JP2001215694A - Composition for forming antireflection film and method of producing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming an antireflection film which suppresses the flocculation and settling of a light absorbing antireflection component and ensures the desired antireflection effect and etching resistance, and a method of producing a semiconductor device using the composition. SOLUTION: The composition for forming the antireflection film which is disposed below a resist film and reduces reflected light from the lower layer side of the resist film in the production of a semiconductor device contains a light absorbing antireflection component containing at least a substituted calixarene derivative or an inclusion complex of a substituted calixarene derivative and a substituted fullerene derivative. An antireflection film 13 is formed with the composition on a substrate (10, 11) to be processed and a resist film 12 is formed on the film 13, patternwise exposed and developed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming an antireflection film and a method of manufacturing a semiconductor device, and more particularly to a photolithography process for patterning a fine wiring layer and forming a contact hole having a fine diameter. The present invention relates to a composition for forming an antireflection film and a method for manufacturing a semiconductor device using the composition.

[0002]

2. Description of the Related Art In recent years, the miniaturization and high integration of semiconductor integrated circuits have progressed to the next generation in three years, and the design rules have been reduced by 70% of the previous generation. Has also been realized. In order to finely process a semiconductor device, for example, the gate length of a gate electrode of a transistor or DR
While the area occupied by the capacitor in the AM or the like has been reduced, it has become necessary to finely process the wiring section, for example, to have a multilayer wiring structure. It is also important to form a contact hole having a fine opening diameter. As devices such as transistors and capacitors have a complicated structure and become three-dimensional, an interlayer insulating film has become thicker, and the aspect ratio of a contact hole to be opened is becoming higher.

[0003] The above miniaturization has been advanced in microfabrication technology in the manufacturing process of semiconductor devices, and in particular, a technology for transferring a circuit pattern to a photosensitive organic film (photoresist) applied on a wafer surface using light. Has been achieved by increasing the resolution in the lithography process. In particular,
The light source used in the lithography process has been shortened,
For example, g-line (436 nm) or i-line (365 nm) is used for pattern transfer of a semiconductor integrated circuit of the 1.0 to 0.5 μm rule, and i-line (365 nm) is mainly used for pattern transfer of the 0.35 μm rule. Lines are used. In addition, a technique for exposing using a KrF excimer laser (248.8 nm) or an ArF excimer laser (193 nm) has been developed for manufacturing a semiconductor integrated circuit having a rule of 0.25 μm or later.

As described above, shortening the wavelength of light used for exposure in a lithography process is very effective in improving resolution. However, shortening the wavelength of light used for exposure, on the other hand, tends to make line widths of openings and wirings formed in the resist film more susceptible to a change in film thickness of a film formed below the resist film. Also, it is difficult to control the line width in the wafer plane and between the wafers.

For example, in a method of manufacturing a semiconductor device, a method of patterning a resist film is described with reference to FIG.
This will be described with reference to FIG. As shown in FIG. 1A, a wiring portion 11 such as a gate electrode made of, for example, polysilicon or a wiring made of a material containing aluminum as a main component is formed in an upper layer of the semiconductor substrate 10.
For example, in order to pattern-process the wiring section 11 described above,
In the case of forming a resist film on the wiring section 11 by a photolithography process, first, an organic photosensitive composition is applied over the entire surface of the wiring section 11 to form a resist film 12, and then a desired film is formed. The resist film is exposed by irradiating light L such as laser light using the mask M on which the pattern is formed.

In the above, a positive resist film which is decomposed by light irradiation and becomes soluble in a developing solution is used as the resist film. The resist film 12a in a region not irradiated with light by the mask M is a region remaining as a mask for etching or the like. However, since the unevenness is formed on the surface of the wiring portion 11 due to, for example, the structure of the underlying layer, light is reflected on the uneven surface of the wiring portion 11 and the resist film 12a in a region to be left as a mask is formed.
Of the resist film 12a (for example, a shoulder portion of the resist film 12a). Therefore, as shown in FIG. 1B, when the resist film 12 is developed with the developing solution in the above case, a resist film 12a having a shape in which, for example, the shoulder is exposed and removed is formed.

As a step after the resist film 12a is patterned, the wiring portion 11 in a region not protected by the resist film 12a is removed by etching such as RIE (reactive ion etching).
Is patterned. However, in this etching, the resist film 12a is not ideally etched as a mask, but is actually slightly etched. When the shoulder of the resist film 12a to be patterned is removed as described above, the resist film in the thinned portion cannot completely protect the wiring portion 11 thereunder, and the wiring portion in this region cannot be protected. 11 is also removed by etching, and as a result, it becomes difficult to pattern the wiring portion 11 into a predetermined pattern.

In order to solve the above problem, a method of forming an antireflection film below a resist film is widely known. In the above method, the anti-reflection film is generally formed of a light-absorbing anti-reflection component having a light absorbing property in an exposure wavelength region and a binder such as an organic polymer that disperses and retains the component. The composition is formed by forming a film by coating or the like. A method of forming a pattern of a resist film by the above method will be described with reference to FIG.

As shown in FIG. 2A, a semiconductor substrate 10
In the upper layer, a wiring portion 11 such as a gate electrode made of polysilicon or a wiring formed of a material mainly containing aluminum is formed. Wiring unit 1
An antireflection film 13 is formed by applying an antireflection component having a light absorbing property and a composition for forming an antireflection film composed of a binder such as an organic polymer which disperses and retains the antireflection component to the upper layer 1. An organic photosensitive composition is applied over the entire surface thereof to form a resist film 12, and then the resist film 12 is irradiated with light L such as laser light using a mask M on which a desired pattern is formed. Is exposed.

In the above description, when a positive resist film is used, the resist film 12a in a region where light is not irradiated by the mask M becomes a region that remains as a mask for etching or the like. At this time, since the antireflection film 13 is formed, the reflection of light is suppressed even if the surface of the wiring portion 11 has irregularities. Therefore, as shown in FIG. 2B, when the resist film 12 is developed with the developing solution in the above case, a resist film 12a having a substantially rectangular cross section is formed. As a step after forming the pattern of the resist film 12a, the wiring portion 11 in a region not protected by the resist film 12a is removed by etching such as RIE, and the wiring portion 11 is patterned. In this etching, since the resist film 12a does not have a shape in which the shoulder is removed, the wiring portion 11 can be patterned into a predetermined pattern.

[0011]

However, a conventional composition for forming an antireflection film has an average particle size of 1.0 μm.
The light-reflective antireflective component in the form of particles having a particle size of about m to 2.0 × 10 ³ μm is dispersed in a polymer dispersant, a solvent, a binder, or the like. If the polymer dispersant deteriorates during storage, aggregation and sedimentation of the light-absorbing anti-reflective component tend to occur. In this case, it is difficult to obtain a desired antireflection effect and etching resistance.

In the above, the root cause of the above problem is that the light absorbing antireflection component is dispersed in a polymer dispersant, a solvent, a binder, and the like and is present in the composition for forming an antireflection film. Has become.

The present invention has been made in view of the above problems, and it is therefore an object of the present invention to suppress aggregation and sedimentation of a light-absorbing anti-reflective component and to achieve a desired anti-reflective effect and etching resistance. An object of the present invention is to provide a composition for forming an antireflection film, which can be obtained, and a method for manufacturing a semiconductor device using the composition.

[0014]

In order to achieve the above object, the composition for forming an antireflection film according to the present invention is provided below a resist film in the manufacture of a semiconductor device. A composition for forming an antireflection film for suppressing light reflected from the side, comprising at least a light-absorbing antireflection component containing a substituted calixarene derivative.

The composition for forming an antireflection film of the present invention preferably contains an inclusion complex of a substituted calixarene derivative and a substituted fullerene derivative as the light absorbing antireflective component.

The composition for forming an antireflection film of the present invention preferably further contains a polymer dispersant, a solvent and a binder.

In the above composition for forming an antireflection film of the present invention, the calixarene derivative is a macrocyclic compound having an aromatic ring as a main skeleton, and has high light absorption and etching resistance. Further, it is possible to relatively easily synthesize a substituted derivative suitable for a desired purpose, and it is possible to control the solubility in an organic solvent by modifying with a substituent. It is possible to suppress aggregation and sedimentation of the light-absorbing anti-reflective component.

The above fullerene derivative is a spherical compound having an aromatic ring as a main skeleton, and has a high light absorption and etching resistance as well as a calixarene derivative. It is possible to synthesize a substituted derivative suitable for the purpose, and by modifying with a substituent, solubility in an organic solvent can be controlled and solubilization can be achieved. In addition, it forms an inclusion complex with the above-mentioned substituted calixarene derivative, facilitates mixing of the light-absorbing antireflective component which has conventionally relied on dispersion, and preserves and rotates the antireflective film-forming composition. Coating characteristics can be improved.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming an antireflection film containing a light-absorbing antireflection component containing at least a substituted calixarene derivative on a substrate to be processed. Forming an anti-reflection film with a composition for use, forming a resist film on the anti-reflection film, exposing the resist film through a mask having a predetermined pattern, and developing the resist film. And performing a pattern processing.

The method for manufacturing a semiconductor device according to the present invention described above comprises:
Preferably, an antireflection film is formed using a composition for forming an antireflection film containing an inclusion complex of a substituted calixarene derivative and a substituted fullerene derivative as the light absorbing antireflective component.

The method of manufacturing a semiconductor device according to the present invention is as follows.
Preferably, the antireflection film is formed using a composition for forming an antireflection film further containing a polymer dispersant, a solvent and a binder.

The method of manufacturing a semiconductor device according to the present invention is as follows.
Preferably, after the step of developing and patterning the resist film, the method further includes a step of performing etching or impurity introduction using the patterned resist film as a mask.

According to the method of manufacturing a semiconductor device of the present invention, when a resist film is patterned on a substrate to be processed, the anti-reflection film formed under the resist film contains a substituted calixarene derivative. Formed using a composition for forming an antireflective film containing a light absorbing antireflective component,
As a composition for forming an anti-reflection film, aggregation and sedimentation of a light-absorbing anti-reflection component are suppressed, and a desired anti-reflection effect and etching resistance can be obtained.

[0024]

Embodiments of the present invention will be described below with reference to the drawings.

First Embodiment The composition for forming an antireflection film according to the present embodiment contains at least a light-absorbing antireflection component containing a substituted calixarene derivative, and further comprises a polymer dispersant, a solvent and The composition for forming an antireflection film can be constituted by containing a binder.

The above-mentioned substituted calixarene derivative is a macrocyclic compound having an aromatic ring as a main skeleton, and for example, as shown in the following (1) to (3), for example, 4 to 8
Benzene rings have a structure in which they are cyclically linked via a methylene group (—CH ₂ —).

[0027]

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[0028]

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[0029]

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In the above structure, an alkoxy group (—OR) is substituted and bonded to the carbon between the sites bonded to the methylene group in the 6-membered ring of each benzene ring. alkyl group (-R ₂₎ is attached by replacing the carbon in the para position Te.

In the above structure, the alkoxy group (—OR) bonded to the carbon between the sites bonded to the methylene group of the 6-membered ring of each benzene ring is a phenol substituted with an alkyl group (—R). A hydroxyl group, and an alkyl group (-
Depending on the type of R), the acidity of the substituted calixarene derivative can be adjusted. Further, an alkyl group (—R ₂ ) bonded to the carbon at the para-position to the alkoxy group is
The substitution modification is relatively easy.

The above substituted calixarene derivative is
It has high light absorption and etching resistance. Further, an alkoxy group (-OR) and an alkyl group (-
By modifying with R ₂ ), solubility in an organic solvent can be controlled, and by solubilizing in an organic solvent, aggregation and sedimentation of the light-absorbing anti-reflective component can be suppressed. . The compounds represented by the above formulas (1) to (3) are examples, and in order to obtain desired properties, as the above substituent, an alkoxy group (-OR) or an alkyl group (-
Instead of R ₂ ), various monovalent substituents can be appropriately selected, substituted, and introduced.

The above substituted calixarene derivative is
It may be contained as an inclusion complex with a substituted fullerene derivative.

The above substituted fullerene derivatives are represented by C _n
(N = 60, 70, 80, 82, 84...) Are spherical compounds having an aromatic ring as a main skeleton.
It has a structure shown in the following (4) to (6).

[0035]

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[0036]

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[0037]

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In the above structure, the compound of the formula (5) may have a divalent substituent (—R ₃ —) bonded to the compound of the formula (4) by crosslinking the aromatic ring. different. In the above structure, the compound of the formula (6) is different from the compound of the formula (4) in that a monovalent substituent (-R ₄ ,-
R ₅ ) is substituted and bonded.

The above substituted fullerene derivatives have high light absorption and etching resistance. Further, the characteristics of the substituted fullerene derivative can be adjusted depending on the type of each of the above substituents (—R ₃ —, —R ₄ , and —R ₅ ).
The solubility in an organic solvent can be controlled and the compound can be solubilized in an organic solvent. Formula (4) above
The compound represented by (6) is an exemplification, and various monovalent substituents can be appropriately selected and substituted as the above-mentioned substituents to obtain desired properties.

The above substituted fullerene derivative is used as an inclusion complex with the substituted calixarene derivative. An example of the above inclusion complex is shown in the following formula (7).

[0041]

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The compound of the above formula (7) is an inclusion complex of the compound of the formula (3) and the compound of the formula (4). There is no particular limitation on the combination used as the inclusion complex, and the inclusion complex can be formed by selecting one from each of the above-mentioned substituted fullerene derivatives and each of the substituted calixarene derivatives.

By forming an inclusion complex of the substituted calixarene derivative and the substituted fullerene derivative,
In addition to facilitating the mixing of the light-absorbing anti-reflective component, which has conventionally relied on dispersion, the storage stability and spin coating characteristics of the anti-reflective film forming composition can be improved.

Second Embodiment Next, a method of manufacturing a semiconductor device according to the present embodiment will be described with reference to FIG.

As shown in FIG. 2A, the semiconductor substrate 10
In the upper layer, a wiring portion 11 such as a gate electrode made of polysilicon or a wiring formed of a material containing aluminum as a main component is formed to constitute a substrate to be processed. A composition for forming an anti-reflection film is applied to the upper layer of the wiring portion 11 by spin coating or the like to form an anti-reflection film 13, and an organic photosensitive composition is applied to the entire upper layer to form a resist film 12. Is formed, and then the resist film is exposed by irradiating light L such as laser light using a mask M on which a desired pattern is formed.

As the composition for forming the antireflection film for forming the antireflection film 13, the composition for forming the antireflection film according to the first embodiment is used.

In the above description, when a positive resist film is used, the resist film 12a in a region not irradiated with light by the mask M becomes a region remaining as a mask for etching or the like. At this time, since the antireflection film 13 is formed, the reflection of light is suppressed even if the surface of the wiring portion 11 has irregularities. Therefore, as shown in FIG. 2B, when the resist film 12 is developed with the developing solution in the above case, a resist film 12a having a substantially rectangular cross section is formed. As a step after forming the pattern of the resist film 12a, the wiring portion 11 in a region not protected by the resist film 12a is removed by etching such as RIE, and the wiring portion 11 is patterned. In this etching, the resist film 12a has a substantially rectangular cross section, and the wiring portion 11 can be patterned into a predetermined pattern.

Alternatively, as a step after patterning the resist film 12a, for example, conductive impurities are ion-implanted using the resist film as a mask to control the conductivity of the wiring portion 11 made of polysilicon or the like. Is also possible.

According to the method of manufacturing a semiconductor device of the present embodiment, when a resist film is patterned on a substrate to be processed, a substituted calixarene derivative is used as an antireflection film formed below the resist film. Formed using a composition for forming an anti-reflective film containing a light-absorbing anti-reflective component containing, as a composition for forming an anti-reflective film, aggregation and sedimentation of the light-absorbing anti-reflective component are suppressed, A desired antireflection effect and etching resistance can be obtained.

As a method of manufacturing a semiconductor device of the present invention,
It can be applied as a manufacturing method for a MOS transistor semiconductor device such as a DRAM, a bipolar semiconductor device, or an A / D converter. A resist film is patterned by a photolithography process to form a fine wiring layer. The method can be used as a method for manufacturing a semiconductor device which performs fine processing such as opening a contact hole having a large diameter.

The present invention is not limited to the above embodiment. For example, the method of manufacturing a semiconductor device is not limited to pattern processing of a wiring layer material and opening of a contact hole.
The present invention can be applied to formation of a resist film for forming a groove or the like in an insulating film such as a metal damascene process and a resist film serving as a mask when a conductive impurity is introduced along a pattern. In addition, various changes can be made without departing from the spirit of the present invention.

[0052]

According to the composition for forming an antireflection film of the present invention, it is possible to relatively easily synthesize a substituted derivative suitable for a desired purpose, having high light absorption and etching resistance. By modifying with a group, solubility in an organic solvent can be controlled, and by solubilizing in an organic solvent, aggregation and sedimentation of a light-absorbing anti-reflective component can be suppressed.

According to the method of manufacturing a semiconductor device of the present invention,
When patterning a resist film on a substrate to be processed, as an antireflection film to be formed below the resist film, a composition for forming an antireflection film containing a light-absorbing antireflection component including a substituted calixarene derivative is used. As a composition for forming an antireflection film formed by using the composition, aggregation and sedimentation of a light-absorbing antireflection component are suppressed, and a desired antireflection effect and etching resistance can be obtained.

[Brief description of the drawings]

FIGS. 1A and 1B are cross-sectional views showing steps of a method of manufacturing a semiconductor device according to a conventional example, in which FIG. 1A shows up to an exposure step of a resist film, and FIG.

FIGS. 1A and 1B are cross-sectional views showing steps of a method of manufacturing a semiconductor device according to the present invention and a conventional example. FIG. 1A shows up to a step of exposing a resist film, and FIG. Show.

[Explanation of symbols]

10: Substrate, 11: Wiring part, 12, 12a, 12b: Resist film, 13: Antireflection film, M: Mask, L: Light.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01L 21/027 H01L 21/30 574

Claims (7)

[Claims] 1. A composition for forming an antireflection film which is provided below a resist film and suppresses light reflected from a lower side of the resist film in the manufacture of a semiconductor device. A composition for forming an antireflective film, comprising a light-absorbing antireflective component containing an allene derivative. 2. The composition for forming an antireflection film according to claim 1, wherein the light absorbing antireflection component contains an inclusion complex of a substituted calixarene derivative and a substituted fullerene derivative. 3. The composition for forming an antireflection film according to claim 1, further comprising a polymer dispersant, a solvent and a binder. 4. A step of forming an antireflection film on a substrate to be processed using a composition for forming an antireflection film containing a light-absorbing antireflection component containing at least a substituted calixarene derivative; A method for manufacturing a semiconductor device, comprising: a step of forming a resist film in an upper layer; a step of exposing the resist film via a mask having a predetermined pattern; and a step of developing and patterning the resist film. 5. An antireflection film is formed by using a composition for forming an antireflection film containing an inclusion complex of a substituted calixarene derivative and a substituted fullerene derivative as the light absorbing antireflective component. The manufacturing method of the semiconductor device described in the above. 6. The method for manufacturing a semiconductor device according to claim 4, wherein the antireflection film is formed using an antireflection film forming composition further containing a polymer dispersant, a solvent and a binder. 7. The method of manufacturing a semiconductor device according to claim 4, further comprising, after the step of developing and patterning the resist film, etching or introducing impurities using the patterned resist film as a mask. .