JPH0876373A - Positive photosensitive composition and fine pattern forming method using same - Google Patents

Abstract

PURPOSE: To faithfully transfer a finer pattern to a substrate by adding a specified benzothiazole compd. or a specified amine salt of a benzothiazole compd. CONSTITUTION: This photosensitive compsn. contains at least alkali-soluble phenolic resin, an o-quinonediazido compd., a solvent having ability to well dissolve them and a benzothiazole compd. represented by formula I and/or an amine salt of a benzothiazole compd. represented by formula II. In the formulae I, II, each of R1 , R2 and R5 -R7 is H, alkyl, alkoxy, etc., at least one of R3 and R4 or at least one of R8 -R10 is a cyclohexyl ring, a morpholine ring or a group such as alkyl or alkoxy having a cyclohexyl ring, R3 and R4 or at least two of R8 -R10 may form a morpholine ring together with N and the others are H, alkyl, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel positive photosensitive composition, more specifically, resolution, sensitivity and adhesiveness used in the manufacture of electronic parts such as semiconductor devices and liquid crystal display devices. The present invention relates to a positive photosensitive composition having excellent developability and suitable for fine processing, and a fine pattern forming method using the same.

[0002]

2. Description of the Related Art Conventionally, various semiconductor wafers, various metal films or conductive films are formed on the surface in the photofabrication process in the manufacture of highly integrated circuit devices such as LSI or liquid crystal display device circuits. Many substrates such as glass substrates and ceramic substrates are used,
A photosensitive composition is formed on these surfaces by a spin coating method or a roller coating method. This film is irradiated with actinic rays,
By forming an image, a target circuit pattern image is formed. After that, the fine circuit element is processed with a metal film or a conductive film to obtain a desired circuit pattern.

In order to form such a fine pattern, an alkali-soluble novolak resin called a phenol resin and a photosensitive composition mainly composed of two components of a photosensitive material having a naphthoquinonediazide group as a photosensitive group are generally used. Is used for. Using such a photosensitive composition (hereinafter, also referred to as a resist), a wide range from an ultra-fine image pattern size of about 0.3 μm to a considerably large size width of about several tens to several hundreds μm An image with dimensions spanning over a wide area is formed, enabling fine processing of various substrates.

The circuit line width of integrated circuit semiconductors is becoming finer as the degree of integration becomes higher, and the line width is expanding from submicron to half micron. On the other hand, in liquid crystal display devices and the like, the line width also becomes thin and tends to become finer.
The control of the design line width is based on the control of the pattern line width in image formation and the dimension control in etching. In particular, in the processing of a high resolution resist pattern accompanying the miniaturization of the design line width, the resolution and the adhesion of the resist to the substrate during etching are important factors for improving the processing accuracy. In particular, in the wet etching method, it is no exaggeration to say that this adhesion controls the accuracy of the substrate processing technology, and has a great influence.

On the other hand, in relation to liquid crystal display elements, new base metal materials have come to be used, and color ST
With the development of N or TFT display elements, the ITO film, which has a long track record as a transparent conductive film, is being made to have lower resistance, that is, thicker film. In order to deal with the etching of thick ITO, it is necessary to perform the treatment for a longer time than the conventional overetching treatment time. For this reason, at the adhesion level that can be used without any problems in the past, in etching a finer pattern, the amount of side etching becomes large, which causes peeling of the fine resist pattern. Therefore, it has been found that a microetching pattern of a predetermined size cannot be obtained, and the demand cannot be sufficiently satisfied. A higher level of adhesion has come to be required.

Representative examples of the substrate used in the liquid crystal display element include ITO, Ta, Mo, Cr, and a nitride film. Similarly to the semiconductor element, dry etching or wet etching is performed using the resist wiring pattern formed on these underlying substrates as a protective film. Since the processing accuracy in etching has a great influence on the device performance, it is necessary to perform the etching process with higher accuracy. For this purpose, it is important that the adhesion of the resist to the substrate is high during the etching process. That is, there is a demand for a resist that has a property of forming a smaller side etch.

In response to such a request, Japanese Patent Laid-Open No. 2-846
No. 54, 2 of quinonediazide / phenolic resin
It is disclosed that the adhesion to various substrates, especially ITO substrates can be improved by adding at least one compound of a urea compound, a thiourea compound and an arylamine compound to a positive resist composed of an original system. However, the technology of liquid crystal display devices is moving toward the development of monochrome and color, small to large, and easy-to-see, fast-response devices that provide clearer images. It is necessary to use a substrate having a conductive film of. In order to increase the processing accuracy, in order to improve the etching accuracy such as in-plane uniformity, the reason for thickening the substrate and increasing the size is
The over-etching process must be performed for a fixed time longer than before. Therefore, in order to cope with this over-etching, the substrate adhesion of the resist film needs to exceed the conventional required level. However, JP-A-2-846
Although the technique disclosed in Japanese Patent No. 54 is at a level that can satisfy the conventional requirements, it is becoming difficult to satisfy the requirement level corresponding to new movements.
For example, good results can be obtained by etching near room temperature, but when etching is performed at a relatively high temperature for a long time, the side etch amount tends to be large and the adhesiveness tends to deteriorate.

Further, in JP-A-2-141754, by adding a specific thiazole compound having a halogen, an alkyl group, an alkoxy group, an amino group or a nitro group as a substituent to a resist matrix composed of a quinonediazide / novolak system. It is disclosed that a photosensitive lithographic printing plate can be obtained which can be a negative type or a positive type and has good printing durability, exposure visible imageability and sensitivity. However, this technique relates to a lithographic printing plate, and in the case of the above overetching treatment, the side etching amount becomes large and the adhesion between the resist and the substrate is insufficient.

[0009]

Therefore, according to the present invention,
A positive photosensitive composition that has much higher adhesion to a substrate than before, improves the processing accuracy in etching processing, particularly over-etching processing, and can transfer a finer pattern to a substrate faithfully. It is an object of the present invention to provide a used fine pattern forming method.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that in a positive-working photosensitive composition containing two components, an alkali-soluble phenol resin and an o-quinonediazide compound, as main components, an adhesion promoter is used. It was found that the effect of contributing to the adhesiveness is different when the substituents in the molecule of the benzothiazole compound added as the agent are different. As a result of further study based on this, in the positive photosensitive composition, at least one compound selected from the group consisting of a benzothiazole compound or an amine salt of a benzothiazole compound having at least one cyclohexyl ring or morpholine ring in the molecule. It was found that the addition or addition of the compound markedly improves the adhesiveness or adhesiveness of the resist to the substrate, and the present invention has been completed based on this finding.

That is, the present invention has the following constitution. (A) Alkali-soluble phenolic resin (b) O-quinonediazide compound (c) Solvent having sufficient ability to dissolve the above-mentioned (a), (b) and the following (d) (d) Represented by the following general formula (I) A benzothiazole compound and / or an amine salt of benzothiazole represented by the following general formula (II).

[0012]

Embedded image

Where R₁, R₂, R_Five, R₆Or R
₇Are each a hydrogen atom, an alkyl group, an alkoxy group or
Represents an aryl group. R₃And R_FourAt least one of
Or R ₈, R₉And R_TenAt least one of the
Cyclohexyl ring, morpholine ring, or cyclohexyl
Ring or morpholine ring-containing alkyl groups, alkoxy groups
Represents a Si group or an aryl group, R₃And R_Four, Or R₈,
R₉And R_TenAt least two of them are
May form a ring to represent a morpholine ring. At this time
The remaining ones are each hydrogen atom, alkyl group or aryl group.
Represent

The present invention will be described in detail below. The alkali-soluble resin used in the present invention contains a novolac resin, a vinylphenol resin, an N- (hydroxyphenyl) maleimide copolymer, a styrene-maleic anhydride copolymer, a carboxyl group, a sulfonyl group, or a phosphonic acid group. Examples thereof include methacrylic resin and acrylic acid-based resin. Examples of alkali-soluble phenolic resins include "Synthetic Resin in Coatin
gs "(HP Press Noyes Development Corporation. 1
965, Pear River NY) and the phenol / formaldehyde condensate novolac or resole resin. In the present invention, novolac resin is more preferable. By using this, it is preferable in that the acid resistance, dry etching resistance and heat resistance are improved.

Novolak resins include phenols, phenols such as p-chlorophenol, o-cresol, p-
Cresols such as cresol and m-cresol, or xylenols such as 2,3-dimethylphenol, 2,4-dimethylphenol, 3,4-dimethylphenol and 3,5-dimethylphenol, alone or in combination with 2
It can be obtained by addition polymerization of 1 to 0.6 mol of aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde or furfural to 1 mol of a combination of two or more kinds in the presence of an acid catalyst. Generally, hydrochloric acid, sulfuric acid, formic acid, oxalic acid and acetic acid are used as the acid catalyst. Among the above novolac resins, phenol novolac resins and cresol novolac resins are more preferable. As a result, in addition to acid resistance, heat resistance and dry etching resistance, resolution, cross-sectional shape and the like are improved.
The thus obtained novolak resin having a molecular weight of 1000 to 50000 exhibits alkali solubility and can be preferably used in the present invention. The above alkali-soluble phenol resin may be used alone or as a mixture of two or more kinds.

The photosensitive material used in the present invention is an o-quinonediazide compound, which is a compound containing a naphthoquinonediazide group as a photosensitive group in its molecule and functions as a dissolution inhibitor in the constituent components of the photosensitive composition. Such compounds include, for example, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,
4,4'-trihydroxybenzophenone, 2,3
Polyhydroxybenzophenone such as 4,4'-tetrahydroxybenzophenone or 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxybenzophenone, and polyhydroxybenzophenone Hydroxyphenyl alkyl ketones, bis (polyhydroxyphenyl) alkanes, polyhydroxybenzoic acid esters, bis (polyhydroxybenzoyl) alkanes or bis (polyhydroxybenzoyl)
A mixture of fully substituted and partially substituted products of an esterification reaction product of aryls with 1,2-naphthoquinonediazide-5 (and / or -4) -sulfonyl chloride, and also in JP-A No. 64-76047. As an example, a mixture of fully and partially substituted products of an esterification reaction product of a polyhydroxyspirobiindane compound and the sulfonyl chloride, and a triphenylmethane-based polyhydroxy compound described in JP-A-1-189644 are exemplified. Can be mentioned. Other examples of the polyhydroxy compound include those described in JP-A-4-274243, but the polyhydroxy compound is not limited to those exemplified here. These naphthoquinonediazide compounds may be used alone or 2
You may use it in mixture of 2 or more types. The photosensitive material is used in the range of 5 to 100 parts by weight, preferably about 5 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the amount of the compound to be mixed is in the range of 5 to 60 parts by weight, the dissolution inhibiting effect can be sufficiently obtained and the film loss of the unexposed portion during development can be suppressed. Therefore, it is possible to form a good profile pattern without causing any inconvenience such as deterioration of the profile accompanying a decrease in the residual film rate. In addition, practical sensitivity can be obtained, and an extreme decrease in sensitivity can be eliminated.
In addition, there is no instability factor such as re-precipitation that occurs when the amount exceeds the appropriate range, and stable storage is possible even after long-term storage.

In the present invention, in order to perform processing with higher accuracy, at least one cyclohexyl ring or morpholine ring is added as a third component in addition to the above alkali-soluble phenol resin and o-quinonediazide compound.
At least one kind or more of the benzothiazole compound and its derivative in the individual molecule and the amine salt of the benzothiazole compound and its derivative are added. In formula (I) or (II), at least one of R ₃ and R ₄ , or at least one of R ₈ , R ₉ and R ₁₀ is a cyclohexyl ring, a morpholine ring, or a cyclohexyl ring or a morpholine ring. An alkyl group having
It represents an alkoxy group or an aryl group, and at least two of R ₃ and R ₄ , or R ₈ , R ₉ and R ₁₀ may form a ring together with a nitrogen atom to represent a morpholine ring.
Here, the alkyl group or the alkoxy group has any one of 1 to 6 carbon atoms, and the aryl group is any of a phenyl group substituted or unsubstituted with an alkyl group having 1 to 3 carbon atoms. And at least one hydrogen atom thereof is substituted with a cyclohexyl ring or a morpholine ring. In the present invention, at least one alkyl group, alkoxy group or aryl group having a cyclohexyl ring, a morpholine ring, a cyclohexyl ring or a morpholine ring is contained in each compound represented by the general formula (I) or (II). , And preferably 3 or less.
Each of R ₃ , R ₄ , R ₈ , R ₉ and R ₁₀ other than these represents a hydrogen atom, an alkyl group or an aryl group.
R ₁ , R ₂ , R ₅ , R ₆ or R ₇ each represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group.

Examples of these compounds are N-cyclohexyl-benzothiazole-2-sulfenamide,
As an example, N, N-dicyclohexyl-benzothiazole-2-sulfenamide, 2-mercaptobenzothiazolecyclohexylamine salt, 2-mercaptobenzothiazole dicyclohexylamine salt, N-oxydiethylene-benzothiazole-2-sulfenamide, etc. Can be mentioned. However, the contents of the present invention are not limited to these. In the photosensitive composition of the present invention, either the compound represented by the general formula (I) or the compound represented by the general formula (II) may be contained, or both of them may be contained. Good.

The compound represented by the general formula (I) or (II) is usually 0.01 to 15% by weight based on 100% by weight of the total solid content of the alkali-soluble phenol resin and the o-quinonediazide compound. It is preferably used in the range of. More preferably, it is in the range of 0.1 to 10% by weight. When the content is within these ranges, the above-mentioned effects of the present invention are more remarkably expressed. That is, the adhesion between the coating layer of the photosensitive composition and the substrate becomes better, and the stability of the photosensitive composition in solution becomes better.

Further, in the photosensitive composition of the present invention, as a solvent having the ability to sufficiently dissolve the alkali-soluble phenol resin, the o-quinonediazide compound and the compound represented by the general formula (I) or (II), Most of the organic solvents used in the conventional naphthoquinonediazide positive resist can be used. For example, glycol ether-based methyl cellosolve, ethyl cellosolve, propyl cellosolve, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and acetylated products thereof, that is, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate,
Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and the like.
The acetic acid ester type includes amyl acetate, butyl acetate, propyl acetate, methyl acetate, ethyl acetate and the like, and the ketone type includes methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone and the like. In addition to these, polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone, ethyl lactate, methyl pyruvate, ethyl pyruvate, ethyl ethoxypropionate, and methylmethoxypropionate can be given. . These solvents can be used alone or as a mixture of two or more kinds. However, depending on the coating method, the desired coating film may not be satisfactorily formed. However, in this case, it can be easily detected by a simple coating test.

Further, in addition to these three components, a surfactant, a modified resin, a plasticizer, etc. may be added to the photosensitive composition of the present invention in order to improve coating performance and coating film properties. You can also Further, a dye or a coloring agent may be added for the purpose of improving visibility or for preventing standing waves. Furthermore, in order to increase the sensitivity, it is possible to add a low molecular weight compound or a low molecular weight resin component that exhibits a sensitizing effect. These addition auxiliaries should be limited to such an amount that the effect of the compound added as the third component is not impaired.

The photosensitive composition of the present invention thus obtained can be used for forming a desired pattern. The photosensitive composition of the present invention can be particularly preferably used in a method for forming a fine pattern. That is, the following method can be preferably used. i) a step of applying the positive photosensitive composition on a substrate ii) a step of irradiating the applied positive photosensitive composition with an actinic ray to form a latent image, and then developing the resist to form a resist pattern iii) A step of etching a substrate using the patterned resist as a mask iv) A step of peeling and removing the resist, which is a fine pattern forming method. By this method, the adhesiveness between the photosensitive composition and the substrate is extremely high, the processing accuracy is improved, and a finer pattern can be faithfully transferred to the substrate.

The photosensitive composition of the present invention is used in the form of a coating film on a substrate, and various roll coater bars using a spinner roll of a spin coating type are used as a coating film forming means. Various methods such as a bar coater can be applied. However, since a glossy and flat coating film may not be obtained depending on the solvent used, it may be necessary to appropriately select a solvent suitable for coating depending on the coating method.

Substrates that can be used include silicon wafers on which various metal films are vapor-deposited or sputtered, metals such as ITO, Cr, Mo, Ta, Al and nitride films, or glass substrates or ceramics on which a transparent conductive film is formed. For example, a substrate. A coating film having a thickness after drying of 0.5 to several μ is formed on these substrates by the above-mentioned method.
The substrate of the present invention is preferably a silicon wafer or a glass substrate on the surface of which the metal film to be etched is preferably formed.

An exposure apparatus having a light source such as a stepper as an active ray, a projection aligner, or a super high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, an arc lamp, a xenon lamp through a mask having a desired pattern on a substrate on which a resist film is formed. To form a latent image. After the latent image is formed, development processing is performed with a predetermined developing solution. The developer may be an organic type or an inorganic type. An example of the organic developer is an aqueous solution of tetramethylammonium hydroxide (abbreviated as TMAH) having a concentration of about 0.5 to 5% by weight. 0.1 to 5% for inorganic developers
As an example, an aqueous solution of caustic soda, caustic potash, sodium silicate, etc. can be mentioned. A desired resist pattern can be obtained by immersing the exposed sample substrate in these developing solutions or contacting them with a shower or paddle for a predetermined period of time and then washing with water.

The resist pattern thus obtained is used as a mask for etching, and wet etching of the substrate is performed using an appropriate etchant or dry etching using plasma or the like is performed. Here, as the etchant, conventionally known ones can be used, but specifically, hydrochloric acid-nitric acid mixed system, HBr, ferrous chloride-hydrochloric acid-nitric acid mixed system, acetic acid type, oxalic acid type, boiling point A nitric acid system or the like can be used. After completion of the etching process, wet stripping using a stripping solution is performed or the resist is stripped and removed by dry ashing using plasma or the like. As the stripping solution in the case of wet stripping, an aqueous solution of sodium hydroxide, potassium hydroxide or the like, a solvent-organic alkali mixture, a phenolic compound-dodecylbenzenesulfonic acid-organic solvent mixture, or the like can be used. A desired fine circuit pattern can be formed through such a series of processes.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 A photosensitive composition solution (resist A) having the following composition was prepared. Solid content concentration 30%, photosensitive composition /
(Photosensitive composition + Novolak) = 0.25 is the prescription ratio.

Resist A component by weight: m / p cresol novolac resin 21.825 m / p ratio = 50/50, molecular weight = 12000 Acid ester-ECA (ethylene glycol monoethyl ether acetate) 70.0-N-cyclohexyl-2-benzothiazole 0.90 sulfenamide (abbreviated as CHBTSA)

On the other hand, for comparison, a comparative resist solution (designated as resist R1) having the same formulation ratio as the resist A and not containing the third component, CHBTSA, was prepared. Resist R1 component parts by weight m / p cresol novolac resin 22.5 m / p ratio = 50/50, molecular weight = 12000 ・ 7.5 1,2-naphthoquinonediazide-5-sulfonate of 2,3,4-trihydroxybenzophenone ECA 70.0

As a second comparative resist solution (resist R2), as an example of a thiourea compound,
Select 1'-Dimethylthiourea and use this as CHBTS
What was added instead of A was prepared. Resist R2 component parts by weight ・ m / p cresol novolac resin 21.825 m / p ratio = 50/50, molecular weight = 12000 ・ 7.275,2,2-naphthoquinonediazide-5-sulfonate of 2,3,4-trihydroxybenzophenone ・ECA 70.0 ・ 1,1'-Dimethylurea 0.90 (abbreviated as 1,1'-DMU)

First, a glass substrate on which an ITO film having a thickness of about 1200 Å was formed by a sputtering method was washed and dried by a predetermined method, and heat-treated for 15 minutes in a clean oven at 200 ° C for dehydration. After cooling, this substrate was used to apply the above resist solutions by a spin coater. For the pre-baking, an adsorption hot plate was used, and heat treatment was performed at 110 ° C./60 seconds. The thickness of the formed coating film of the photosensitive composition was 1.6 μm.
Then, this ITO substrate was passed through a test reticle having a predetermined mask pattern and exposed to ghi-mix UV light emitted from an ultra-high pressure mercury lamp using a Canon mask aligner PLA-501F to carry out proximity exposure. After that, a development process was carried out by a dipping method at 23 ° C. for 60 seconds using a caustic soda aqueous solution adjusted to 0.75% as a developing solution. After a predetermined time, DIW was performed for 30 seconds with running water, and water drops were removed with an air knife to obtain a desired resist pattern.

The thus treated ITO substrate was post-baked for 240 seconds on a heating plate kept at 120 ° C. using an adsorption hot plate.

Subsequently, the substrate after the post-baking treatment was wet-etched. The etchant used was 36% HCl: 35% FeCl ₂ : H ₂ O = 8:
It was prepared at a ratio of 1: 1 (weight ratio). The etching was performed by a dipping method under the temperature condition of 40 ± 1 ° C.
Prior to the etching test, the just etch time of the ITO substrate used was measured and found to be about 60 seconds. Therefore, the etching of the substrate with the resist pattern is just etch time (60 seconds), 120 seconds 180
The processing was performed for four types of time, ie, seconds and 600 seconds. This is normally done on the production line as opposed to Just Etch 2
˜3 times overetching time and a large excess of forced overetching time are taken into consideration for comparison.

After the etching, the dimensions of the resist pattern were measured, and then the resist was dissolved and removed with a 5% aqueous sodium hydroxide solution to obtain an ITO pattern. The dimensions of this ITO pattern were measured in the same manner as the resist pattern. IT of the resist pattern from the difference between the resist size and the ITO size
The transfer accuracy to the O film was comparatively measured.

As a result, when the pattern having a mask size of 20 μm is measured, the resist A has a side etching amount of about 2.
While the amount was 9 μm, the amount of the resist R1 was about 4.5 μm. The value of the resist R2 was 3.8 μm. Here, the one side etching amount is a value obtained by dividing the difference between the measured resist dimension and the ITO pattern dimension by two.

That is, the resist A had the smallest amount of side etching, and the transfer accuracy of the resist pattern to the ITO film was the best. Next, the resist R2 to which the 1,1'-thiourea compound having no cyclohexyl ring in the molecule was added was good. It was found that the resist R1 to which the adhesion assistant was not added had a lower resist pattern transfer processing accuracy than the other resists. Therefore, the effect of improving the processing accuracy of CHBTSA added as the third component in the resist A is clarified, and it is understood that the adhesion between the coating layer of the photosensitive composition and the substrate is remarkably improved.

Examples 2 to 3 In the above-mentioned Example 1, CHB based on the total amount of the alkali-soluble phenol resin and the o-quinonediazide compound.
The amount of TSA added was 1% by weight (referred to as resist B) and the same amount of 5% by weight (referred to as resist C) had a solid content concentration of 30% and a photosensitive composition / (photosensitive composition + The ratio of novolac) was adjusted to 25%, and the other conditions were adjusted in the same manner as in Example 1. These resists were processed up to etching in the same manner as in Example 1, and the processing accuracy was compared. As a result, the following values were obtained.

Example Resist CHBTSA Side etch amount on one side 2 B 1% by weight 3.1 μm 3 C 5% by weight 3.4 μm Comparative example R10 0% by weight 4.5 μm Comparative example R2 1.1-DMU 3% by weight 3.8 μm Example Similar to the result of No. 1, in Examples 2 and 3 of the present invention, it was clearly recognized that the side etching amount was smaller than that of Comparative Example and the processing accuracy was better.

Examples 4 to 7 The same experiment as in Example 1 was conducted except that the CHBTSA used in Example 1 was replaced with the compound shown below. In this experiment, the amount of the compound added was fixed to 3% by weight as shown in the table below for comparison.

Example Resist Additive Amount Side Etch 4 D AD1 3 wt% 2.9 μm 5 E AD2 3 wt% 3.2 μm 6 F AD3 3 wt% 3.0 μm 7 G AD4 3 wt% 3.3 μm Comparison Example R1 0 4.5 μm Comparative example R2 AD5 3% by weight 3.8 μm Comparative example R3 AD6 3% by weight 3.8 μm Comparative example R4 AD7 3% by weight 4.1 μm

AD1: 2-mercaptobenzothiazole dicyclohexylamine salt AD2: 2-mercaptobenzothiazole cyclohexylamine salt AD3: N, N-dicyclohexyl-benzothiazole-2-sulfenamide AD4: N-oxydiethylene-benzothiazole-2
-Sulfenamide AD5: 1,1-dimethylurea AD6: Mercaptobenzothiazole AD7: Methylbenzothiazole

It can be seen that in the resist of the present invention, the adhesiveness is improved as compared with the case where the third component additive is not used and the case where the adhesive aid of the present invention is not used. As described above, according to the present invention, the improvement of the adhesiveness in etching is extremely effective for the processing of a finer substrate.

[0043]

EFFECTS OF THE INVENTION The positive photosensitive composition and the method for forming a fine pattern using the same according to the present invention improve the adhesion between the metal substrate and the coating layer of the photosensitive composition and improve the workability. At the same time, the processing accuracy is improved, and precise photo-etching, in which the circuit pattern becomes finer, is enabled. Further, the improvement of processing accuracy also contributes to the improvement of yield. Since the side etching amount is small, the etchant can be strengthened to shorten the etching time, and the throughput can be expected to be improved by improving the etching process.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroaki Matsuura, Inventor Hiroaki Matsuura, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Hunt Electronics Technology Stock Company In-house

Claims (4)

[Claims] 1. (a) Alkali-soluble phenolic resin (b) o-quinonediazide compound (c) Sufficiently dissolving (a), (b) and (d) below.
Solvent having the ability to induce (d) Benzothiazole formation represented by the following general formula (I)
Compound and / or benzoti represented by the following general formula (II)
Positive-type photosensitive group comprising at least an amine salt of azole
Adult. [Chemical 1]Where R₁, R₂, R_Five, R₆Or R₇Is the hydrogen source
Child, alkyl group, alkoxy group or aryl group
You R₃And R_FourAt least one of them, or R ₈, R
₉And R_TenAt least one of them is cyclohexyl
Ring, morpholine ring, cyclohexyl ring or mole
Alkyl group, alkoxy group or ant having a holin ring
Represents a group, R₃And R_Four, Or R₈, R₉And R_Tenof
At least two of them form a ring with the nitrogen atom
It may represent a morpholine ring. What remains at this time is each
It represents a hydrogen atom, an alkyl group or an aryl group. 2. The addition amount of the compound represented by the general formula (I) and / or the compound represented by the general formula (II) is based on the total amount of the alkali-soluble phenol resin and the o-quinonediazide compound. , 0.01% to 15% by weight
The positive photosensitive composition according to claim 1, wherein 3. A step of i) applying the positive photosensitive composition according to claim 1 on a substrate, and ii) irradiating the applied positive photosensitive composition with actinic rays to form a latent image. A step of developing, to form a resist pattern, iii) a step of etching the substrate using the patterned resist as a mask, and iv) a step of peeling and removing the resist, a fine pattern forming method. 4. The method for forming a fine pattern according to claim 3, wherein the substrate is a metal film to be etched formed on a silicon wafer or a glass substrate.