JP2647065B2 - Pattern formation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a resist pattern used for manufacturing a semiconductor device or the like.
The present invention relates to a pattern forming method for forming a positive pattern using, for example, ultraviolet light of 400 nm or less, an excimer laser, or the like as an exposure energy source.

[0002]

2. Description of the Related Art In recent years, with high-density integration of semiconductor devices, the light source wavelength of an exposure apparatus used for microfabrication, especially for photolithography, has been increasingly shortened. At this stage, i-line (365 nm) has entered the practical stage. KrF excimer laser (248.4 nm) has been studied.
However, resist pattern forming materials, especially KrF
Excimer lasers and those suitable for the deep ultraviolet wavelength range have not yet been developed. For example, M is said to have high sensitivity to KrF excimer laser light and far ultraviolet light and high transmittance.
Even when P2400 (Shipley) is used, the pattern shape after pattern formation can be used very poorly because of the large surface absorption of the novolak resin itself, which is the base polymer, and the poor photoreaction of the naphthoquinonediazide compound as a photosensitizer. Not really.

Further, a resist comprising a 2-diazo-1,3-dione compound has been reported as a polymer having a high transmittance for far ultraviolet light having a wavelength of around 248.4 nm as a pattern forming material for far ultraviolet rays. However, in this resist, the transmittance of the pattern forming material after exposure is only 45% while the base polymer has a transmittance of 70%, and thus, sufficient photobleaching property is not obtained. As a result of a pattern formation experiment, a pattern having an angle of about 70 degrees and a satisfactory shape of an etching mask having a vertical shape has not been obtained.

The sensitivity of this pattern forming material is 14
It was clear that the sensitivity was as low as about 0 to 150 mJ / cm ² . That is, a highly transparent pattern forming material using a 2-diazo-1,3-dione compound has low sensitivity, and practical use of such a material is particularly difficult when using a KrF excimer laser beam with low energy efficiency.

In recent years, as a means for reducing the amount of exposure energy, a material comprising, for example, poly [tert-butoxycarbonate] styrene and an onium salt has been proposed. This is a chemically amplified pattern forming material using an acid generated by exposure as a medium. I
Toly Polym. Eng. Sci. , 23 volumes, 101
2 (1983)]. A conventional pattern forming method using a chemically sensitized pattern forming material will be described with reference to FIG. A pattern forming material 12 is spin-coated on a substrate 1 such as a semiconductor and
Soft bake at 0 ° C. for 90 seconds to obtain a pattern forming material having a thickness of 1.0 μm (FIG. 4A). Note that an insulating film, a conductive film, and an oxide film are often formed on the substrate 1. Next, exposure is performed through a mask 5 with a 248.4 nm KrF excimer laser 4 to cause the following chemical change in the acid generator to generate an acid (FIG. 4B). And hot plate 3

[0006]

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By heating the above-mentioned material film at 130 ° C. for 90 seconds, the following chemical change occurs in the resin,
The resin is made alkali-soluble (FIG. 4 (c)).

[0008]

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Finally, an alkali developer (MF-31)
9 (Shipley Co., Ltd.), the exposed portions 12b of the pattern forming material 12 are dissolved and removed to obtain positive patterns 12a and 12c (FIG. 4D).

[0010]

However, according to this method, when the pattern size is 1.0 μm or less, especially 0.5 μm or less, the fine pattern 12c cannot be formed on the substrate as shown in FIG. It has been found. The broken line indicates that there is no pattern that should be left. According to the study of the present inventors, it has been found that the adhesion between the pattern forming material and the substrate is not good. This development does not cause a problem as in the above example when fabricating a device at a level of several μm, but is a serious fatal problem in the process of forming a fine pattern of 1 μm or less, particularly an ultrafine pattern of 0.5 μm or less at a high density. As a result, a device with a submicron rule cannot be manufactured.
According to the study of the present inventors, it has been found that the reason why an ultrafine pattern cannot be formed is that the adhesion between the pattern forming material and the substrate is low. A poly-t-BOC styrene resin used for a conventional pattern forming material does not have a hydrophilic group in its molecule, so that when it is made into a thin film, the film becomes hydrophobic. Before forming the pattern forming material film, the substrate is subjected to hydrophobic treatment with hexamethyldisilazane (HMDS) in order to make the state of the substrate surface uniform. Thus, the substrate surface is hydrophobic. The hydrophobic substrate and the hydrophobic pattern forming material have poor adhesion due to the study of the present inventors, and during development,
At the same time as the exposed portion was dissolved and removed, it was clarified that the unexposed portion which was not originally dissolved could not be formed on the substrate due to low adhesion. This phenomenon is particularly remarkable in a fine pattern having a pattern size of 1 μm or less. That is, to prevent this, it is particularly necessary that the dimension is 1 μm or less and 0.5 μm
The following ultrafine patterns are formed and are extremely important in the production of ultrafine semiconductor integrated circuits with high yield. Accordingly, an object of the present invention is to provide a method for reliably forming a fine pattern having a good shape and no film peeling by using a chemically amplified pattern forming material and improving adhesion.

[0011]

According to the present invention, there is provided a pattern forming method comprising the steps of: forming a pattern having a size of 0.5 μm or less on a substrate subjected to a hydrophobic treatment ;
Form a pattern with width by exposure using far ultraviolet light
To do this, place the above-mentioned substrate on an alkaline
Copolymer having soluble functional group and hydrophilic group, for exposure
Photosensitive compounds, copolymers and photosensitizers that generate more acid
To form a pattern forming material film containing a solvent that can dissolve the compound.
Process and the pattern forming material film
Selectively exposing the film and forming the pattern forming material film in a developing solution.
More developed to remove the exposed part of the pattern forming material film
Having a step of, in particular, the photosensitive compound described above,
It contains any of the sulfonyl compounds
You.

General formula

[0013]

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(Wherein R ¹ and R ² are each independently a straight-chain
, Branched or cyclic alkyl groups, haloalkyl groups,
Ruiha

[0015]

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(However, q represents 0 or a natural number, and R ³
And R ⁴ are each independently a hydrogen atom, a halogen atom,
Chain, branched or cyclic alkyl, haloalkyl,
Represents an alkoxy group, a nitro group or a cyano group), or
Is the general formula

[0017]

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(Wherein, Y represents a carbonyl group, a sulfonyl group, a sulfinyl group, R ⁵ is a lower alkyl group,
A trifluoromethyl group, a phenyl group or an alkyl-substituted phenyl group; R ⁶ and R ⁷ each independently represent a lower alkyl group, a halogen atom or a hydrogen atom; R ⁸ represents a hydrogen atom, a halogen atom, a lower Represents an alkyl group, an alkoxy group or an alkylthio group. ) .

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention will be described specifically. A photosensitive compound exposed to KrF excimer laser light or far ultraviolet light generates an acid according to a photoreaction. When heat treatment is performed after the exposure step, the functional group of the resin undergoes a chemical change by an acid, becomes alkali-soluble, and elutes in a developing solution during development. On the other hand, since no acid is generated in the unexposed portion, no chemical change occurs even by heat treatment, and no alkali-soluble group is expressed. As a result, according to the method of the present invention, a positive pattern having good contrast is formed. Further, since the acid generated by the exposure acts as a catalyst, the exposure only needs to generate the necessary acid, and the amount of exposure energy can be reduced. Peeling of a fine pattern generated during development is a serious problem in fabricating a device with a submicron rule. That is, a pattern forming method that can add a hydrophilic property to a resin in order to hydrophilize a pattern forming material and form a good shape without peeling of a pattern is indispensable for fabricating a device according to an ultrafine rule.
The present invention, by further adding a component having a hydrophilic resin (copolymer), a pattern formation material using the resin becomes hydrophilic, undergone hydrophobic substrate (hydrophobic treatment
Substrate) is improved. That is, 1.0 μm
Furthermore, an ultrafine pattern of 0.5 μm or less can be formed without peeling off during development.

[0020] The present inventors have made various studies a component having a hydrophilic, hydroxyl, carboxyl, scan Rufon acid or

[0021]

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(Where R ⁹ is a hydroxyl group, a carboxyl group ,
Represents a scan Rufon group, R ^10, R ¹¹ are each independently a hydrogen atom, a halogen atom, a lower alkyl represents a group), etc., to improve the hydrophilicity of the resin, the functional group which becomes alkali-soluble under an acid atmosphere It has been found that a pattern-forming material using a material copolymerized with a component having a high hydrophilicity and having no peeling of the resist pattern during development. The component having hydrophilicity is not limited to the above. As the functional group, t Ert- butyl, methoxymethyl, Lee Seo propoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, trimethylsilyl, te
Examples thereof include rt-butoxycarbonyl, isopropoxycarbonyl, and the like, but are not limited thereto as long as they show alkali solubility in an acid atmosphere. The same applies to the acid generator, as long as it generates an acid upon exposure may anything, for example, nitrobenzyl compounds, onium salts, sulfone Honiru compound, carboxylic acid compounds, and the like, among others specific sulfonium
When a compound (described later) is used, solution stability and acid generation
Efficiency is improved . The same applies to the solvent, as long as it can dissolve the resin and the acid generator. Hereinafter, the present invention will be described in more detail using specific examples,
The present invention is not limited to these specific examples.

Reference Example 1 A reagent was prepared with the following composition to obtain a pattern forming material.

(1)

[0025]

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(2) 2,6-dinitrobenzyl p-toluenesulfonate 1 g (3) 70 g of diethylene glycol dimethyl ether Here, the resin of (1) is tert- (tert-butoxy) butoxy as a functional group showing alkali solubility in an acid atmosphere. This is an example in which a hydroxyl group (hydroxystyrene) is used as a component having hydrophilicity. As shown below, the tert-butoxy group breaks the C—O bond under an acid atmosphere, thereby forming a hydroxyl group.

[0027]

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(2), which is used as an acid generator, causes the following reaction upon exposure.

[0029]

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(3) is an example of a solvent capable of dissolving both of them, and has a high transmittance in the deep ultraviolet region.
Good results are expected as a solvent for the F excimer laser pattern forming material. The pattern forming method of the present invention will be described with reference to FIG. A resist thin film is formed by spin-coating a pattern forming material 2 prepared with the above composition on a semiconductor substrate 1 such as silicon to form a resist thin film. Remove,
A thin film of a pattern forming material having a thickness of 1.0 μm is obtained (FIG. 1).
(A)). In many cases, an insulating film, a conductive film, a semiconductor film, and the like are formed on the surface of the substrate 1. Next, 248.4 nm
The KrF excimer laser 4 is exposed through the mask 5 to photolyze the acid generator (2) as described above. (FIG. 1 (b)). Then, the substrate is baked (PEB) at 130 ° C. for 90 seconds on a hot plate 3 to react alkali-soluble tertiary butoxy groups as described above (FIG. 1).
(C)). The pattern forming material 2 is developed for 60 seconds with an alkali developing solution (2.38% aqueous solution of tetramethylammonium hydroxide (TMAH)).
Dissolves and removes the exposed portion 2b of the positive pattern 2a, 2c
Was obtained (FIG. 1 (d)).

As described above, the pattern 2a and the fine pattern 2c of 1.0 μm or less can be formed without peeling off from the substrate 1 by the above method. Therefore, it is possible to perform a process of selectively etching the surface portion of the substrate 1 accurately using the resist patterns 2a and 2c as a mask.

The pattern forming material (film thickness 1) used in the present invention
FIG. 2 shows ultraviolet spectral curves before and after the exposure of μm). The transmittance did not substantially change before and after the exposure, showing a high value of about 65%. As a result of the pattern formation experiment, the resist pattern 2a
It was possible to form a 0.3 μm line and space pattern having a good shape. FIG. 3 shows the irradiation characteristics of the pattern forming material (1 μm). γ value5.
5. Sensitivity was 10 mJ / cm ² , high contrast and high sensitivity. Here, the limit pattern resolution and pattern angle on each substrate method using a specific example of the pattern forming material and the conventional material of the present invention in the following table.

[0033]

[Table 1]

According to the pattern forming method of the present invention, by introducing a hydrophilic group into a resin, an ultrafine pattern that cannot be formed by a conventional pattern forming method using a chemically amplified resist can be formed with a good pattern angle and sensitivity. Could be formed. Further, the pattern forming method of the present invention was able to form a pattern having a good shape without peeling on a (SiO ₂ ) or spin-on-glass (SOG) film, which is conventionally considered to have poor adhesion, like a silicon substrate. . That is, the pattern forming method of the present invention is applied to a method of forming a pattern having a thickness of
It is possible to reliably form an ultra-fine resist pattern of less than m in good shape and with good sensitivity. As a result, it becomes possible to manufacture devices as designed, and to produce ultra-fine semiconductor integrated circuit devices with sub-half micron rules. Is significant in the production of

Reference Example 2 The same experiment as in Reference Example 1 was performed except that the resin (1) was changed to the following composition.

[0036]

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This resin has a hydrophilic group (hydroxyl group).
Was introduced at a lower ratio than that of Reference Example 1. As a result of an experiment, good adhesion was obtained even when the present resin was used, and the same results as in Reference Example 1 were obtained.

( Reference Example 3 ) The same experiment as in Reference Example 1 was carried out, except that the resin (1) was changed to the following composition.

[0039]

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This resin is a component having hydrophilicity,
Sulfonic acid is introduced. As a result of the experiment, the same good results as in Reference Example 1 were obtained.

Reference Example 4 The same experiment as in Reference Example 1 was performed except that the resin was changed to the following composition.

[0042]

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The purpose of this resin is to improve the heat resistance by introducing polyparavinylphenol and C≡N in the molecule, and to simultaneously improve the adhesion by introducing a hydroxyl group. Things. As a result, a 0.3 μm pattern having high heat resistance could be formed with good adhesion.

Reference Example 5 The same experiment as in Reference Example 4 was performed except that the developing solution was changed to 2.38% TMAH (tetramethylammonium hydroxide) and a 10% aqueous solution of isopropanol.
It has been found that by mixing an alcohol such as isopropanol into the developer, a polarity is generated in the developer and the wettability with the pattern forming material film is improved. Improving the wettability between the developing solution and the pattern forming material film increases the dissolution rate of the pattern forming material in the exposed area, so that higher sensitivity can be achieved. As a result, a result similar to that of Reference Example 4 was obtained.
It was obtained with a very high sensitivity of 3.5 mJ / cm ² .
In the present embodiment it has been described with reference to highly stable tertiary butoxy group as the group indicating the alkali-soluble by an acid atmosphere, in the present invention, other tertiary butoxy carbonate group, isopropoxycarbonyl carbonate group , An isopropoxy group, a detrahydropyranyl group, a tetrahydrofuranyl group, a trimethylsilyl group, and the like, but are not limited thereto.

[0045] In the present invention, although the same is true for the acid generator, sulfonylation <br/> compound represented by the following general formula, solution stability, the acid generation efficiency or the like is good, this patterning When used as a material, good results are expected, but any material that generates an acid upon exposure may be used, and is not limited thereto.

General formula

[0047]

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( Wherein R ¹ and R ² are each independently a linear, branched or cyclic alkyl group, haloalkyl group or

[0049]

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(Where q represents 0 or a natural number; R ³
And R ⁴ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, an alkoxy group, a nitro group or a cyano group. )).

General formula

[0052]

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( Wherein , Y represents a carbonyl group, a sulfonyl group, or a sulfinyl group; R ⁵ is a lower alkyl group;
A trifluoromethyl group, a phenyl group or an alkyl-substituted phenyl group; R ⁶ and R ⁷ each independently represent a lower alkyl group, a halogen atom or a hydrogen atom; R ⁸ represents a hydrogen atom, a halogen atom, a lower alkyl group; , An alkoxy group or an alkylthio group).

As for the solvent, diethylene glycol dimethyl ether having a small absorption in the far ultraviolet region is used in the above specific example, but any solvent can be used as long as it can dissolve the resin and the acid generator, for example, ethyl cellosolve acetate, methyl cellosol acetate. , Ethyl lactate, methyl lactate, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like, but are not limited thereto. The same can be said for the exposure light source, and anything may be used as long as it generates an acid upon exposure, such as a g-line (436 nm), an i-line (365 nm), an electron beam, and an X-ray. Of course, this is not the case.

[0055]

According to the present invention, there is provided a pattern forming method using a novel pattern forming material having high sensitivity to ultraviolet light, particularly to a KrF excimer laser, high contrast, and ultra-fine lithography process. According to the present invention, it is possible to apply the present invention to ultra-fine devices such as the 0.3 μm rule and the like, which leads to miniaturization of semiconductor elements and the like and improvement in yield, thereby exhibiting great industrial value.

[Brief description of the drawings]

FIG. 1 is a process sectional view of a pattern forming method of the present invention.

[Figure 2] pattern forming ultraviolet spectral curves of the material of the present invention (where the solid line is the pre-exposure, the broken line after exposure)

Emission characteristic view of pattern forming material of the present invention; FIG

FIG. 4 is a process sectional view of a conventional pattern forming method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Silicon substrate 2 Pattern forming material film of this invention 2a, 2c Resist pattern 3 Hot plate 4 KrF excimer laser 5 Mask

Claims (3)

(57) [Claims] 1. A photosensitive compound which contains a copolymer having a functional group and a hydrophilic group which becomes alkali-soluble in an acid atmosphere and a sulfonyl compound on a substrate which has been subjected to a hydrophobic treatment, and which generates an acid upon exposure to light. Forming a pattern forming material film containing the copolymer and a solvent capable of dissolving the photosensitive compound, selectively exposing the pattern forming material film with far ultraviolet light, and forming the pattern forming material film. Developing with a developer to remove an exposed portion of the pattern forming material film to form a pattern having a width of 0.5 μm or less, wherein the sulfonyl compound has a general formula: (Wherein, R ¹ and R ² are each independently a linear, branched or cyclic alkyl group, haloalkyl group, or (However, q represents 0 or a natural number, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, an alkoxy group, a nitro group. Or a cyano group) or a general formula (Wherein, Y represents a carbonyl group, a sulfonyl group, a sulfinyl group, R ⁵ represents a lower alkyl group, a trifluoromethyl group, a phenyl group or an alkyl-substituted phenyl group, and R ⁶ and R ⁷ each independently represent Represents a lower alkyl group, a halogen atom or a hydrogen atom, and R ⁸ represents a hydrogen atom, a halogen atom, a lower alkyl group, an alkoxy group or an alkylthio group. ) . Wherein the hydrophilic group is a hydroxyl group, a carboxyl group, scan Ruff <br/> O phospho groups, or is embedded image (Wherein, R ⁹ represents a hydroxyl group, a carboxyl group, a substituent is a scan Rufon group, R ^10, R ¹¹ are each, independently a hydrogen atom, a halogen atom, a substituted group is a lower alkyl group) either The pattern forming method according to claim 1, further comprising: 3. The method according to claim 1, wherein the functional group is tert-butyl or methoxymethyl.
Le, i Seo propoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, trimethylsilyl, tert- butoxycarbonyl or pattern forming method according to claim 1, characterized in that it comprises any of isopropoxycarbonyl.