate) esters, and mixtures thereof.
13. The process of claim 1, wherein the resist comprises a base resin selected from the group consist-ing of phenol-formaldehyde resins, novolak cresol-form-aldehyde resins, styrene-maleic anhydride copolymers, methacrylic acid-methyl methacrylate copolymers, and mixtures thereof.
14. The process of claim 13, wherein the resist contains 1-20 parts by weight of the diazoquinone sensitizer per 100 parts by weight of the base resin.
15. The process of claim 13, wherein the resist contains 1-20 parts by weight of the carboxyl-inactivating agent per 100 parts by weight of the base resin.
16. The process of claim 1, wherein the water-containing hating medium is hot water.
17. The process of claim 1, wherein the water-containing heating medium is water-containing paraffin.
18. The process of claim 1, wherein carboxyl-inactivating agent is selected from the group consisting of methylethylimidazoline, 2-phenyl-4-methylimidazole.
2-phenylimidazole, 1-benzyl-2-methylimidazole, 4,4'-methylenebis(2-chloroaniline).
2-phenylimidazole, 1-benzyl-2-methylimidazole, 4,4'-methylenebis(2-chloroaniline).
19. The process of claim 1, wherein the diazo-quinone sensitizer is selected from the group consisting of o-naphthoquinonediazide and o-naphthoquinonediazido-4-sulfonyl chloride.
20. An image-reversal developing apparatus for forming a negative resist pattern from a presensitized and imagewise-exposed plate carrying thereon a sensitized resist layer containing a diazoquinone sensitizer, comprising:
(i) a means for conveying the plate through the apparatus from an inlet to an outlet;
(ii) a means for treating with a water-containing heating medium the plate transferred by the conveyor means;
(iii) a means for eliminating the water-containing heating medium still remaining on the plate;
(iv) a means for subjecting the plate to full-face exposure; and (v) a means for developing the plate with an alkaline developer solution; and said treatment means (ii), elimination means (iii), full-face exposure mans (iv) and developing means (v) being arranged successively along the conveyor means (i) from a side of the inlet toward a side of the out-let.
(i) a means for conveying the plate through the apparatus from an inlet to an outlet;
(ii) a means for treating with a water-containing heating medium the plate transferred by the conveyor means;
(iii) a means for eliminating the water-containing heating medium still remaining on the plate;
(iv) a means for subjecting the plate to full-face exposure; and (v) a means for developing the plate with an alkaline developer solution; and said treatment means (ii), elimination means (iii), full-face exposure mans (iv) and developing means (v) being arranged successively along the conveyor means (i) from a side of the inlet toward a side of the out-let.
21. The apparatus of claim 20, wherein said con-.
veyor means (i) is a power-operated roller conveyor.
veyor means (i) is a power-operated roller conveyor.
22. The apparatus of claim 20, wherein said treat-ment means (ii) is a hot water spray means.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27455988A JPH02123363A (en) | 1988-11-01 | 1988-11-01 | Formation of resist pattern |
| JP274559 | 1988-11-01 | ||
| JP280358 | 1988-11-08 | ||
| JP28035888A JPH02127646A (en) | 1988-11-08 | 1988-11-08 | Image forming method |
| JP171432 | 1988-12-30 | ||
| JP17143288U JPH0290847U (en) | 1988-12-30 | 1988-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2001852A1 true CA2001852A1 (en) | 1990-05-01 |
Family
ID=27323491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2001852 Abandoned CA2001852A1 (en) | 1988-11-01 | 1989-10-31 | Process and apparatus for the formation of negative resist pattern |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA2001852A1 (en) |
| DE (1) | DE3936502A1 (en) |
| GB (1) | GB2224362B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2305517B (en) * | 1995-08-23 | 1999-07-28 | Kodak Ltd | Improvements in imaging systems |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL280959A (en) * | 1961-07-28 | |||
| GB1492600A (en) * | 1974-01-02 | 1977-11-23 | Occidental Petroleum Corp | Process for treating coal to produce a carbon char of low sulphur content |
| FR2274072A1 (en) * | 1974-06-06 | 1976-01-02 | Ibm | PROCESS FOR FORMING IMAGES IN PHOTORESISTANT MATERIAL, APPLICABLE ESPECIALLY IN THE SEMICONDUCTOR INDUSTRY |
| JPS566236A (en) * | 1979-06-28 | 1981-01-22 | Fuji Photo Film Co Ltd | Photosensitive material and pattern forming method using it |
| JPS5890636A (en) * | 1981-11-24 | 1983-05-30 | Fuji Photo Film Co Ltd | Method for forming image with photosensitive material using photopolymerizable composition and developing unit |
| DE3325023A1 (en) * | 1983-07-11 | 1985-01-24 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING NEGATIVE COPIES BY MEANS OF A MATERIAL BASED ON 1,2-CHINONDIAZIDES |
| GB2171530B (en) * | 1985-02-27 | 1989-06-28 | Imtec Products Inc | Method of producing reversed photoresist images by vapour diffusion |
| GB2188448B (en) * | 1986-03-13 | 1989-11-15 | Horsell Graphic Ind Ltd | Reversal processing of exposed lithographic printing plates |
-
1989
- 1989-10-31 CA CA 2001852 patent/CA2001852A1/en not_active Abandoned
- 1989-10-31 GB GB8924488A patent/GB2224362B/en not_active Expired - Fee Related
- 1989-11-02 DE DE19893936502 patent/DE3936502A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE3936502A1 (en) | 1990-05-03 |
| GB2224362B (en) | 1993-05-19 |
| GB8924488D0 (en) | 1989-12-20 |
| GB2224362A (en) | 1990-05-02 |
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