KR100760110B1 - Resist Composition, Method For Forming Resist Pattern, Semiconductor Device, And Method For Manufacturing Thereof - Google Patents

Abstract

A composition comprising a resist material and an ammonium sulfonate salt. The resist pattern formed from the composition can be uniformly thickened by a resist thickening material to form a fine pattern beyond the resolution limit of the exposure apparatus.

Resist pattern, thickening, resist composition, ammonium sulfonic acid salt

Description

Resist Composition, Method For Forming Resist Pattern, Semiconductor Device, And Method For Manufacturing Thereof}

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the mechanism which thickens the resist pattern formed from the resist composition of this invention using a resist pattern thickening material, and shows the state which provided the resist pattern thickening material to the surface of a resist pattern.

2 is an explanatory diagram of a mechanism for thickening a resist pattern formed from the resist composition of the present invention using a resist pattern thickening material, and shows a state in which the resist pattern thickening material has penetrated the resist pattern surface.

3 is an explanatory diagram of a mechanism for thickening a resist pattern formed from the resist composition of the present invention using a resist pattern thickening material, and shows a state where the resist pattern is thickened by the resist pattern thickening material.

4 is a schematic view for explaining an example of a method of forming a resist pattern of the present invention, and showing a state in which a resist film is formed.

5 is a schematic view for explaining an example of a method of forming a resist pattern of the present invention, and showing a state in which a resist pattern is formed by patterning a resist film.

6 is a schematic view for explaining an example of a method of forming a resist pattern of the present invention, and showing a state in which a resist pattern thickening material is applied to the resist pattern surface.

7 is a schematic view for explaining an example of a method of forming a resist pattern of the present invention, in which mixing occurs near the interface between the resist pattern surface and the resist pattern thickening material, and the resist pattern thickening material penetrates into the resist pattern. Indicates a state.

8 is a schematic view for explaining an example of a method of forming a resist pattern of the present invention, and showing a state in which a resist pattern thickening material is developed.

9 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, and showing a state in which an interlayer insulating film is formed on a silicon substrate.

FIG. 10 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, showing a state where a titanium film is formed on the interlayer insulating film shown in FIG. 9.

Fig. 11 is a schematic view for explaining an example of a method of manufacturing a semiconductor device of the present invention, and showing a state in which a resist pattern is formed on a titanium film to form a hole pattern on the titanium film.

12 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, showing a state where a hole pattern is also formed in an interlayer insulating film.

FIG. 13 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, and showing a state where a Cu film is formed on an interlayer insulating film on which a hole pattern is formed.

Fig. 14 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, showing a state in which Cu deposited on an interlayer insulating film other than the hole pattern is removed.

Fig. 15 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, and showing a state in which an interlayer insulating film is formed on a Cu plug and an interlayer insulating film formed in a hole pattern.

FIG. 16 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, and showing a state where a Cu plug is formed by forming a hole pattern in an interlayer insulating film as a surface layer.

17 is a schematic view for explaining an example of a method for manufacturing a semiconductor device of the present invention, and showing a state in which wiring of a three-layer structure is formed.

18 is a plan view showing an example of a FLASH EPROM manufactured by the method for manufacturing a semiconductor device of the present invention.

It is a top view which shows the other example of FLASH EPROM manufactured by the manufacturing method of the semiconductor device of this invention.

20 is a schematic cross-sectional view illustrating a method of manufacturing a FLASH EPROM that is an example of the method of manufacturing a semiconductor device of the present invention.

FIG. 21 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is an example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG. 20.

22 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is one example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG. 21.

FIG. 23 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is an example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG.

24 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is one example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG.

25 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is one example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG.

FIG. 26 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is one example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG.

27 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is one example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG.

FIG. 28 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is an example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG. 27.

29 is a schematic cross-sectional view showing the manufacturing method of a FLASH EPROM which is another example of the manufacturing method of the semiconductor device of the present invention.

30 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is another example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG. 29.

FIG. 31 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is another example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG.

32 is a schematic cross-sectional view showing the manufacturing method of a FLASH EPROM which is still another example of the manufacturing method of the semiconductor device of the present invention.

33 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is still another example of the manufacturing method of the semiconductor device of the present invention, and shows the next step of FIG. 32.

34 is a schematic cross-sectional view showing the manufacturing method of the FLASH EPROM which is still another example of the manufacturing method of the semiconductor device of the present invention, and shows the next step in FIG. 33.

35 is a schematic cross-sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head.

FIG. 36 is a schematic cross-sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 35.

FIG. 37 is a schematic cross-sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 36.

FIG. 38 is a schematic sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG.

 FIG. 39 is a schematic cross-sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 38.

FIG. 40 is a schematic cross-sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 39.

FIG. 41 is a schematic cross-sectional view illustrating an example where a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 40.

FIG. 42 is a schematic cross-sectional view illustrating an example where a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 41.

FIG. 43 is a schematic cross-sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 42.

FIG. 44 is a schematic cross-sectional view illustrating an example in which a resist pattern formed from the resist composition of the present invention is thickened using a resist pattern thickening material and applied to the manufacture of a recording head, and shows the next step in FIG. 43.

45 is a plan view illustrating one example of a recording head manufactured via the steps of FIGS. 35 to 44.

46A is a schematic explanatory diagram showing an example of a resist pattern having a gap change, and FIG. 46B is a schematic explanatory diagram showing an example of a state after thickening of a resist pattern having a gap change.

47A is a schematic explanatory diagram showing an example of a rectangular resist pattern, and FIG. 47B is a schematic explanatory diagram showing an example of a state after thickening the rectangular resist pattern.

48 is a graph showing an example of a relationship between an exposure amount and a thickening amount when a conventional resist pattern is thickened.

Fig. 49 is a graph showing an example of the relationship between the exposure amount and the thickening amount when thickening is performed on a resist pattern prepared from a non-photosensitive resin to which ammonium sulfonate is added.

It is a schematic explanatory drawing which shows an example of the relationship between the exposure amount and the thickening amount at the time of thickening the resist pattern formed using the resist composition of this invention.

FIG. 51 is a graph showing an example of a relationship between an exposure amount and a thickening amount when thickening is performed on a resist pattern formed using the resist composition of the present invention. FIG.

52A is a schematic explanatory diagram showing a resist pattern before thickening in Example 1, and FIG. 52B is a schematic explanatory diagram showing a resist pattern after thickening in Example 1. FIG.

Fig. 53 is a schematic explanatory diagram showing a resist pattern before thickening in Example 3;

Cross-Reference to Related Applications

This application is filed on August 23, 2005, and claims priority based on Japanese Patent Application No. 2005-241665, the entire contents of which are incorporated herein by reference.

Background of the Invention

The present invention provides a resist composition suitable for a resist pattern used when manufacturing a semiconductor device, a method of forming a resist pattern by thickening the resist pattern to form a fine gap pattern exceeding an exposure limit of a light source of a conventional exposure apparatus, A semiconductor and a method of manufacturing a semiconductor using the resist composition.

<Description of Related Technology>

At present, high integration of semiconductor integrated circuits has progressed, and LSI and VLSI have been put into practical use. With this, wiring patterns have been miniaturized to a size of 0.2 μm or less and to a size of 0.1 μm or less. In forming the fine wiring pattern, the substrate is covered with a resist film, and the resist film is developed after performing selective exposure to the resist film to form a resist pattern, and dry etching is performed using the resist pattern as a mask. The lithographic technique of obtaining the desired pattern by removing the resist pattern is very important. In forming a fine wiring pattern using this lithography technique, it is necessary to shorten the wavelength of the light source of the exposure apparatus and to develop a resist material having a high resolution and suitable for the characteristics of the light.

However, in order to shorten the wavelength of the light source of the exposure apparatus, an improvement of the exposure apparatus is required, which requires enormous cost. On the other hand, development of a resist material suitable for short wavelength exposure light is not easy.

For this reason, the technique which thickens a preformed resist pattern using a resist pattern thickening material (also called a "resist swelling agent") and refines a space | interval pattern is proposed. For example, Japanese Patent Laid-Open No. Hei 10-73927 discloses a resist pattern formed by exposing a positive or negative resist material to exposure light such as deep ultraviolet KrF (krypton fluoride) excimer laser light (wavelength 248 nm). Thereafter, a coating film is provided to cover the resist pattern by using a water-soluble resin composition, and the resist pattern is made to interact with the coating film and the resist pattern at its contact interface by the action of the residual acid contained in the resist pattern. The thickness between the resist patterns is shortened by thickening (hereinafter also referred to as "swelling") to form a fine gap pattern, and then a desired pattern (for example, a wiring pattern) having the same dimensions as the gap pattern is formed. A technique called Resolution Enhancement Lithography Assisted by Chemical Shrinkage (RELACS) is proposed. The.

However, in the case of the RELACS technique, the KrF resist used is formed of an aromatic resin composition such as a novolak resin or naphthoquinone diazide, and the aromatic ring contained in the aromatic resin composition is KrF (krypton fluoride). The excimer laser light (wavelength 248 nm) can be transmitted, but since the ArF (argon fluoride) excimer laser light (wavelength 193 nm), which is shorter, is absorbed and cannot be transmitted, when the KrF (krypton fluoride) resist is used, As the exposure light, there is a problem in that the ArF (argon fluoride) excimer laser light cannot be used and a finer wiring pattern or the like cannot be formed. In addition, the resist swelling agent is effective for thickening (swelling) the KrF resist pattern, but has a problem in that it is not effective for thickening (swelling) the ArF resist pattern. In addition, the resist swelling agent has low etching resistance. Therefore, when swelling the ArF resist pattern having low etching resistance, it is not possible to pattern the same dimensions as the swelled pattern on the substrate to be treated. Furthermore, even when the KrF resist having relatively satisfactory etching resistance is swollen, etching cannot be performed precisely when the etching conditions are severe, when the KrF resist pattern is fine, when the resist film is thin, etc., and the same dimensions as the swollen pattern There is a problem in that a pattern having? Cannot be obtained.

From the viewpoint of forming a fine wiring pattern, as a light source of the exposure apparatus, light having a shorter wavelength than KrF (krypton fluoride) excimer laser light (wavelength 248 nm), for example, ArF (argon fluoride) excimer laser light (wavelength 193 nm) And the like are required. On the other hand, in the case of pattern formation using X-rays, electron beams, and the like having shorter wavelengths than the ArF (argon fluoride) excimer laser light (wavelength 193 nm), the productivity is lowered at high cost, so the ArF (argon fluoride) excimer laser light ( Wavelength 193 nm) is required.

Therefore, in the RELACS technique, the resist swelling agent does not function effectively with respect to the ArF resist pattern. The resist pattern thickening material which can improve affinity with the said ArF resist pattern by surfactant, and can form a micro pattern was proposed by the present inventors (Japanese Unexamined-Japanese-Patent No. 2003-131400). However, the resist pattern thickening material composition often exhibits a dependency on the pattern size before thickening. That is, when the pattern size before thickening becomes large, the amount of reduction of the pattern size due to thickening can increase in proportion to this. Therefore, when the resist pattern thickening material is used in the line-space pattern used for the wiring layer of LOGIC LSI in which resist patterns of various sizes are mixed, there is a problem that the burden on the exposure mask design cannot be sufficiently reduced.

That is, when thickening a resist pattern formed of a conventional resist composition using a resist pattern thickening material, a short side direction of the resist pattern, or an area where elements of the resist pattern are far apart from each other (gap of elements of the resist pattern) In this long region, the thickening amount is small because the exposure amount near the pattern is small, whereas in the region where the long side direction of the resist pattern or the elements of the resist pattern are close to each other (the region where the elements of the resist pattern are short), the exposure amount is large. Because of this thickening amount is large. Therefore, the thickening amount of the resist pattern changes greatly depending on the change in the direction and / or spacing of the resist pattern.

This situation is illustrated in Figures 46A-47B of the present invention. 46A shows resist patterns with non-uniform spacing. That is, the resist pattern disclosed in Fig. 46A is a region in which the elements of the resist pattern are coarsely located, that is, the regions where the elements of the resist pattern are spaced apart from each other and the regions of the resist pattern are densely located, that is, the elements of the resist pattern. It has a short interval. As used herein, "element of a resist pattern" generally means one pattern forming a resist pattern including a plurality of patterns. If the resist pattern disclosed in Fig. 46A is thickened, as shown in Fig. 46B, the thickening amount is small in the region where the elements of the resist pattern are coarsely located with each other, and the thickening amount is large in the region where the elements of the resist pattern are densely located with each other. Further, when the rectangular resist pattern as shown in Fig. 47A is thickened, as shown in Fig. 47B, the thickening amount is larger in the long side direction of the resist pattern than in the short side direction.

Fig. 48 shows the relationship between the exposure amount (pattern exposure to the area around the pattern) and the thickening amount of the resist pattern during patterning. As shown in FIG. 48, the area where the elements of the resist pattern are coarsely located with each other or in the short side direction (see B of FIG. 48) is less exposed to the area around the pattern, and the areas of the resist pattern are densely located with each other. Alternatively, in the long side direction (see FIG. 48C), the exposure amount for the area around the pattern is larger, and accordingly, the thickening amount changes according to the difference in the exposure amount for the area around the pattern. Thus, the resist pattern exhibits uneven development results depending on the spacing and / or direction of the resist pattern. The thickening amount greatly increases before and after the specific exposure amount. When the exposure amount that increases the thickening amount approaches the patterning-exposure amount (see A of FIG. 48), the difference in the exposure amount causes a large difference in the thickening amount. The thickening effect of the resist pattern thickening material generally depends on the acid concentration of the exposed area of the resist pattern. In the art, resist compositions contain photoacid generators and the acid is produced, for example, by exposure in the exposed areas. Therefore, the thickening amount usually increases around the exposure amount, and accordingly, the thickening amount is greatly changed by the resist pattern. To solve this problem, the exposure dose can be adjusted away from the exposure dose (see X in FIG. 48) which increases the thickening amount.

The thickening amount of the resist pattern is equal to or less than the initial film thickness (see Y in FIG. 48) of the resist pattern thickening material.

Also, typically, high resolution of the resist pattern has been achieved by the addition of a basic material such as a quencher. The quencher controls the diffusion of acid generated from the photoacid generator by exposure in the resist pattern. The compound used as such a quencher is usually selected from tetraalkyl ammonium hydroxide, amines, and the like. When a combination of a commercially available resist composition containing these materials and a commercially available resist pattern thickening material is used, various problems such as size dependence are encountered. Easy to occur In addition, since the basic material used as the quencher is difficult to control the diffusion of acid into the resist pattern thickening material, the reaction between the resist pattern and the resist pattern thickening material cannot be controlled.

In summary, in the prior art using RELACS material on KrF or novolak resist pattern, due to the strong absorption of exposure by KrF resist, ArF (argon fluoride) excimer laser light can be used as the light source of the exposure apparatus for patterning. none. In addition, conventional ArF resist patterns and the like cannot be sufficiently thickened by the above-mentioned resist swelling materials used in RELACS technology. In addition, it is difficult to form a fine gap pattern or a wiring pattern at low cost while applying electron beam or X-ray exposure. Therefore, it is desirable to improve the RELACS technology.

This invention makes it a subject to solve the conventional problem and to achieve the following objectives.

The present invention can use ArF (argon fluoride) excimer laser light as the exposure light at the time of patterning, and after exposure and development to form a resist pattern, by applying a resist pattern thickening material on the surface of the resist pattern, the resist pattern It is suitable for thickening the film, and is uniformly thickened to exceed the exposure limit or resolution limit in the light source of the exposure apparatus without depending on the direction and / or gap change of the resist pattern and the components of the resist pattern thickening material. It is an object of the present invention to provide a resist composition capable of easily and efficiently forming a fine gap pattern at low cost.

In addition, the present invention can use ArF (argon fluoride) excimer laser light as the exposure light at the time of patterning, and does not depend on the change of the direction and / or spacing of the resist pattern and the components of the resist pattern thickening material, It is an object of the present invention to provide a resist pattern forming method that can be thickened uniformly and is suitable for easily and efficiently forming a fine gap pattern exceeding an exposure limit or resolution limit in a light source of an exposure apparatus at low cost.

In addition, the present invention can use ArF (argon fluoride) excimer laser light as the exposure light at the time of patterning, and does not depend on the change of the direction and / or spacing of the resist pattern and the components of the resist pattern thickening material, It can be thickened uniformly and is suitable for easily and efficiently forming a fine gap pattern exceeding the exposure limit or resolution limit in the light source of the exposure apparatus at low cost, and the fine wiring formed by using this fine gap pattern An object of the present invention is to provide a method for manufacturing a semiconductor device capable of mass-producing a high-performance semiconductor device having a pattern, and a high-performance semiconductor device manufactured by the method for manufacturing the semiconductor device and having a fine wiring pattern.

MEANS TO SOLVE THE PROBLEM The present inventors earned the following discoveries as a result of earnestly examining in view of the said subject. That is, when the sulfonate ammonium salt is added to the resist composition, interaction between the resist composition and the resist pattern thickening material is performed irrespective of the exposure amount, and thus the direction, gap change, etc. of the resist pattern and the thickness of the resist pattern are thickened. The resist pattern is thickened in a good and uniform manner without being influenced by the components of the material.

The present invention is based on the experience and findings of the inventors. The resist composition of the present invention includes an ammonium sulfonate salt. When the resist pattern is formed using the resist composition of the present invention, and the formed resist pattern is thickened using a resist pattern thickening material, the resist pattern thickening material may be formed by the direction of the resist pattern, a change in spacing, or the like. It is not affected, and the resist pattern is thickened both well and uniformly.

As described above, when thickening a resist pattern formed of a conventional resist composition using a resist pattern thickening material, the thickening amount of the resist pattern is greatly changed by the direction and spacing of the resist pattern. However, in the case of the present invention, when the resist pattern thickening material is applied onto a resist pattern formed using the resist composition of the present invention, one of the applied resist pattern thickening materials is near the interface with the resist pattern. It penetrates into the resist pattern and interacts with (mixes) the resist pattern composition. At this time, since the ammonium sulfonate salt causes the interaction regardless of the exposure amount near the pattern, the resist pattern thickening material and the resist pattern interact with each other on the surface of the resist pattern as an inner layer. The surface layer (mixing layer) is formed efficiently. As a result, the resist pattern is thickened efficiently by the resist pattern thickening material. The thickened resist pattern (hereinafter also referred to as "thickness resist pattern") is uniformly thickened by the resist pattern thickening material. For this reason, the gap pattern formed by the thickening resist pattern has a finer structure beyond the exposure limit (resolution limit). The term “space pattern” in the context of the present invention generally means a hole, trench, recess or other void space formed by a resist pattern. Therefore, the resist composition of the present invention can be used to form resist patterns such as line and gap patterns in a wiring layer of LOGIC LSI in which resist patterns of various sizes are mixed.

The method of forming a resist pattern of the present invention includes forming a resist pattern using the resist composition of the present invention and applying a resist pattern thickening material to cover the surface of the resist pattern.

In the method of forming the resist pattern, after the resist pattern is formed using the resist composition of the present invention, the resist pattern thickening material is applied onto the resist pattern. What is near the interface with the infiltrate the resist pattern to interact with (mix) the resist composition. Therefore, a surface layer (mixing layer) formed on the surface of the resist pattern as an inner layer and interacting with the resist pattern thickening material and the resist pattern is formed. In this way, the resist pattern is uniformly thickened by the resist pattern thickening material. For this reason, the gap pattern formed by the thickening resist pattern has a finer structure beyond the exposure limit (resolution limit). In addition, since the resist composition includes the ammonium sulfonate salt, the resist pattern formed by using the resist composition does not depend on the change in the direction and / or spacing of the resist pattern and the components of the resist pattern thickening material. It can be thickened favorably and uniformly. The thickening of the resist pattern is not dependent on the direction and / or spacing change of the resist pattern and the components of the resist pattern thickening material. For this reason, the method of forming the resist pattern is preferably applicable not only to the contact hole pattern but also to the formation of resist patterns such as line-gap patterns used in wiring layers of LOGIC LSI in which resist patterns of various sizes are mixed.

In the method for manufacturing a semiconductor device of the present invention, forming a resist pattern using the resist composition of the present invention on a surface to be processed, and applying the resist pattern thickening material to cover the surface of the resist pattern, thereby forming the resist pattern. Thickening, etching and patterning the surface to be processed using the thickened resist pattern as a mask.

In the method of manufacturing the semiconductor device, first, a resist pattern is formed on the processed surface, which is a target for forming a pattern such as a wiring pattern, in the resist pattern forming step by using the resist composition of the present invention, and then the surface of the resist pattern The resist pattern thickening material is applied so as to cover. In this case, among the resist pattern thickening materials, those near the interface with the resist pattern penetrate the resist pattern and cause interaction (mixing) with the material of the resist pattern. Therefore, the resist pattern thickening material and the resist pattern interact with each other to form a surface layer (mixing layer) on the surface of the resist pattern as an inner layer. The thickened resist pattern thus thickened is uniformly thickened by the resist pattern thickening material. Therefore, the gap pattern formed by the thickening resist pattern has a finer structure beyond the exposure limit (resolution limit). In addition, since the resist composition contains the ammonium sulfonate salt, a resist pattern formed by using the resist composition is good regardless of the direction of the resist pattern, a change in spacing, etc., and regardless of the components of the resist pattern thickening material. While also thickening uniformly. The thickening process of the resist pattern has no dependence on the direction and spacing change of the resist pattern, the components of the resist pattern thickening material, and the like. For this reason, not only the contact hole pattern but also thickening resist patterns such as line-gap patterns used in the wiring layer of LOGIC LSI, which is a semiconductor device in which resist patterns of various sizes are mixed, are easily and precisely formed.

Next, by etching the surface to be processed using the thickened resist pattern, the surface to be processed is fine, high precision, and patterned with good dimensional accuracy, so that a wiring pattern having a very fine, high precision and excellent dimensional accuracy is obtained. The high quality and high performance semiconductor device which has is manufactured efficiently.

The semiconductor device of this invention is manufactured by the manufacturing method of the said semiconductor device of this invention, It is characterized by the above-mentioned. This semiconductor device has a very fine and high precision and has a pattern such as a wiring pattern which is excellent in dimensional accuracy, and is of high quality and high performance.

Best Mode for Carrying Out the Invention

The present invention provides a resist composition comprising a resist material and an ammonium sulfonate salt.

The resist material of the present invention can generally be used as a chemically amplified resist system. The resist material may include resins, photoacid generator (s), quencher (s), surfactant (s), and may further include other materials as needed.

When the resist pattern is formed using the resist composition of the present invention and a resist pattern thickening material described later is applied on the resist pattern, the resist pattern thickening material is located near an interface with the resist pattern. Penetrates into the trace pattern and interacts with (mixes) the material of the resist pattern. At this time, since the ammonium sulfonate salt has high reactivity with the resist pattern thickening material, the resist pattern thickening material and the resist pattern interact with each other on the surface thereof with the resist pattern as an inner layer (a mixing layer). ) Is formed efficiently. As a result, the resist pattern is efficiently thickened by the resist pattern thickening material, and the thickened resist pattern (hereinafter, referred to as a "thinned resist pattern") is uniformly made by the resist pattern thickening material. It is thickened. For this reason, the gap pattern formed by the thickening resist pattern has a finer structure beyond the exposure limit (resolution limit).

Since the resist composition of the present invention contains the ammonium sulfonate salt, it exhibits a good and uniform thickening effect regardless of the components of the resist pattern thickening material. Further, the resist composition is hardly affected by the size, gap change, direction of the resist pattern, components of the resist pattern thickening material, and the like.

The resist pattern thickening material generally includes a resin. Therefore, the ammonium sulfonate salt contained in the resist composition can cause an interaction (reaction) with the resist pattern thickening material to thicken the resist pattern, and the interaction is performed irrespective of exposure. Fig. 49 shows the relationship between the exposure amount and the thickening amount of the resist pattern when the sulfonate salt is added to the resin having no photoreactivity to thicken the resist pattern. As shown in Fig. 49, the sulfonate ammonium salt showed a certain amount of thickening effect without depending on the exposure dose. 50 shows the relationship between the exposure amount and the thickening amount of the resist pattern when forming a resist pattern from a resist composition containing an ammonium sulfonate salt. As shown in FIG. 50, the thickening amount of a resist pattern becomes the size which thickened amount which depended on a normal exposure amount, and the thickening amount which does not depend on an exposure amount by the said ammonium sulfonate salt sum together. At this time, the maximum value of the thickening amount does not exceed the initial film thickness of the resist pattern thickening material. As a result, the thickening amount rising exposure amount can be set away from the patterned exposure amount, whereby the thickening amount difference can be reduced.

(Sulfonic Ammonium Salt)

As described above, the resist composition includes an ammonium sulfonate salt. The ammonium sulfonate salt can be appropriately selected according to the purpose. Since the ammonium sulfonate salt is neutral and the amount of use of the resist composition is small, it does not adversely affect the function of the resist composition.

The sulfonate ammonium salt has a sulfonic acid residue and an ammonium residue. The sulfonic acid residue may be appropriately selected depending on the purpose, but may be derived from trifluoromethanesulfonic acid, toluenesulfonic acid, and the like, that is, trifluoromethanesulfonic acid anion and p-toluenesulfonic acid anion in view of ease of synthesis and availability. . When the resist composition comprises one or more sulfonate ammonium salts, the sulfonic acid residues are the same or different from one another and may be selected from the ions listed above.

The ammonium moiety can be appropriately selected depending on the intended purpose. The ammonium moiety may be a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, or the like. When the resist composition comprises at least one ammonium sulfonate salt, the ammonium moieties are the same or different from one another and may be selected from the ions listed above. If the ammonium moiety is selected from quaternary ammonium ions such as ammonium ions (NH ₄ ⁺ ), tetramethylammonium ions, tetraethylammonium ions, or the like, they do not react with the resist pattern thickening material or significantly lack reactivity. Do.

In view of ease of synthesis or availability and appropriate reactivity, the ammonium moiety may be represented by the following formula (1).

<Formula 1>

N ⁺ R ¹ R ² R ³ R ⁴

In the formula (1), N represents a nitrogen atom. R ¹ to R ⁴ has at least one represents hydrogen and the other is selected from alkyl group and a phenyl group in C _{1 -4.}

Specific examples of the ammonium sulfonate salt include p-toluenesulfonic acid triethylammonium salt, trifluoromethanesulfonic acid methylphenylammonium salt, trifluoromethanesulfonic acid dimethylammonium salt, and p-toluenesulfonic acid monoethylammonium salt. The ammonium sulfonate salts may be used alone or in combination in the resist composition of the present invention.

Content in the said resist composition of the said ammonium sulfonate salt can be suitably selected according to the objective. The content of the ammonium sulfonate salt in the resist composition may, in one embodiment, be 0.01 to 5% by mass relative to the total solids of the resist composition, and in other embodiments may be 0.05 to 2% by mass.

If the content is less than the lower limit with respect to the mass of the total solid of the resist composition, the reactivity with the resist pattern thickening material may be inferior. When the content exceeds the upper limit with respect to the mass of the total solids of the resist composition, the resist characteristics may be deteriorated due to precipitation of salt or the like.

In addition, the ammonium sulfonate salt is added at the time of preparation of the resist composition or to a commercially available resist composition.

There is no restriction | limiting in particular as a presence confirmation method of the said sulfonate ammonium salt in the said resist composition, For example, it can confirm by liquid chromatography.

(Resist material)

The resist material of this invention can be suitably selected according to the objective as long as the said resist material and ammonium sulfonate salt form the resist composition of this invention. The resist composition has a sensitivity to exposure light having a wavelength of 440 nm or less, and may be exposed using exposure light having a wavelength of 440 nm or less.

The exposure light is not particularly limited as long as the exposure wavelength is 440 nm or less, and can be appropriately selected according to the purpose. Examples of the exposure light include g line (wavelength 436 nm), i line (wavelength 365 nm), KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (wavelength 157 nm), Electron beams; and the like.

The resist composition may comprise a resist material that is patternable by exposure light, and these may be selected from known negative or positive resist materials. Examples of the resist material include g-ray resist, i-ray resist, KrF resist, ArF resist, F ₂ resist, electron beam resist and the like. These are chemically amplified resists or non-chemically amplified resists. Among these, KrF resists, ArF resists, and resists made of acrylic resins are preferred. From the viewpoint of finer patterning, improvement in throughput, and the like, ArF resists requiring an extension of exposure limit and acrylic resins are included. The resist produced is more preferred.

The ArF resist can be appropriately selected depending on the purpose. The ArF resist may be an alicyclic resist.

As said alicyclic resist, an acrylic resist which has an alicyclic functional group in a side chain, a cycloolefin maleic anhydride (COMA) resist, a cycloolefin resist, a hybrid (alicyclic acrylic-COMA copolymer) resist, etc. are mentioned, for example. . These can be modified with fluorine.

Moreover, the said alicyclic functional group can be suitably selected according to the objective. The alicyclic functional group may be an adamantyl group, a norbornyl functional group, or the like. In addition, the cycloolefin-based resist may be a resist containing a cycloolefin containing adamantane, norbornane, tricyclononane and the like in the main chain.

(Formation method of resist pattern)

The formation method, size, thickness, and the like of the resist pattern can be appropriately selected according to the purpose, and the thickness can be appropriately determined depending on the surface to be processed, the etching conditions, and the like, but is generally about 0.2 to 700 µm.

The thickening of the resist pattern using the resist composition will be described below with reference to the drawings.

As shown in FIG. 1, after forming the resist pattern 3 using the said resist composition of this invention on the to-be-processed surface (base material) 5, the resist pattern thickening material on the surface of the resist pattern 3 is carried out. (1) is given (applied). Prebaking (warming and drying) forms a coating film. Next, a resist film is exposed by exposure light through an appropriate mask pattern. The exposed film is baked, developed in alkaline developer and washed in deionized water. The resist pattern thickening material is then coated onto the resist pattern and baked. At the interface between the resist pattern 3 and the resist pattern thickening material 1, mixing (penetration) of the resist pattern thickening material 1 into the resist pattern 3 occurs. As shown in Fig. 2, the mixed (penetration) portion reacts at the interface between the inner layer resist pattern 10b (resist pattern 3) and the resist pattern thickening material 1 to react with the surface layer (mixing layer) 10a. ) Is formed. At this time, since the sulfonate ammonium salt is contained in the resist composition of the present invention, it is thickened without depending on the change in the direction or the interval of the inner layer resist pattern 10b (resist pattern 3).

Thereafter, as shown in FIG. 3, the portion of the resist pattern thickening material 1 applied (developed) by developing, which does not interact (mix) with the resist pattern 3 to the interaction (mixing) This weak part (part with high water solubility) is dissolved and removed, and the thickened resist pattern 10 thickened uniformly is formed (developed).

In addition, the development treatment may be performed using water or an alkaline developer.

The thickened resist pattern 10 has a surface layer (mixing layer) 10a formed by reacting the resist pattern thickening material 1 on the surface of the inner layer resist pattern 10b (resist pattern 3). Since the thickened resist pattern 10 is thickened by the thickness of the surface layer (mixing layer) 10a compared with the resist pattern 3, the size of the gap pattern formed by the thickened resist pattern 10 (adjacent) The distance between the thickened resist patterns 10 or the aperture diameter of the hole pattern formed by the thickened resist pattern 10) is smaller than that formed by the resist pattern 3 before thickening. For this reason, the gap pattern formed by the said resist pattern exceeds the exposure limit (resolution limit) of the light source of the exposure apparatus at the time of forming the resist pattern 3. That is, when the resist pattern is patterned using ArF excimer laser light, and the resist pattern is thickened using a resist pattern thickening material, the gap pattern formed by the thickened resist pattern is patterned using an electron beam. It can exhibit the same microscopic state as one. The gap pattern formed by the thickened resist pattern 10 is finer and has higher precision than the gap pattern formed by the resist pattern 3.

Since the resist composition of the present invention contains the ammonium sulfonate salt, after exposure and development to form a resist pattern, a resist pattern thickening material is applied to the surface of the resist pattern, so that the resist pattern is preferably thickened. Further, regardless of the direction of the formed resist pattern, change in spacing, or the like, the thickness is uniformly thickened by the resist pattern thickening material without depending on the type of the resist pattern thickening material. Beyond the limit (resolution limit), fine spacing patterns can be easily and efficiently formed at low cost. Moreover, the resist composition of this invention can be used especially suitably for the formation method of the resist pattern of this invention, the manufacturing method of the semiconductor device of this invention, etc.

The resist composition of this invention is used suitably for the resist pattern formation method of this invention, and the semiconductor device manufacturing method of this invention.

As described above, the realization of high resolution and the securing of a good thickening amount cannot be achieved simultaneously in the past. However, by using the resist composition of the present invention, the reaction (interaction) between the resist pattern and the resist pattern thickening material can be controlled without controlling the diffusion of acid, so that the size of the resist pattern is realized while realizing high resolution. The dependency of the thickening effect on can be reduced.

In general, the method for forming a resist pattern of the present invention includes forming a resist pattern using the resist composition of the present invention and then applying a resist pattern thickening material to cover the surface of the resist pattern. The formation method of the resist pattern of this invention can further include the other process suitably selected as needed.

Details of the resist composition are as described above in the resist composition section of the present invention.

The resist pattern may be formed on the surface to be processed (substrate). The surface to be processed (base material) can be appropriately selected according to the purpose. When the resist pattern is formed in a semiconductor device, the processing surface (substrate) is, for example, a semiconductor substrate surface. As a specific example, board | substrates, such as a silicon wafer, various oxide films etc. are mentioned.

The resist pattern thickening material can be appropriately selected from known ones according to the purpose as long as the resist pattern is thickened by applying it onto the resist pattern. The resist pattern thickening material may contain a surfactant or the like, may be a commercial item, or may be appropriately synthesized.

The application method of the resist pattern thickening material can be appropriately selected from known application methods according to the purpose. For example, a spin coating method etc. are mentioned preferably. In the case of the spin coating method, the conditions thereof include, in one embodiment, about 100 to 10,000 rpm, in another embodiment 800 to 5,000 rpm, a duration of about 1 second to 10 minutes in one embodiment, and another embodiment. From 1 second to 90 seconds.

As application thickness at the time of the said application | coating, it is about 100-10,000 mm (10-1,000 nm) in one embodiment normally, and is 1,000-5,000 mm (100-500 nm) in another embodiment.

At the time of the application and thereafter, the applied resist pattern thickening material is prebaked (heated and dried) to form the resist pattern of the resist pattern thickening material at an interface between the resist pattern and the resist pattern thickening material. Mixing (penetration) of ene can be generated efficiently.

In addition, the conditions, methods, and the like of the prebaking (heating and drying) may be selected so as not to soften the resist pattern, and may be appropriately selected according to the purpose. For example, the number of prebakings may be one or two or more times. In the case of two or more times, the temperature of the prebaking in each time may be constant, and may differ. If the temperature is constant, in one embodiment it may be on the order of 40-150 ° C., in other embodiments it may be 70-120 ° C., and also as its time, in one embodiment it may be on the order of 10 seconds to 5 minutes, and in other embodiments From 40 seconds to 100 seconds.

**

In addition, it can be baked after prebaking (warming and drying) if necessary in view of efficiently advancing mixing or penetration at the interface between the resist pattern and the resist pattern thickening material.

The baking conditions, methods and the like can be appropriately selected according to the purpose. However, temperatures higher than those in prebaking (heating and drying) are usually used. Baking conditions can be, for example, a temperature of about 70 to 150 ° C. in one embodiment, 90 to 130 ° C. in another embodiment, and its time may also be on the order of 10 seconds to 5 minutes in one embodiment, and In embodiments, from 40 seconds to 100 seconds.

In addition, after the baking, development may be performed on the applied resist pattern thickening material. In this case, the above development is performed by dissolving and removing a portion of the applied resist pattern thickening material that does not interact (mix) with the resist pattern or a portion having a weak interaction (mixing) with a high thickness resist. It is preferred in that the pattern can be developed (obtainable).

In addition, the developing treatment may be water development, or may be development by an alkaline developer. In terms of low cost and efficiency, water development can generally be carried out.

When the resist pattern thickening material is applied onto the resist pattern and interacts with (mixes) the resist pattern, a layer formed by interacting the resist pattern thickening material and the resist pattern on the surface of the resist pattern ( Mixing layer) is formed. As a result, the resist pattern is thickened by an amount corresponding to the thickness of the mixing layer, thereby forming a thickened resist pattern.

The diameter to width of the gap pattern formed by the thickened resist pattern is thus smaller than the diameter to width of the gap pattern formed by the resist pattern before thickening. As a result, the finer said beyond the exposure limit (resolution limit) of the light source of the exposure apparatus used at the time of patterning the resist pattern (less than the limit of the opening to the pattern interval size patternable to the wavelength of light used for the light source) A gap pattern is formed. That is, when patterning a resist pattern using ArF excimer laser light and thickening it using the resist pattern thickening material, the gap pattern formed by the thickened resist pattern is spaced from that patterned using an electron beam. It becomes fine and high precision like a pattern.

In addition, the thickening amount of the resist pattern can be controlled in a desired range by appropriately adjusting the viscosity, coating thickness, baking temperature, baking time and the like of the resist pattern thickening material.

According to the present invention, the pattern size variation may be limited to less than 20 nm in one embodiment, and to less than 15 nm in other embodiments. In the present invention, the term “pattern size variation” generally means the difference between the size of the narrow side and the size of the wide side or the width and length of the elements of the resist pattern.

Here, the formation method of the resist pattern of this invention is demonstrated, referring drawings.

As shown in FIG. 4, after applying the resist composition 3a of this invention on the to-be-processed surface (substrate) 5, as shown in FIG. 5, this is patterned and the resist pattern 3 is formed. Next, as shown in FIG. 6, the resist pattern thickening material 1 is apply | coated to the surface of the resist pattern 3, and it pre-bakes (heats and dries) to form a coating film. As a result, mixing (penetration) of the resist pattern thickening material 1 into the resist pattern 3 occurs at the interface between the resist pattern 3 and the resist pattern thickening material 1. As shown in Fig. 7, the mixed (penetrated) portion at the interface between the resist pattern 3 and the resist pattern thickening material 1 further reacts or interacts with each other. Subsequently, as shown in FIG. 8, when the development treatment is performed, a portion of the applied resist pattern thickening material 1 that does not react with the resist pattern 3 or a weak interaction (mixing) is weak (high water solubility). The portion) is dissolved and removed to form (develop) the thickened resist pattern 10 having the surface layer 10a on the inner layer resist pattern 10b (resist pattern 3).

The thickened resist pattern 10 is thickened by the resist pattern thickening material 1, and is formed by reacting the resist pattern thickening material 1 on the surface of the inner layer resist pattern 10b (resist pattern 3). It has surface layer 10a. At this time, since the resist composition 3a contains the ammonium sulfonate salt, the direction of the inner layer resist pattern 10b (resist pattern 3), the change in the spacing, and the like, depending on the type of the resist pattern thickening material 1 It is thickened without being adversely affected. The thickened resist pattern 10 is thickened by the thickness of the surface layer 10a compared with the resist pattern 3 (inner layer resist pattern 10b). The width of the gap pattern formed by the thickened resist pattern 10 is smaller than the width of the gap pattern formed by the resist pattern 3 (inner layer resist pattern 10b), and is formed by the thickened resist pattern 10. The gap pattern is fine.

The method of forming the resist pattern of the present invention is suitable for forming various gap patterns, for example, line & space patterns, hole patterns (for contact holes, etc.), trench (groove) patterns and the like. The thickened resist pattern formed by the method of forming the resist pattern can be used as a mask pattern, a reticle pattern, or the like, and can be used as a metal plug, various wirings, a recording head, an LCD (liquid crystal display), a PDP (plasma display panel), and a SAW. Functional parts, such as a filter (elastic surface wave filter), optical components used for connection of light wiring, micro components, such as a micro actuator, can be used for manufacture of a semiconductor device, and are suitable for the manufacturing method of the semiconductor device of this invention mentioned later Can be used.

(Manufacturing Method of Semiconductor Device)

In the method of manufacturing a semiconductor device of the present invention, after forming a resist pattern using the resist composition of the present invention on the surface to be processed, the resist pattern thickening material is applied to cover the surface of the resist pattern, and then subjected to the resist pattern. Thickening, and then etching the surface to be processed using the thickened resist pattern as a mask to pattern the surface to be processed. The manufacturing method of the semiconductor device of this invention can further include another process as needed.

The resist pattern forming step is a step of forming a resist pattern using the resist composition of the present invention on the surface to be processed, and the applying step is performed by applying a resist pattern thickening material to cover the surface of the resist pattern. It is the process of thickening. In this manner, a thickened resist pattern is formed on the workpiece surface.

Detailed description of the resist pattern forming process is the same as the method of forming the resist pattern of the present invention.

Although the surface layer of the various member in a semiconductor device is mentioned as said to-be-processed surface, The board | substrate, such as a silicon wafer, its surface, various oxide films, etc. are mentioned preferably. The resist pattern is as described above. The coating method is as described above. In addition, after the said application, the above-mentioned prebaking, baking, etc. can be performed.

The said etching process is a process of patterning the said to-be-processed surface by performing the etching using the said thickening resist pattern formed by the said resist pattern formation process (as a mask pattern etc.).

The said etching method can be suitably selected from a well-known method according to the objective. In one embodiment dry etching may be used. The said etching conditions can be suitably selected according to the objective.

As said other process, surfactant coating process, image development process, etc. are mentioned.

The surfactant coating step is a step of applying a surfactant to the surface of the resist pattern before applying the resist pattern thickening material.

The surfactant may be appropriately selected from cationic surfactants, anionic surfactants, and nonionic surfactants (they do not contain metal atoms or ions) according to the purpose. Suitable examples include polyoxyethylene-polyoxypropylene condensates, polyoxyalkylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, glycerin fatty acid esters, primary alcohol ethoxylates, phenol ethoxyls Latex, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, oleyl alcohol ethoxylate, fatty acid ester, amide, natural alcohol, ethylene diamine, secondary alcohol ethoxylate, alkyl cation, amide Type quaternary cation, ester type quaternary cation, amine oxide, a betaine surfactant, etc. are mentioned.

The said developing process process is a process of developing the apply | coated resist pattern thickening material after the said resist pattern formation process and before the said etching process. In addition, the said developing process is as above-mentioned.

According to the manufacturing method of the semiconductor device of this invention, various semiconductor devices including a flash memory, DRAM, FRAM, etc. can be manufactured efficiently, for example.

Hereinafter, although the Example of this invention is described, this invention is not limited to these Examples at all.

(Example 1)

Preparation of Resist Composition

A resist composition having the following composition was prepared.

tert-butoxycarbonyloxystyrene: Resin prepared by mixing with p-hydroxystyrene = 20:80 (molecular weight: about 10,000) .. 100 parts by mass

Triphenylsulfonium perfluorobutanesulfonate ... 5 parts by mass

p-toluenesulfonic acid triethylammonium salt ... 1 mass part

Ethyl lactate ... 800 parts by mass

Formation of resist pattern

The resist composition of the present invention prepared above was coated on a silicon wafer (manufactured by Mitsubishi Material Corporation) by spin coating for 20 seconds at a speed of 3,500 rpm, and then prebaked at 110 ° C for 120 seconds. Next, 250 nm by irradiating KrF excimer laser light under the conditions of 80 mJ / cm <^2> through a mask, performing post-exposure baking at 110 degreeC for 120 second, and developing for 1 minute using 2.38 mass% TMAH aqueous solution, A rectangular isolation pattern of 1,000 nm was formed. In addition, the film thickness of the obtained resist pattern was 500 nm.

On the obtained resist pattern, a resist pattern thickening material (&quot; AZ R500 &quot;; AZ Electronic Materials) was applied by spin coating at 3,500 rpm / 60 sec. And then baked at 110 &lt; 0 &gt; C / 60 sec. A thickened resist pattern was formed by rinsing the resist pattern thickening material with pure water for 60 seconds to remove unreacted portions that did not interact (mixed), and developing a resist pattern thickened by the resist pattern thickening material.

The resist pattern before the thickening (the resist pattern) is shown in Fig. 52A, and the resist pattern after the thickening (the thickening resist pattern) is shown in Fig. 52B. Measure the size X1 and X2 of the short side direction and the size Y1 and Y2 of the long side direction, respectively, and calculate the pattern size change amount (X2-X1) of the short side direction and the pattern size change amount (Y2-Y1) of the long side direction, respectively. It was. As a result, the pattern size change amount was 52 nm in the short side direction and 55 nm in the long side direction. As mentioned above, when the resist composition of Example 1 was used, it turned out that the resist pattern can be thickened uniformly without being influenced by the direction of a resist pattern.

(Comparative Example 1)

At the time of preparation of the resist composition, a thickening resist pattern was formed in the same manner as in Example 1 except that p-toluenesulfonic acid triethylammonium salt was not added, and the amount of change in the pattern size in the short and long side directions was calculated. . As a result, the pattern size change amount was 15 nm in the short side direction and 35 nm in the long side direction. As mentioned above, in the resist composition of the comparative example 1 which does not add p-toluenesulfonic acid triethylammonium salt as an ammonium sulfonate salt, the thickening amount is remarkably different according to the direction of a resist pattern, especially the thickening amount compared with a short side direction in a long side direction. I could see that it grew.

(Example 2)

In Example 1, except having manufactured the resist composition based on the following composition, the thickening resist pattern was formed like Example 1, and the pattern size change amount of the short side direction and the long side direction was computed.

Preparation of Resist Composition

KrF resist ("DX5200P"; manufactured by AZ Electronic Materials)

Trifluoromethanesulfonic acid methylphenylammonium salt ... 3 mg

Moreover, content of the said ammonium salt with respect to solid content mass of the said KrF resist is about 0.3-0.6 mass%.

The pattern size change amount was 59 nm in the short side direction and 63 nm in the long side direction. As mentioned above, it turned out that using the resist composition of Example 2 can thicken a resist pattern uniformly without being influenced by the direction of a resist pattern.

(Comparative Example 2)

A thickening resist pattern was formed in the same manner as in Example 2 except that trifluoromethanesulfonic acid methylphenylammonium salt was not added during the preparation of the resist composition, and the pattern size variation in the short and long side directions was calculated. As a result, the pattern size change amount was 22 nm in the short side direction and 53 nm in the long side direction. As mentioned above, in the resist composition of the comparative example 2 which does not add the trifluoromethanesulfonic acid methylphenylammonium salt as an ammonium sulfonate salt, the thickening amount is remarkably different with the direction of a resist pattern, especially the thickening amount compared with a short side direction in a long side direction. I knew it grew.

(Example 3)

A thickening resist pattern was formed in the same manner as in Example 2 except that the resist pattern was formed in the pattern shape shown in FIG.

In Fig. 53, the pattern shape is one in which 300 squares of one side 300 nm are arranged in four in the horizontal direction and three in the vertical direction, and the spacing between the resist patterns is 300 nm in the horizontal direction and H in the vertical direction. 600 nm.

In the same manner as in Example 1, the pattern size change amounts of the resist patterns in the horizontal and vertical directions were measured for the 12 square patterns, and the average value thereof was calculated. The horizontal direction is 60 nm and the vertical direction is 55, respectively. nm. As mentioned above, it turned out that using the resist composition of Example 2 can thicken a resist pattern uniformly without being influenced by the change of the space | interval of a resist pattern.

(Comparative Example 3)

In Example 3, except that the resist composition of Comparative Example 2 was used, a resist pattern was formed in the pattern shape shown in FIG. 51 in the same manner as in Example 3, and thickened with a resist pattern thickening material to obtain a resist pattern. The average value of the pattern size change amount was measured. As a result, the transverse direction was 51 nm and the longitudinal direction was 25 nm. As mentioned above, when the resist composition of the comparative example 2 was used, it turned out remarkably with respect to the change of the space | interval of a resist pattern, and especially the thickening amount in the direction in which a resist pattern is dense became large.

(Example 4)

Preparation of Resist Composition

A resist composition having the following composition was prepared.

ArF resist ("AR1244J"; manufactured by JSR) ... 5 g

Trifluoromethanesulfonic acid dimethylammonium salt ... 2 mg

Moreover, content of the said ammonium salt with respect to the solid content mass of the said ArF resist is 0.2-0.4 mass%.

Formation of resist pattern

The resist composition of the present invention prepared above was coated on a silicon wafer (manufactured by Mitsubishi Material Co., Ltd.) under a spin coating method under conditions of 3,500 rpm / 20 seconds, and then prebaked under conditions of 110 ° C / 60 seconds. . Next, the ArF excimer laser light was irradiated through a mask under conditions of 40 mJ / cm ² , post-exposure baking was performed under conditions of 110 ° C./60 seconds, and then developed for 1 minute using a 2.38 mass% TMAH aqueous solution. A rectangular isolated pattern of nm × 500 nm was formed. In addition, the film thickness of the obtained resist pattern was 250 nm.

Production of Resist Pattern Thickening Material

A resist pattern thickening material having the following composition was prepared.

Polyvinyl acetal resin ("KW-3"; Sekisui Kagaku) ... 16 parts by mass

2-hydroxybenzyl alcohol ... 1 part by mass

Pure water ... 95.5 parts by mass

Isopropyl alcohol ... 0.5 parts by mass

Nonionic surfactant ("PC-6"; manufactured by Asahi Denka, polynuclear phenol ethoxylate surfactant) ... 0.08 parts by mass

On the obtained resist pattern, the prepared resist pattern thickening material was applied by spin coating on the condition of 3,500 rpm / 20 sec, and baked under the condition of 110 ° C./60 sec, and then the resist pattern thickening material was pure water. A thickened resist pattern was formed by rinsing for 60 seconds to remove unreacted portions that did not interact (mixed), and developing a thickened resist pattern with a resist pattern thickening material.

When the pattern size change amount was measured, the short side direction was 36 nm and the long side direction was 40 nm.

(Example 5)

In Example 4, the thickening resist pattern was formed like Example 4 except having used the resist pattern thickening material manufactured by the following method.

Production of Resist Pattern Thickening Material

A resist pattern thickening material having the following composition was prepared.

Polyvinyl acetal resin ("KW-3"; Sekisui Kagaku) ... 16 parts by mass

Tetramethoxymethylglycoluril (surfactant, acid and chemicals) ... 1.35 parts by mass

Pure water ... 98.6 parts by mass

Isopropyl alcohol..0.4 mass parts

Nonionic surfactant ("PC-6"; manufactured by Asahi Denka, polynuclear phenol ethoxylate surfactant) ... 0.12 parts by mass

The pattern size change amount was measured in the same manner as in Example 4. The pattern size change amount was 46 nm in the short side direction and 51 nm in the long side direction. As mentioned above, even when using the resist pattern thickening material containing surfactant, it turned out that a resist pattern can be thickened uniformly without being influenced by the magnitude | size and the direction of a resist pattern.

(Comparative Example 4)

A thickening resist pattern was formed in the same manner as in Example 5, except that trifluoromethanesulfonic acid dimethylammonium salt was not added in the preparation of the resist composition in Example 5, and the pattern sizes in the short and long side directions were formed. The amount of change was calculated. As a result, the pattern size change amount was 21 nm in the short side direction and 46 nm in the long side direction. As mentioned above, in the resist composition of the comparative example 4 which does not add the trifluoromethanesulfonic acid dimethylammonium salt as an ammonium sulfonate salt, the thickening amount is remarkably different by the direction of a resist pattern, especially the thickening amount compared with a short side direction in a long side direction. I knew it grew.

(Example 6)

A thickening resist pattern was formed in the same manner as in Example 1 except that the sulfonic acid triethylammonium salt was changed to p-toluenesulfonic acid monoethylammonium salt, and the pattern size change in the short side direction and long side direction was calculated. The pattern variation of the resist pattern was 40 nm in the short side direction and 43 nm in the long side direction. Therefore, it was found that the resist composition containing p-toluenesulfonic acid monoethylammonium salt can uniformly thicken the resist pattern without being affected by the direction of the resist pattern.

(Example 7)

In Example 1, it carried out similarly to Example 1 except having replaced 1 mass part of said p-toluenesulfonic acid triethylammonium salts with the combination of 0.5 mass part of p-toluenesulfonic acid triethylammonium salts, and 0.5 mass part of p-toluenesulfonic acid triethylammonium salts. The thickening resist pattern was formed, and the pattern size change amount of the short side direction and the long side direction was computed. The pattern variation of the resist pattern was 44 nm in the short side direction and 47 nm in the long side direction. Therefore, it was found that the resist composition containing two ammonium sulfonate salts can uniformly thicken the resist pattern without being affected by the direction of the resist pattern.

(Example 8)

In Example 1, except having changed the addition amount of p-toluenesulfonic acid triethylammonium salt into 0.005 mass%, the thickening resist pattern was formed like Example 1, and the pattern size change amount of the short side direction and the long side direction was changed. Calculated. The pattern variation of the resist pattern was 20 nm in the short side direction and 35 nm in the long side direction.

(Example 9)

A resist composition was prepared in the same manner as in Example 1 except that the amount of p-toluenesulfonic acid triethylammonium salt added was changed to 7% by mass, and then, the resist pattern was formed using the resist composition to thicken the resist pattern. It was. In Example 9, the resist sensitivity was lowered by about 30%, which affected the patterning. Therefore, it was found that when the ammonium sulfonic acid salt was added in excess of 7% by mass in the resist composition, the effect on the resist performance itself was large.

(Example 10)

The resist composition was prepared like Example 1 except having changed p-toluenesulfonic acid triethylammonium salt into quaternary ammonium salt, ie, p-toluenesulfonic acid tetramethylammonium salt and p-toluenesulfonic acid tetraethylammonium salt. However, these quaternary ammonium salts were not dissolved in the solvent of the resist material.

In addition, after forming a resist pattern similarly to Example 1, it thickened. However, the results were similar to those without adding quaternary ammonium salts.

Table 1 shows the pattern change amounts of the resist patterns of Examples 1 to 10 and Comparative Examples 1 to 4. FIG. In addition, in Table 1, "content" shows content (mass%) of the sulfonate ammonium salt with respect to the mass of resin contained in a resist material.

From Table 1, it turned out that the resist pattern formed using the resist composition of this invention is thickening uniformly and favorably.

(Example 11)

As shown in FIG. 9, the interlayer insulation film 12 was formed on the silicon substrate 11, and as shown in FIG. 10, the titanium film 13 was formed on the interlayer insulation film 12 by sputtering. Next, as shown in FIG. 11, the resist pattern 14 is formed by a well-known photolithography technique, using this as a mask, the titanium film 13 is patterned by reactive ion etching, and the opening part 15a is formed. Formed. Subsequently, the resist pattern 14 was removed by reactive ion etching, and as shown in FIG. 12, the opening 15b was formed in the interlayer insulating film 12 using the titanium film 13 as a mask.

Next, the titanium film 13 is removed by a wet treatment, and as shown in FIG. 13, the TiN film 16 is formed on the interlayer insulating film 12 by sputtering, and then on the TiN film 16. The Cu film 17 was formed into a film by the electroplating method. Subsequently, as shown in Fig. 14, the CMP is planarized to leave the barrier metal and the Cu film (the first metal film) only in the groove portion corresponding to the opening 15b (Fig. 12), and the wiring 17a of the first layer is formed. Was formed.

Subsequently, as shown in FIG. 15, after the interlayer insulating film 18 is formed on the wiring 17a of the first layer, the wiring of the first layer is shown in FIG. 16 in the same manner as in FIGS. 9 to 14. A Cu plug (second metal film) 19 and a TiN film 16a were formed to connect (17a) with the upper wiring formed later.

By repeating the above-described steps, as shown in FIG. 17, the wiring 17a of the first layer, the wiring 20 of the second layer, and the wiring 21 of the third layer are included on the silicon substrate 11. A semiconductor device having a multilayer wiring structure was prepared. In addition, in FIG. 17, the illustration of the barrier metal layer formed under the wiring lower layer of each layer is omitted.

In Example 11, after the resist pattern 14 was formed using the resist composition of the present invention, the resist pattern 14 was manufactured in the same manner as in Examples 1 to 7 using a resist pattern thickening material. It is a thickening resist pattern.

(Example 12)

Flash memory and its manufacture

Example 12 is an example of the semiconductor device of the present invention and the manufacturing method thereof using the resist composition of the present invention. In Example 9, the following resist films 26, 27, 29, and 32 form a resist pattern using the resist composition of the present invention, and then a resist pattern thickening material is used. It was thickened by the same method as in Examples 1 to 7 using the same.

18 and 19 are top views (top views) of FLASH EPROM called FLOTOX type or ETOX type. 20 to 28 are schematic cross-sectional views for explaining an example of the method for manufacturing the FLASH EPROM. The left view in these is a memory cell portion (first element region), and a cross section (AA direction cross section) in the gate width direction (X direction in FIGS. 18 and 19) of a portion where a MOS transistor having floating gate electrodes is formed. ) Schematic diagram. The center view is a memory cell portion of the same portion as the left side, and is a schematic diagram (BB direction cross section) of the gate length direction (Y direction in FIGS. 18 and 19) orthogonal to the X direction, and the right side diagram shows a peripheral circuit portion ( It is a schematic diagram (section AA direction in FIG. 18 and FIG. 19) of the part in which the MOS transistor of the 2nd element area | region is formed.

First, SiO ₂ is selectively added to the device isolation region on the p-type Si substrate 22. To form a film, thereby SiO ₂ A field oxide film 23 of the film was formed (FIG. 20). Thereafter, SiO ₂ is thermally oxidized so as to have a thickness of 100 to 300 kHz (10 to 30 nm) as the first gate insulating film 24a in the MOS transistor of the memory cell portion (first element region). A film was formed. In another step, SiO ₂ is formed as a second gate insulating film 24b in the MOS transistor of the peripheral circuit portion (second device region) by thermal oxidation so as to have a thickness of 100 to 500 kPa (10 to 50 nm). A film was formed. In the case where the first gate insulating film 24a and the second gate insulating film 24b have the same thickness, an oxide film may be formed simultaneously in the same process.

Next, the peripheral circuit portion (right side of FIG. 20) is controlled for the purpose of controlling a threshold voltage for forming a M0S transistor having an n-type deflation type channel in the memory cell portion (left and center views of FIG. 20). Masking was performed by the resist film 26. In addition, phosphorus (P) or arsenic (As) having a dose of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² as an n-type impurity is introduced into an area to be a channel region immediately below the floating gate electrode by an ion implantation method. The first threshold control layer 25a was formed. In addition, the dose amount and conductivity type of an impurity at this time can be suitably selected according to whether a channel is a deflation type or an accumulation type.

Next, the memory cell portion (left and center views in FIG. 21) is resisted for the purpose of controlling the threshold voltage for forming an MOS transistor having an n-type deflation type channel in the peripheral circuit portion (right side in FIG. 21). Masked by membrane 27. In addition, phosphorus (P) or arsenic (As) having a dose amount of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² as an n-type impurity is introduced into an area to be a channel region immediately below the gate electrode by an ion implantation method. Two threshold control layers 25b were formed.

Next, the floating gate electrode of the MOS transistor of the memory cell portion (left and center views of FIG. 22) and the gate electrode of the MOS transistor of the peripheral circuit portion (right side of FIG. 22) have a thickness of 500 to 2,000 mW ( 50-200 nm) of 1st polysilicon film (1st conductor film) 28 was formed in the whole surface.

Thereafter, as shown in FIG. 23, a resist film 29 is formed, and the first polysilicon film 28 is patterned using the resist film 29 as a mask to form the memory cell portion (left view of FIG. 23). And a floating gate electrode 28a in the MOS transistor of the center diagram). At this time, as shown in Fig. 23, the X-direction is patterned to have a final dimension width, and the Y-direction is not patterned, whereby the region to be a source-drain (S / D) region layer is formed by the resist film 29. Covered as it was.

Next, after the resist film 29 is removed, the capacitor insulating film 30a formed of the SiO ₂ film is thermally oxidized to a thickness of about 200 to 500 kPa (20 to 50 nm) to cover the floating gate electrode 28a. It was formed as (left and center view in Figure 24). At this time, a capacitor insulating film 30b formed of an SiO ₂ film is also formed on the first polysilicon film 28 of the peripheral circuit portion (right side in FIG. 24). The capacitor insulating films 30a and 30b are formed of only SiO ₂ films, but may be formed of a composite film in which two or three SiO ₂ films and Si ₃ N ₄ films are stacked.

Next, in order to cover the floating gate electrode 28a and the capacitor insulating film 30a, the second polysilicon film (second conductor film) 31 serving as a control gate electrode has a thickness of 500 to 2,000 kPa (50 to 200 kPa). nm) (FIG. 24).

Next, as shown in FIG. 25, the memory cell portion (left and center views in FIG. 25) is masked by the resist film 32, and the second polysilicon film in the peripheral circuit portion (right side in FIG. 25) is next masked. 31 and the capacitor insulating film 30b were sequentially removed by etching to expose the first polysilicon film 28.

Next, as shown in FIG. 26, only the second polysilicon film 31, the capacitor insulating film 30a, and the first polysilicon film patterned in the X direction of the memory cell portion (left and center views in FIG. 26). Using the resist film 32 as a mask for (28a), patterning in the Y direction was performed such that the first gate portion 33a became the final dimension. Thus, a laminate formed by the control gate electrode 31a / capacitor insulating film 30c / floating gate electrode 28c having a width of about 1 탆 in the Y direction was formed. Further, the first polysilicon film 28 of the peripheral circuit portion (right side in FIG. 26) is patterned so that the second gate portion 33B becomes the final dimension using the resist film 32 as a mask. A gate electrode 28b of about 1 mu m was formed.

Next, the Si substrate in the element formation region is formed by using a laminate of the control gate electrode 31a / capacitor insulating film 30c / floating gate electrode 28c of the memory cell portion (left and center views in FIG. 27) as a mask. Phosphorus (P) or arsenic (As) having a dose of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ^-2 is introduced into the (22) by ion implantation, and the n-type S / D region layers 35a and 35b are introduced. ) Was formed. In addition, with the gate electrode 28b of the peripheral circuit portion (right side in FIG. 27) as a mask, the dose of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻ as an n-type impurity on the Si substrate 22 in the element formation region. a phosphorus (P) or arsenic (As) of the ^second introduction by ion implantation, followed by forming a S / D region layer (36a) and (36b).

Next, in order to cover the first gate portion 33a of the memory cell portion (left and center views in FIG. 28) and the second gate portion 33b of the peripheral circuit portion (right side in FIG. 28), an interlayer insulating film ( 37) a PSG (phosphate-silicate glass) film having a thickness of about 5,000 GPa (500 nm).

Thereafter, contact holes 38a, 38b, 39a, and 39b are formed in the interlayer insulating film 37 on the S / D region layers 35a, 35b, 36a, and 36b. Then, S / D electrodes 40a, 40b, 41a, and 41b were formed. Further, in order to form the contact holes 38a, 38b, 39a, and 39b, a hole pattern by the resist composition of the present invention is formed, and thickened using the resist pattern thickening material, A fine gap pattern (hole pattern) was formed. Subsequently, a contact hole was manufactured according to a conventional method.

As mentioned above, FLASH EPROM was manufactured as a semiconductor device (FIG. 28).

In this FLASH EPROM, after the second gate insulating film 24b of the peripheral circuit portion (right side in FIGS. 20 to 28) is formed, it is covered with the first polysilicon film 28 or the gate electrode 28b. The second gate insulating film 24b remains as it is when it is first formed because it is formed (right side view in FIGS. 20 to 28). For this reason, it is possible to easily control the thickness of the second gate insulating film 24b and to adjust the conductivity type impurity concentration for controlling the threshold voltage easily.

In the above embodiment, patterning is first performed at a predetermined width in the gate width direction (the X direction in FIGS. 18 and 19), and then patterned in the gate length direction (the Y direction in FIGS. 18 and 19) to give a final predetermined width. Thus, the first gate portion 33a is formed. Alternatively, after patterning with a predetermined width in the gate length direction (Y direction in FIGS. 18 and 19), patterning is performed in the gate width direction (X direction in FIGS. 18 and 19) to obtain a final predetermined width. It may be.

The manufacture example of FLASH EPROM shown in FIGS. 29-31 is the same as that of the said Example except having changed after the process shown in FIG. 28 as shown in FIG. 29-31 in the said Example. That is, as shown in FIG. 29, the 2nd polysilicon film 31 of the said memory cell part (left side and center view in FIG. 29) and the 1st polysilicon film of the said peripheral circuit part (right side of FIG. 29) are shown. On the 28, a refractory metal film (fourth conductor film) 42 formed of a tungsten (W) film or a titanium (Ti) film is formed so as to have a thickness of about 2,000 kPa (200 nm), and a polyside film is provided. It differs from the above embodiment only in that respect. The subsequent steps of FIG. 29, that is, the steps shown in FIGS. 30 to 31 were performed in the same manner as FIGS. 26 to 28, and detailed descriptions thereof were omitted. 29 to 31, the same symbols as those in FIGS. 26 to 28 are denoted by the same symbols.

In this way, a FLASH EPROM was manufactured as a semiconductor device (FIG. 31).

In the FLASH EPROM, since the refractory metal films (fourth conductor films) 42a and 42b are provided on the control gate electrode 31a and the gate electrode 28b, the electrical resistance value can be further reduced.

In addition, although the refractory metal films (4th conductor film) 42a and 42b are used as a refractory metal film (4th conductor film), refractory metal silicide films, such as a titanium silicide (TiSi) film, can also be used here. .

Another FLASH EPROM was produced by the manufacturing process in the above-mentioned embodiment except for the steps shown in FIGS. 32-34. Specifically, the second gate portion 33c of the peripheral circuit portion (second element region) (right side in FIG. 32) is the memory cell portion (first element region) (left and center views in FIG. 32). The first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second polysilicon film 31b (second), similarly to the first gate portion 33a of Conductor film) in this order. The first polysilicon film 28b and the second polysilicon film 31b are short-circuited to form a gate electrode (FIGS. 33 and 34).

Here, as shown in Fig. 33, the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second polysilicon film 31b (second conductor film) is formed. An opening 52a penetrating, for example, is formed on a portion different from the second gate portion 33c shown in FIG. 32, for example, the insulating film 54, and a third conductor film, for example, is formed in the opening 52a. For example, the first polysilicon film 28b and the second polysilicon film 31b are short-circuited by embedding a refractory metal film 53a such as a W film or a Ti film. In addition, as shown in Fig. 34, the first polysilicon film (28b) (first conductor film) / SiO ₂ film (30d) to form an opening (52b) passing through the (capacitor insulating film), the bottom of the opening (52b) After exposing the lower first polysilicon film 28b to the portion, the first poly film is embedded in the opening 52b by embedding a third conductive film, for example, a refractory metal film 53b such as a W film or a Ti film. The silicon film 28b and the second polysilicon film 31b are shorted.

In this FLASH EPROM, the second gate portion 33c of the peripheral circuit portion has the same structure as the first gate portion 33a of the memory cell portion. Therefore, when forming the memory cell portion, the peripheral circuit portion can be formed at the same time, and the manufacturing process can be easily performed, which is efficient.

In this case, the third conductor film 53a or 53b and the refractory metal film (fourth conductor film) 42 are formed separately. Alternatively, these films may be formed simultaneously as a common refractory metal film.

(Example 13)

-Manufacture of magnetic head

Example 13 relates to the production of a magnetic head as an application example of the resist pattern of the present invention using the resist composition of the present invention. In addition, in the thirteenth embodiment, the following resist patterns 102 and 126 form resist patterns using the resist composition of the present invention, and then in Examples 1 to 7 using a resist pattern thickening material. It is thickened by the same method as that of.

35 to 38 are process drawings for explaining the manufacture of the magnetic head.

First, a resist film was formed on the interlayer insulating layer 100 so as to have a thickness of 6 µm, and exposed and developed to form a resist pattern 102 having an opening pattern for forming a spiral thin film magnetic coil (FIG. 35). .

Next, on the interlayer insulating layer 100, on the resist pattern 102 and on the portion where the resist pattern 102 is not formed, that is, on the exposed surface of the opening 104, the Ti adhesion film having a thickness of 0.01 μm and the thickness thereof are formed. A plated work surface 106 formed by laminating a Cu adhesion film having a thickness of 0.05 μm was formed by a vapor deposition method (FIG. 36).

Next, Cu having a thickness of 3 μm on the surface where the resist pattern 102 is not formed on the interlayer insulating layer 100, that is, the surface of the plated workpiece surface 106 formed on the exposed surface of the opening 104. The thin film conductor 108 formed of the plating film was formed (FIG. 37).

Next, when the resist pattern 102 is dissolved and removed, the film is lifted off from the interlayer insulating layer 100, whereby the thin film magnetic coil 110 is formed by the swirl pattern of the thin film conductor 108 ( 38).

The magnetic head was manufactured from the above.

The magnetic head obtained here is a thin-film magnetic coil because the swirl pattern is finely formed by the resist pattern 102 which thickens the resist pattern formed by using the resist composition of the present invention by using a resist pattern thickening material. 110 is fine and precise. The magnetic head can also be mass produced satisfactorily.

39 to 44 are process charts for explaining the manufacture of another magnetic head.

The gap layer 114 was coat-covered and formed on the ceramic nonmagnetic substrate 112 by sputtering (FIG. 39). In addition, on the non-magnetic substrate 112, although not shown, the electrically conductive to-be-processed surface containing an insulator layer and Ni-Fe permalloy by silicon oxide previously is coat | covered by sputtering method, and contains Ni-Fe permalloy. The lower magnetic layer is further formed. In addition, the resin insulating film 116 was formed with the thermosetting resin in the predetermined area | region on the gap layer 114 except the part which becomes the magnetic tip part of the said lower magnetic layer which is not shown in figure. Next, a resist material was applied onto the resin insulating film 116 to form a resist film 118.

Next, the resist film 118 was exposed and developed to form a swirl pattern (FIG. 40). The vortex pattern resist film 118 was thermally cured at several hundred ° C. for about 1 hour to form a projection-shaped first swirl pattern 120 (FIG. 41). In addition, in order to cover the surface of the first vortex pattern 120, a conductive workpiece surface 122 including Cu was formed.

Next, a resist material is applied on the conductive workpiece surface 122 by spin coating to form a resist film 124, and then the resist film 124 is patterned on the first spiral pattern 120. The resist pattern 126 was formed (FIG. 42).

Next, the Cu conductor layer 128 was formed by the plating method on the exposed surface of the conductive workpiece surface 122, that is, on the portion where the resist pattern 126 was not formed (FIG. 43). Thereafter, the resist pattern 126 was dissolved and removed to lift off from the conductive workpiece surface 122, thereby forming a spiral thin film magnetic coil 130 by the Cu conductor layer 128 (FIG. 44).

As mentioned above, the magnetic head which manufactured the magnetic layer 132 on the resin insulating film 116 and provided with the thin film magnetic coil 130 on the surface as shown to the top view of FIG.

The magnetic head obtained here is thin-film porcelain because the vortex pattern is finely formed by the resist pattern 126 which thickens the resist pattern formed using the resist composition of the present invention using a resist pattern thickening material. The coil 130 is fine and precise. The magnetic head can also be mass produced satisfactorily.

The present invention solves the conventional problems and can achieve the above object.

The present invention can use ArF (argon fluoride) excimer laser light as the exposure light at the time of patterning, and after exposure and development to form a resist pattern, by applying a resist pattern thickening material on the surface of the resist pattern, the resist pattern It is suitable for thickening the film, and is uniformly thickened to exceed the exposure limit or resolution limit in the light source of the exposure apparatus without depending on the direction and / or gap change of the resist pattern and the components of the resist pattern thickening material. There is provided a resist composition capable of easily and efficiently forming a fine gap pattern at low cost.

The present invention can use ArF (argon fluoride) excimer laser light as the exposure light at the time of patterning, and uniformly resist pattern without depending on the direction and / or spacing change of resist pattern and components of the resist pattern thickening material. Provided is a method of forming a resist pattern that can be thickened and suitable for easily and efficiently forming a fine gap pattern exceeding an exposure limit or resolution limit in a light source of an exposure apparatus at low cost.

The present invention can use ArF (argon fluoride) excimer laser light as the exposure light at the time of patterning, and uniformly resist pattern without depending on the direction and / or spacing change of resist pattern and components of the resist pattern thickening material. It can be thickened and is suitable for easily and efficiently forming a fine gap pattern exceeding an exposure limit or a resolution limit in a light source of an exposure apparatus at low cost, and using the fine gap pattern formed using this fine gap pattern Provided are a method of manufacturing a semiconductor device capable of mass-producing a high-performance semiconductor device having a high efficiency, and a high-performance semiconductor device manufactured by the method of manufacturing the semiconductor device and having a fine wiring pattern.

After the resist composition of the present invention is exposed and developed to form a resist pattern, a resist pattern thickening material is applied to the surface of the resist pattern to thicken the resist pattern, and the direction of the formed resist pattern, Irrespective of the change in the gap and the like, the thickness is uniformly thickened by the resist pattern thickening material without depending on the kind of the resist pattern thickening material, and is a fine interval beyond the exposure limit (resolution limit) in the light source of the exposure apparatus. It can use suitably for formation of a pattern. Therefore, the resist composition of this invention can be preferably applied to various patterning methods, the manufacturing method of a semiconductor, etc., and can be used especially for the formation method of the resist pattern of this invention, and the manufacturing method of the semiconductor device of this invention.

The method of forming the resist pattern of the present invention includes, for example, a mask pattern, a reticle pattern, a magnetic head, an LCD (liquid crystal display), a plasma display panel (PDP), a SAW filter (elastic surface wave filter), and the like. It can apply suitably to manufacture of micro components, such as an optical component micro actuator used for connection, and a semiconductor device, and can use preferably for the manufacturing method of the semiconductor device of this invention.

The manufacturing method of the semiconductor device of this invention can be used suitably for manufacture of various semiconductor devices including flash memory, DRAM, FRAM, etc.

The present invention has been described based on the embodiments considered by the inventors of the present invention to be the best embodiments. However, the present invention is not limited to the specific examples disclosed herein, and those skilled in the art can modify the above embodiments within the scope of the present invention.

Claims (15)

A resist composition comprising a resist material and an ammonium sulfonate salt, wherein the ammonium sulfonate salt comprises a sulfonic acid residue and an ammonium residue, wherein the sulfonic acid residue is at least one selected from trifluoromethanesulfonic acid anion and toluenesulfonic acid anion. delete The composition of claim 1, wherein the ammonium sulfonate salt comprises a sulfonic acid moiety and an ammonium moiety, wherein the ammonium moiety is at least one selected from primary ammonium cations, secondary ammonium cations and tertiary ammonium cations. The composition of claim 1, wherein the ammonium sulfonate salt comprises a sulfonic acid residue and an ammonium residue, wherein the ammonium residue is represented by the following formula. <Formula 1> N ⁺ R ¹ R ² R ³ R ⁴ However, In the formula 1, N is a nitrogen atom, at least one of R ¹ to R ⁴ is a hydrogen atom and the other is selected from the group consisting of alkyl group and phenyl group in C _{1 -4.} The composition of Claim 1 whose content of the said ammonium sulfonate salt is 0.01-5 mass% with respect to the mass of the total solid of a resist composition. The composition of claim 1, wherein the resist composition is at least one selected from the group consisting of an acrylic resist comprising an acrylic resin having a cycloaliphatic functional group in the side chain, a cycloolefin-maleic anhydride resist, and a cycloolefin resist. 7. The cycloaliphatic functional group according to claim 6, wherein the alicyclic functional group is selected from the group consisting of adamantyl functional groups and norbornane groups, and the cycloolefin resist comprises at least one member selected from the group consisting of norbornane and adamantane. A composition comprising a cycloolefin contained in the main chain. The composition of claim 1, wherein said composition has a sensitivity to exposure light having a wavelength of 440 nm or less. The composition according to claim 8, wherein the exposure light is at least one selected from the group consisting of g-rays, i-rays, KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light and electron beam. Forming a resist pattern from a composition comprising a resist material and an ammonium sulfonate salt; And Applying a resist pattern thickening material on the resist pattern to cover the surface of the resist pattern, Wherein said ammonium sulfonate salt comprises a sulfonic acid residue and an ammonium residue, wherein said sulfonic acid residue is at least one selected from trifluoromethanesulfonic acid anions and toluenesulfonic acid anions. The method of claim 10 further comprising developing the resist pattern thickening material after the applying step. The method of claim 11, wherein the developing step is performed using water. Forming a resist pattern on the surface to be processed from the composition comprising a resist material and an ammonium sulfonate salt; Thickening the resist pattern by applying a resist pattern thickening material on the resist pattern to cover the surface of the resist pattern; And Etching the processed surface by using the thickened resist pattern as a mask to pattern the processed surface, The sulfonate ammonium salt comprises a sulfonic acid residue and an ammonium residue, wherein the sulfonic acid residue is at least one selected from trifluoromethanesulfonic acid anion and toluenesulfonic acid anion. The method of claim 13, further comprising coating a nonionic surfactant on the surface of the resist pattern prior to the application of the resist pattern thickening material, wherein the nonionic surfactant is a polyoxyethylene-polyoxypropylene condensate, poly At least one selected from the group consisting of oxyalkylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, glycerin fatty acid esters, primary alcohol ethoxylates and phenol ethoxylates . Forming a resist pattern on the surface to be processed from a resist composition comprising an ammonium sulfonate salt, wherein the resist pattern includes elements of the resist pattern and the spacing between the elements of the resist pattern is varied; Thickening the resist pattern by applying a resist pattern thickening material on the resist pattern to cover the surface of the resist pattern; And Etching the work surface using the thickened resist pattern as a mask to pattern the work surface, wherein the ammonium sulfonate salt comprises a sulfonic acid residue and an ammonium residue, wherein the sulfonic acid residue is trifluorine The semiconductor device manufactured by the method of at least 1 sort (s) chosen from a romethane sulfonic acid anion and a toluene sulfonic acid anion.

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