JPH02132448A - Formation of pattern - Google Patents

Abstract

PURPOSE:To prevent a reduction in the thickness of a resist pattern and a dimensional change and to increase the aspect ratio of the pattern by allowing a dyestuff to be adsorbed on the exposed part of a resist or to react with the exposed part to make the exposed part insoluble in a developing soln. CONSTITUTION:A substrate 1 is coated with a positive type resist and the resist is baked to form a resist film 2. This film 2 is exposed with g-rays 4 through a mask 3 to form an exposed region 20 and the substrate 1 is immersed in an aq. soln. of a dyestuff such as cyanine dye to form a dyestuff layer 5. The entire surface of the film 2 is then exposed with g-rays 4 to expose the resist 2 through the layer 5 as a mask and a pattern 2A is formed by development with an alkaline developing soln. The resist pattern formed on the substrate may be exposed and coated with a dyestuff layer by immersion in an aq. soln. of an alkaline dyestuff compd. contg. a metal to etch the substrate through the dyestuff layer as a mask.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a pattern forming method in semiconductor manufacturing processes and the like.

2. Description of the Related Art As the miniaturization of semiconductor devices progresses, lithography techniques are also required to form patterns in the submicron region with good shape. In particular, among the current phosphorography techniques, there is a need to improve the resolution and shape of resin pattern formation in the photolithography process.

The resolution and shape of the resin pattern mainly depend on the exposure equipment.According to the reduction projection exposure equipment (stepper) among the exposure equipment currently used, 1.
A pattern of 0 μm or less can be formed.

However, for example, current devices cannot adequately support devices (such as 16 megabit D}tAM) that require a pattern around 0.5 μm.

A conventional pattern forming method will be explained with reference to FIG.

A positive resin (Shipley Co., Ltd., lJi4MPs 1400-27) was applied onto a substrate 1 such as a semiconductor that had been subjected to hydrophobic treatment, and after hot plate prebaking for 2 minutes at 9oC, 1.2
A resist film 2 of μm thickness was obtained (FIG. 7a).

Next, q-ray (436 nm) light 4 is transmitted through a mask (reticle) 3 and a projection lens (not shown). ) exposure was performed. At this time, the numerical aperture (
NA) was 0.42 (Figure 7b). lastly,
A pattern was formed by developing for 60 seconds with an alkaline developer (MF319 manufactured by Shipley) (FIG. 7C). Although the obtained resist Baku 72D had a resolution of 0.6 μm, it had film burrs in the unexposed 6 and -7 light areas of more than h, and its shape was a defective shape close to a triangle. there were.

The reason for this is that the film thickness t of Resinuto 2 is as thick as about 1 μm.
In addition, since the distance d between the mask 3 and the resist 2 is large, the light μ that wraps around from the mask edge etc. enters the region 2a that should not be exposed.

As a result, the developed resist pattern should remain as a resist pattern 2D, as shown by the broken line in FIG. 2C.

Such defective patterns of 0.5 .mu.m formed by the conventional method have been a problem that has to be taken into account when used in semiconductor manufacturing, as it may lead to a decrease in yield.

In addition, photolithography has a resolution limit of around 0.5 μm due to the diffraction development of light, and it is difficult to form patterns with good precision and shape on complex semiconductor substrates with many steps. Cases will arise.

Problems occurring at stepped portions in the conventional pattern forming method will be explained using FIG. 8. A positive resist 147 (MPS1400; Shipley Corporation) is formed to a thickness of 1.2 μm on the substrate 11 having a step of 0.6 μm. At this time, a portion where the resist film thickness becomes large or small occurs due to the influence of the step (FIG. 8a). After this, 4
36 nm light 3 was selectively exposed through a mask 4. Exposure was done using Nikon NSR1505G4C (NA 0.4
2) gave an energy of 9200 ml/crl (
Figure 8b). MF319 alkaline developer (Shipley)
A resist pattern 14A was formed by developing for 60 seconds (
Figure 8C).

Pattern 14A has the desired pattern size of 0.50μ
The dimensions of the pattern varied by more than 10 inches from m, and the pattern shape was also deteriorated9, resulting in a decrease in yield in subsequent steps.

Causes of such pattern defects include, in addition to the reasons mentioned above, unevenness in film thickness and the resolution limit of the photoluminescence device.

In order to eliminate such defects, a method has been devised in which a planarization layer is formed and a highly resistant Si-containing resist is formed on the planarization layer as an etching mask. However, even with this method, there is a problem with the solution, and this is shown in Figure 3. 1. ○ Apply planarization material RG-3900B (manufactured by Hitachi Chemical) on a substrate 1' such as a semiconductor on which a step of 2.0 μm is formed, and open bake at 200° C. for 30 minutes. The substrate 1' was planarized as a planarization layer 7 (FIG. 9a). On this upper layer is a conventional Si-containing resinuate 1.
7, RG-8500P (manufactured by Hitachi Chemical) was applied, and 8
A resist film 17 of 0.5 μm was obtained by baking at 0° C. for 20 minutes (FIG. 9b). Q-line stenopa (NA0.4
2) The film was exposed to q-ray light 4 through a mask 3 at an exposure dose of 6 o rn/ca (FIG. 9C).

Next, a resin pattern 17A with 0.5 μm line and space was obtained by immersion development in an NMD-3 alkaline developer (Tokyo Ohka) for 60 seconds (FIG. 9d).

However, the pattern 17A obtained by the method shown in FIG. 9 had a poor shape with an aspect ratio of 6o0, and also had a film edge of 2Q.

Using this pattern 178 as a mask, the lower layer 7 was etched by 02R I E (reactive ion etching), but the pattern 7B of the layer 7 reflected the defect in the upper layer pattern 17A, resulting in a 20% dimensional variation. In addition, the resulting pattern had 25% pattern film loss (FIG. 3e).

Such defective patterns caused a decrease in yield in subsequent processes.

In this way, not only this figure 9, but also resists containing Si in general, compared to ordinary photo-positive resists,
Poor sensitivity leads to a decrease in sloop soto9. Also,
The poor pattern shape leads to a decrease in device yield. Such a situation has been a worrying problem in semiconductor manufacturing.

Problems to be Solved by the Invention An object of the present invention is to form a fine resin pattern with a good shape even on a step, which cannot be achieved by conventional methods.

A further object of the present invention is to provide a method in which the resolution of a pattern is not affected by the thickness of the resist and is determined by exposure of the resist surface (approximately 0.1 μm).

10,, Another object of the present invention is to provide a method for forming a contact mask on a resist so that the distance between the mask and the resist is substantially O.

Another object of the present invention is to form a resist pattern with excellent etching resistance during dry etching.

Still, the present invention provides a method in which excess light entering the resist from the mask ethos can be reduced.

Means for Solving the Problems The present invention provides that after pattern exposure is performed on a positive resin,
This is a method of forming a fine pattern with a good shape by adsorbing or reacting a dye to the exposed area of the resist and developing the resist so as to leave the adsorbed or reacted area to form a resist pattern.

The present invention also provides a method of forming a positive resist pattern, exposing the entire surface of the pattern to light, and then forming an alkaline dye compound containing metal.

Furthermore, the present invention includes dyes on the positive resist.
, 7 provides a method for forming a Regime 1 pattern by forming a film and performing pattern exposure.

Note that a positive resist containing an onium salt may be used.

For production The present inventors first focused on the following.

Generally, the dye selectively reacts with or adsorbs to indenecarboxylic acid, which is a photoreaction product of naphthoquinonediazide that is formed in the exposed areas of the resist.

This is because if the dye is alkaline, an acid/alkali neutralization reaction is occurring, or if the dye is neutral/acidic, adsorption that forms a type of complex due to the association of molecules. Conceivable.

Further, in particular, cyanine dyes have the property of absorbing light in the ultraviolet region. For example, if there is a layer of cyanine dye of 0.1 μm, this completely acts as a mask for the underlying layer and does not allow light to pass through. At the same time, the exposed area becomes insoluble in the developer due to the bond between the indenecarboxylic acid and the cyanine dye in the exposed area.

From the above, in particular, if the entire surface is exposed to light (ultraviolet light) after adsorption of cyanine dye, only the unexposed areas of the original pattern where cyanine dye has not been adsorbed will undergo a photoreaction, and will not be dissolved in the developer. As a result, a pattern is formed in which the cyanine dye, which is the original light-emitting area, is adsorbed.

Of course, general dyes other than cyanine dyes have the same characteristics as cyanine dyes such as ml, and produce similar effects, although there are differences in size. Examples of other dyes include merocyanine dyes, oxonol dyes, acridine dyes, coumarin dyes, azo dyes, quinoline dyes, nitro chromophores, nitroso dyes, azhi dyes, carbonium dyes, and quinone imine dyes. In addition, if the dye has atoms that are resistant to acidic plasma such as silicon or tin, it is necessary to perform dry ethoching with violet plasma after the dye has reacted or adsorbed. The unexposed areas are ethoched (dry development) to form a pattern in which the dye adsorbed or reacted with the originally exposed areas.

One method of the present invention provides the above method.

13. In this method, only the surface of the resist to be colored needs to be exposed during pattern exposure of the resist, so the exposure intensity may be weak and the thickness of the resist does not affect the exposure conditions. That is, in the method of the present invention, the resolution of the resist pattern is determined by exposing only the resist surface of about 0.1 μm, and the resolution of the pattern is improved in the same way as when exposing an extremely thin resist. The colored layer acts as a mask that is in direct contact with the resist during full-surface exposure, and the distance between the resist and the mask becomes 0, eliminating light wraparound (light diffraction) and ensuring accurate exposure. becomes possible. Further, the dye layer serves as an etching mask during 02 dry etching, and a well-shaped resist pattern is formed.

In the present invention, the first pattern exposure is ultraviolet light q
In addition to line (43enm) and i-line (365nm) light, excimer laser light (248nm, 193nm, 308nm)
nm), ion beam, electron beam, or X-ray.

As mentioned above, the pattern resolution of the present invention is determined by the initial pattern light, so it goes without saying that short wavelength, high NA light is advantageous. In this first pattern exposure, it is sufficient to react only the surface of the resist, but in consideration of the resolution of the pattern and the photomaskability of the dye layer, it is desirable that the dye penetrate into the resist to a thickness of 0.5 μm or less.

The easiest method for reacting or adsorbing the dye to the light part is to dissolve the dye in water and immerse the substrate in the solution, but there are other methods in which the dye is reacted or adsorbed from a gas. can also be considered. Of course, the method is not limited to these methods.

For full-surface exposure, any ultraviolet light that the dye exhibits light absorption may be used, and the UV light may be q-ray, i-ray, or d-ray. or,
In the case of pattern formation by dry development (O2 dry etching), the dye layer is required to have etching resistance compared to 02, so the solid content of the dye should contain approximately 1% or more of Si or Sn by weight. It is desirable that

Example (Example 1) 15 of the pattern forming method of the present invention using FIG. An example will be described.

A positive resist (MP1400-27 manufactured by Shipley Co., Ltd.) is applied on a substrate 1 such as a semiconductor that has been subjected to hydrophobic treatment.
After baking on a hot plate for 2 minutes at .degree. C., a resist film 2 of 1.2 .mu.m was obtained (FIG. 1a). An insulating film or conductive film 100 is often formed on the surface of the substrate 1. next,
A semiconductor integrated circuit pattern was exposed to q-ray (4senm) light 4 through a mask 3. 20 is an exposed area. At this time, the NA of the optical device for q-ray optical output is 0.
．． It was 42. In addition, the exposure energy is 5/4 of the conventional
It was 0 mJ/crtl (Fig. 1b). The substrate 1 on which the exposed resist was formed was immersed for 60 seconds in a cyanine dye aqueous solution having the following composition.

After immersion, a layer 5 of cyanine dye with a thickness of 0.3 μm was adsorbed on the exposed area (FIG. 1C). Next, the entire surface is exposed to q-ray light 4 at an energy of 150 m/cA to form the layer 5.
Using the mask as a mask, resist 2 was exposed (Fig. 1d)
. Finally, aqueous alkaline solution (MF319 manufactured by Shipley)
Resist film 2 without layer 5 formed by 60 seconds development
The portion 2A was removed to form an inverted resist pattern 2A (FIG. 1e). Pattern 2A was a good 0.5 μm pattern with an aspect ratio of 88° and no film loss. Using this pattern 2A as a mask, for example, the underlying film 100 is selectively etched to form pattern 1 of the film 100.
0oA is formed.

Note that the cyanine dye is not limited to the one used in this embodiment, and the concentration of the aqueous solution thereof can be set arbitrarily, and a concentration of about a few centimeters is enough to function as a mask. Similar merocyanine dyes may be used as the cyanine dye, and similar good results can be obtained.

Other examples of cyanine dyes include the following compounds.

17,, 18. , -7 resist (MP1400-27 manufactured by Shipley) was applied, and after hot plate baking at 90° C. for 2 minutes, a 1.2 μm resist film 2 was formed (FIG. 2a).

Next, exposure to q-line (436 nm) light 4 was performed through a mask 3 to form an exposed portion 20. At this time, the NA of the exposure apparatus for outputting q-ray light was 0.42, and the light energy was 40 mJ/ctrl, which is the conventional value (Fig. 2b). Thereafter, a cyanine dye layer 6l as shown below was formed in the exposed area 2o by dipping in water (FIG. 2C).

(Example 2) An example of the pattern forming method of the present invention will be described with reference to FIG. In addition, in FIG. 2, the film 100 is omitted.

Boji OCH2 is placed on a substrate 1 such as a semiconductor that has been subjected to hydrophobic treatment.
CH2Sn(C2H5)3 19 Any of these dyes may be used. Of course, it is not limited to these.

Thereafter, using the cyanine dye layer d containing metal atoms as a mask, the resist is etched with O2 plasma 6 (Fig. 2 d) to form a sharp pattern 2B with a good shape.
(o.5 μm line and ● space) was obtained (Fig. 2e).

Next, an example will be described in which a flattening material and a colored layer are combined. This method uses an alkaline dye compound containing metal to improve etching resistance by 02 gas,
The lower layer is etched using a pattern using this compound as a mask.

The metal-containing alkaline dye compound used in the method of the present invention selectively forms neutralizing bonds and coordination with acids and alkalis with indene carboxylic acid generated by the edges of the positive resist, forming a dye compound on the pattern. can do. As a method of formation, for example, an aqueous solution of an alkaline dye compound containing a metal is brought into contact with a resist (coating, dipping, spraying, meniscus, etc.).

As described above, in the present invention, by forming a dye compound, it is possible to form a resist pattern that has no film ridges and has a good shape as an etching mask, and thus enables desired highly accurate etching using this resist pattern.

The present inventors have discovered that the dye solution containing St atoms as the dye compound according to the present invention selectively adsorbs and reacts with indenecarboxylic acid, radicals, ions, etc. in the glaucoma. Ta. This is thought to be because unsaturated bonds, ions, unpaired electrons, etc. in the dye formed bonds or complexes with the acid, radicals, ions, etc. generated in the exposed areas of the resist.

This phenomenon is particularly noticeable when Si atoms are present in the dye, and is thought to be because Si activates electrons and ions in the dye molecules.

The pattern-forming material of the present invention adsorbed and reacted with the exposed areas of the resist in this way is oxidized by the action of its Si atoms.
Since the RIE resistance is improved, this can be used as a mask for a two-layer resist, and by o2R processing, it is possible to form a pattern with a good shape and precision that cannot be achieved with conventional methods.

The solid content of Si atoms in the dye according to the present invention is 0.
Considering the 2 RIE resistance, it is desirable that the resistance is 5 or higher. Examples of dyes include azo dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, nitrone dyes, cyanine dyes, coumarin dyes, acridine dyes, and mixtures thereof. Not limited.

Any Si-containing molecular form may be mixed with the dye. It may be mixed with a dye as a resin such as siloxane, silanol, silane, siloxane, or a derivative resin thereof.

Examples of the solvent in the solution include water, ethinoresonolepacetate, acetone, diethylene glycol dimethyl ether, and are not particularly limited as long as they can dissolve the dye.

Possible methods for adsorbing and reacting the dye according to the present invention include immersion in a liquid, vaporization, and then vapor deposition.

Since the dye-containing film in the present invention has the property of absorbing ultraviolet light, it absorbs the scattered light from the mask edge and prevents it from entering the resist, resulting in a mask with strong ultraviolet light intensity. Only the light that has passed through the opening will be incident on the resin, resulting in an improved pattern shape.

Of course, since a certain percentage of the light from the mask opening is absorbed by the film, the exposure energy increases by a certain percentage depending on the transmittance of the film.

Regarding the transmittance of the film, it is effective in principle if it is greater than ○, but if you take into consideration the prevention of scattered light at the mask edge and the amount of exposure energy from the mask opening, it is recommended that it be less than 80%. It's as expected.

As for the components of the film, any dye that works to lower transmittance in the ultraviolet region, particularly in the exposure region, may be used, such as azo dyes, carbonium dyes, quinoneimine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, It is sufficient if it contains dyes such as cyanine dyes, merocyanine dyes, coumarin dyes, acridine dyes, etc. As a binder for rM, water-soluble resins such as polyvinylpyrrolidone, polyvinyl alcohol, pullulan, polystyrene sulfonic acid, etc. , novolak resin, polystyrene resin, and the like. Of course, these dyes and resins may be used in combination. Examples of the solvent include water, ethyl cellulsol acetate, diethylene glycol dimethyl ether, and the like.

The transmittance of the membrane can be arbitrarily controlled by changing the proportions of the dye, resin, and bath medium constituting the above group.

In addition, in the pattern forming method of the present invention, when the film is a non-aqueous solvent, a water-soluble film may be formed as an intermediate layer, depending on the case, so as not to mix with the resist.

(Example 3) This example is a method in which after a resist pattern is formed, an alkaline dye compound containing a metal is formed on the resist pattern, and the underlying layer is etched with 02-based gas, as shown in Figure 3.

RG-390oB (Hitachi Chemical), which is a planarization material, is applied on the semiconductor Si substrate 1' with a step of 1.0 μm, and
The substrate 1' was planarized by open baking at .degree. C. for 30 minutes to form a planarization layer 7 of 2.0 .mu.m.

Note that although a conductive or insulating film is often formed on the substrate 1' as shown in FIG. 3, it is omitted in FIG. 3 (FIG. 3a). On this upper layer, MP S-1 400-17 (Shipley), which is a general positive type photoresist, was applied and subjected to PPO at 86°C for 25 minutes. A resist film 8 of s μm was obtained (FIG. 3b). After this, 200 mJ/c was applied using q-ray stesopa (NA0.42).
Exposure 4 was carried out through mask 3 with a light intensity of rA (3rd
Figure C). Next, immersion development was performed for 60 seconds using MF-319 alkaline developer (Shipley), and 0.6 μm line/
An and space pattern 8A was obtained (Fig. 3d).

The entire surface of this pattern 8A is exposed to ultraviolet light 9 using an Xe-Hg lamp (1oornJ/cr!: a
t 4senm) was performed (Fig. 3e).

In the aqueous solution of an alkaline dye compound having a metal according to the pattern forming method of the present invention having the following composition,
The substrate was immersed for 10 seconds to form a 0.3 μm alkaline dye layer 1o on the pattern 8A (FIG. 3f). Pattern 8A having this dye layer 1Q had a good shape with an aspect ratio of 89°, and no film thinning was observed at all. Using this pattern 8A as a mask, the lower layer 7 is etched by 02RIE, and the resulting pattern Ryohachi is a good 0.5 μm line and space pattern that reflects the good upper layer pattern 8A without any dimensional variation or film loss. There was (Fig. 3q).

Color 26 containing metal according to the pattern forming method of the present invention,
, Composition of aqueous solution of elementary compound The following examples can be given as the dye compound according to the present invention, and similar good results can be obtained when these are used. Of course, it is not limited to these.

S 1 (CHs)s Note that the exposure to the 6f di-type resist 8 is performed by X-rays, etc., and the subsequent entire surface exposure is also performed by the same method.

(Example 4) This example also uses an alkaline dye compound containing a metal, and will be explained in conjunction with FIG. 4.

RG-3900B (manufactured by Hitachi Chemical), which is a flattening material, was applied on a substrate such as a semiconductor with a step of 0.5 μm (manufactured by Hitachi Chemical), and an open bake was performed at 200° C. for 30 minutes to form a 2.0 μm layer.
A film 7 of m was obtained. The stepped portion of the substrate was completely flattened by the film 7 of 1'tG-3900B (FIG. 4a). In addition,
An insulating or conductive film or the like is often formed on this substrate 11 as well.

Next, PosiResinut 8 (MPS1400, Shipley) was formed to a thickness of 0.6 μm (FIG. 4b).

Thereafter, 4 36 nm light 4 was selectively exposed through a mask 3 to form an exposed region 20 .

Exposure is Nikon NSR1505G4C (NA0.42)
(Fig. 4C). The substrate 11 carrying the exposed resinite 8 was immersed in the pattern forming material of the present invention having the following composition for 5 minutes, and the layer 12 of the pattern forming material of the present invention was absorbed into the exposed area (Fig. 4). d). By o2RIE,
Using the layer 12 of the patterning material of the present invention as a mask, the underlying layer 7 of RG-3900B was anisotropically etched (
Figure 4e). The layer 12 of patterning material of the present invention is 02 RIE resistant enough to etch the underlying layer 7 and has a 0.65 μm pattern 7 A with 90° kerfs.
/was gotten.

30,\1) In addition to this example, the following examples of dyes in the pattern forming material of the present invention may be mentioned. Of course, it is not limited to these.

N(CH3)2 b z (C H3)s Note that the metal atoms in these compounds can be replaced by St, Se, Ti
, Te, Sn, etc. may be used instead.

The metal used in the present invention is not limited as long as it is resistant to O2 etching of the underlying substrate, such as St, S
n, To, Se, Ti, etc., and in consideration of etching resistance, it is desirable that the overlapping ratio in the dye compound be 5 or more, but this is not limited depending on the etching conditions.

Examples of the dye compounds used in the present invention include cyanine dyes, merocyanine purple, coumarin dyes, acridine dyes, and azo dyes. It should be 9 alkaline.

(Example 6) This example is a method in which a film containing a dye is formed on a resist, and then exposed to light to form a resist pattern.
This will be explained with figures.

According to this method, a film containing a dye with an appropriate transmittance absorbs the diffracted light from the mask etching, avoids image blurring of the resist pattern due to the diffracted light, and forms a steep pattern with a high aspect ratio. Can be done.

Positive resist 2 (Shipley MP
1400) to have a thickness of 1.2 μm (6th
Diagram a). Next, a film 13 containing the dye according to the present invention having the following composition is formed to have a thickness of 0.3 μm (FIG. 5b).

(]Which is preferable, but not limited to, 3 of the salts in the dye
4. In addition to this embodiment, the following examples can be cited.

Of course, it is not limited to these.

The transmittance of this film 13 was 30 cm at 435 nm. Thereafter, using a desired mask 3, exposure is performed with F) q-line (43 enm) light 4 using a reduction projection exposure apparatus NSR1505G4C (NA 0.42) manufactured by Nikon Corporation.

The exposure energy at this time was 300 ml/crl (FIG. 5C). Finally, the film 13 was removed by immersion development for 60 seconds using an alkaline developer (Shipley Corporation MF319), and at the same time, the resist 2 was developed to selectively remove the exposed area to form a turn 2C (No. Figure 5 d).

The obtained pattern 2C had a good line and space of 0.56 μm with an aspect ratio of 89° and a film burr of 0%.

Further, the material of the membrane 13 containing the dye according to the present invention and another example will be described next.

In the present invention, a positive resist containing an onium salt can also be used. When exposed to light, a large amount of acid is generated from both the onium salt and the diazonaphthoquinone ester, which is the photoreceptor in the positive resin. Therefore, the exposed area is easily dyed with alkaline dye and serves as a mask for subsequent full-surface irradiation to block ultraviolet light. In alkaline aqueous solution development after irradiating the entire surface with this alkali-dyed mask,
As a result, when the entire surface is irradiated, a negative pattern is formed in which the pattern of the alkali dyed area that was not irradiated with light remains. Note that, of course, even without the generation of acid due to the action of such an onium salt, such good pattern formation is possible and useful just by the generation of acid from a positive resin containing a normal diazonaphthoquinone compound.

This kind of pattern is covered with the alkaline dye on top and is insolubilized in the developer, so there is no film burr.
Furthermore, since the principle is similar to that of contact M light, a pattern with high contrast is obtained without being affected by diffracted light.

Examples of the onium salt include (Xil-j: SbF6, AsF6 halogen atom, etc.), but are not limited thereto. Incidentally, these onium salts generate an acid called 19HX when exposed to light, and in order to promote the generation of this acid, heating (about 10Q to 20°C) may be performed before or after exposure.

Alkaline dyes generally include azo dyes, carbonium dyes, coumarin dyes, acridine dyes, quinone imine dyes,
Examples include methine dyes, cyanine-based, merocyanine-based, quinoline-based, nitro dyes, nitrone dyes, or mixtures thereof, but any dye that absorbs ultraviolet light or deep ultraviolet light that blocks such overall irradiation light may be used. There are no particular limitations.

Possible methods for alkaline dye solution treatment include dipping the wafer into the solution, lifting the solution in a paddle shape onto the wafer, or spraying the solution.

(Example 6) Using FIG. 6, the pattern forming method of the present invention was applied to M P 140 containing 10% by weight of Cl'-nium salt.
0 positive resist 15 to 1. 0 μm thick (6th
Diagram a). Next, exposure 4 of 100 m I /cII was performed using a Q-line Nuteppar with NA of 0.42 through a mask 3 to form an exposed region 20 (FIG. 6b). Next, a 20% aqueous solution 16 of the raw material was poured in a paddle shape, and the mixture was left at rest for 2 minutes (FIG. 6C). To the dyed exposed area 16A'38-
Using No. 7 as a mask, the entire surface was irradiated with ultraviolet light (FIG. 6 d), and a pattern 15A was formed by paddle development for 60 seconds using an alkaline developer MF319 (FIG. 6 e). The obtained pattern 15A was a 0.6 μm line fist-and-● base pattern with an aspect ratio of 88° and no film loss or dimensional variation.

Effects of the Invention As described above, the present invention forms a colored portion on a resist,
By using this to selectively expose the resist or use it as a dry etching mask, it is possible to form fine resist patterns with no film loss or dimensional variation, and a high aspect ratio. It becomes possible to realize integrated circuits.

The present invention is a method in which a positive resist is formed on a substrate, a desired pattern is exposed to energy rays, a dye is adsorbed or reacted to the exposed area, and the adsorbed or reacted area is developed so as to remain. . Alternatively, a film containing a dye may be formed on the resist, or an onium salt may be included in the positive resist.

According to these methods, a well-shaped pattern can be obtained by wet or dry development regardless of whether it is on a stepped substrate or a flat substrate. Note that a positive resist containing an onium salt is effective because its exposed areas tend to adsorb or react with dyes.

[Brief explanation of drawings]

FIG. 3 is a process diagram for forming a resist pattern. 1...Substrate, 2...Resist, 3...
...Mask, 4...Q-ray light, 5...
Cyanine dye layer, 20...exposed area, 2A...
...Resist pattern. Name of agent: Patent attorney Shigetaka Awano and 1 other person! Kagu regret ward q〕 ward U〕 懺

Claims (14)

[Claims] (1) After forming a positive resist on a substrate and selectively exposing the resist to a desired pattern using energy rays, the exposed portion of the resist adsorbed or reacted with the dye, causing the dye to adsorb or react. A pattern forming method comprising developing the resist so as to leave a portion to form a pattern of the resist. (2) Form a positive resist on a substrate, selectively expose a desired pattern to light, develop to form a resist pattern, fully expose the resist pattern, and then apply an alkaline dye compound containing metal to the resist. A pattern forming method comprising forming a pattern on a pattern, and etching a substrate using an oxygen-based gas using the resist pattern as a mask. (3) forming a resist on a substrate; forming a film containing a dye on the resist; selectively exposing the film and the resist to a desired pattern; and removing the film. A pattern forming method comprising the steps of developing the resist and removing the resist in the exposed area. (4) A positive resist containing an onium salt is formed on a substrate, the resist is selectively exposed, the resist is treated with an alkaline dye solution, the entire surface of the resist is irradiated with energy rays, and then an aqueous alkaline solution is applied to the resist. A pattern forming method comprising developing the resist and removing exposed portions of the resist. (5) The pattern forming method according to claim 1, wherein the dye is adsorbed or reacted in a liquid. (6) The pattern forming method according to claim 1, wherein the dye is a cyanine dye. (7) The pattern forming method according to claim 6, wherein the cyanine dye contains an oxygen plasma-resistant atom. (8) The pattern forming method according to claim 1, wherein development is performed using an alkaline developer after the entire surface is exposed to ultraviolet rays or far ultraviolet rays. (9) The pattern forming method according to claim 1, wherein the development is performed by etching with oxygen. (10) The pattern forming method according to claim 9, wherein the plasma-resistant atoms are silicon or tin. (11) The pattern forming method according to claim 2, wherein the metal is any one of Si, Sn, Se, Ti, Te, or a mixture thereof. (12) The pattern forming method according to claim 2, wherein the metal-containing alkaline dye compound is a dye solution containing Si atoms. (13) The pattern forming method according to claim 4, wherein heat treatment is performed before or after selective exposure. (14) The pigment or pigment compound or dye is an azo dye, carbonium dye, quinone imine dye, methine dye, quinoline dye, nitro dye, nitroso dye, cyanine dye, merocyanine dye, coumarin dye, acridine dye, or any of these dyes. 5. The pattern forming method according to any one of claims 1 to 4, characterized in that the pattern forming method is selected from mixtures.