JPH07106220A - Manufacturing method of semiconductor device - Google Patents

Abstract

PURPOSE:To provide the manufacturing method of semiconductor device having the high resolving power of a resist pattern as well as avoiding the fluctuation in film thickness and pattern dimension, etc., while stably preserving the resist characteristics. CONSTITUTION:When positive resist films formed on a processed substrate 1 are exposed to a specific resist pattern and then developed to form a resist pattern, the resist layers to be formed are multilayer structured of alternately laminated resists 2 and 4 in different kinds and barrier layers 5 comprising alkali soluble composition furthermore, respective resist layers are selected to meet the requirement of the higher the layer, the lower the melting down rate by the same exposure amount while the barrier layers 5 are to be composed of a nitrene compound having the in-film multireflection reducing effect and the phototransparency. In such a multilayer structure, the difference in the absorption factors between the higher the more resist layer and the lower resist layer part such as hole pattern, etc., where the light hardly reach can be diminished thereby enabling the melting down phenomenon in the not yet exposed part to be suppressed for reducing the in-film multireflection effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a semiconductor device, and more particularly to a method for forming a resist pattern suitable for forming a fine structure such as a semiconductor integrated circuit.

[0002]

2. Description of the Related Art FIG. 6 is a sectional view for explaining a method of forming a photoresist pattern according to a conventional example in the order of steps. In the figure, 1 is a substrate to be processed, 7 is a mask, 8 is a resist layer formed on the substrate to be processed 1, 9 is a resist formed by exposing the resist layer 8 through the mask 7 and then developing it. The pattern is shown.

Next, a method for forming a resist pattern will be described in detail. The resist layer 8 is formed by applying one type of positive photoresist on the substrate 1 to be processed (see FIG. 6A). Next, the resist layer 8 is exposed through the mask 7 (see FIG. 6B). afterwards,
By developing the resist layer 8 with an alkaline developer,
Only the exposed portion is removed, whereby the resist pattern 9 is formed (see FIG. 6C).

By the way, FIG. 7 shows a distribution diagram of the exposure intensity formed in the resist layer 8, and the numbers in the horizontal row indicate the relative values of the exposure intensity in the resist layer 8 when a certain amount of light is incident. Shows. In FIG. 7, a standing wave is created by the interaction between the light incident on the resist layer 8 and the light reflected on the substrate 1 to be processed, and the resist layer 8 is exposed to light by the multiple reflection inside the film. It has been shown that layers of relatively high intensity and layers of relatively low intensity can be alternated, whereby the upper layer portion of the resist layer 8 has a higher exposure intensity, while the lower layer portion has a relatively lower exposure intensity. .

For this reason, the sensitivity and the resist finish size vary greatly due to the above-described intra-film multiple reflection effect in the resist layer 8, and as shown in FIG. 8, the resist finish size becomes large due to the variation in the film thickness of the resist layer 8. While changing, as shown in FIG. 9, the contrast of the light actually incident on the resist layer 8 through the mask 7 does not clearly show the difference between the exposed portion and the unexposed portion.

As a result, in FIG. 10 showing the change of the dissolution rate in the alkali developing solution depending on the position in the depth direction in the resist layer 8, the exposure is performed by the in-film multiple reflection effect in the resist layer 8 shown in FIG. 7 described above. The strength of the upper layer portion (front surface side) of the resist layer 8 is larger than that of the lower layer portion (substrate side). With one type of resist, the higher the exposure intensity,
Since the dissolution rate with the alkaline developer also increases, the dissolution rate decreases from the surface side to the substrate side.
Further, it has a maximum value and a minimum value corresponding to the standing wave.

[0007]

Since the conventional method of forming a resist pattern is performed as described above, when exposed, the light intensity becomes stronger toward the upper layer portion of the resist layer 8 and, conversely, the lower layer. The light gets harder to reach and becomes weaker toward the part. For this reason, the amount of decomposition of the photosensitive group is different, and it becomes easier to dissolve toward the upper layer portion of the resist layer 8 during development, and the pattern profile deteriorates. Further, since the developing solution is in contact with the upper layer portion for a longer time, the phenomenon is accelerated.

Further, due to the above-mentioned intra-film multiple reflection effect,
Sensitivity to variations in the film thickness of the resist layer 8 and the dimensions of the resist finish vary, and the resist characteristics become unstable. Further, the contrast of the incident light intensity between the exposed portion and the unexposed portion is not clear, and the pattern profile is deteriorated due to the wraparound of the light to the unexposed portion.

The present invention has been made in order to solve the above-mentioned problems associated with the conventional example, and it is possible to obtain a high resolution of the resist pattern, and at the same time, variation in the thickness of the resist layer, variation in the dimension of the resist pattern, etc. It is an object of the present invention to obtain a method for manufacturing a semiconductor device, which can eliminate the above problem and can stably maintain the resist characteristics.

[0010]

According to a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, wherein a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and the positive resist is then exposed. In the method for manufacturing a semiconductor device in which a resist pattern is formed by developing, the positive resist film is sequentially formed on the substrate from one having a high dissolution rate to a developing solution at the same exposure amount to one having a slow dissolution rate. The method is characterized by including a step of forming and forming a patterning layer having a multilayer structure, a step of exposing the patterning layer of the multilayer structure, and a step of developing with a developing solution after exposure.

In the method of manufacturing a semiconductor device according to a second aspect of the present invention, a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and then the positive resist is developed to form a resist pattern. In the method for manufacturing a semiconductor device, the positive type resist film is sequentially formed on the substrate from one having a high dissolution rate to a developing solution at the same exposure amount to one having a slow dissolution rate,
A step of forming a barrier layer made of a soluble composition to form a patterning layer having a multilayer structure between the respective positive resist layers, a step of exposing the patterning layer having the multilayer structure, and a step of developing with a developer after exposure are performed. It is characterized by having.

In the method of manufacturing a semiconductor device according to a third aspect of the present invention, a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and then the positive resist is developed to form a resist pattern. In the method for manufacturing a semiconductor device, the positive type resist film is sequentially formed on the substrate from one having a high dissolution rate to a developing solution at the same exposure amount to one having a slow dissolution rate,
Forming a barrier layer of a soluble composition between the positive resist layers, and forming a barrier layer of the soluble composition on the uppermost layer of the positive resist film to form a patterning layer having a multilayer structure; The method is characterized by having a step of exposing a patterned layer having a multilayer structure and a step of developing with a developing solution after exposure.

Further, in the method for manufacturing a semiconductor device according to a fourth aspect, a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and then the positive resist is developed to form a resist pattern. In the method for manufacturing a semiconductor device, the positive resist film is sequentially formed on the substrate from one having a high dissolution rate to an alkaline developing solution at the same exposure amount to one having a slow dissolution rate, and each positive resist film is formed. A step of forming a barrier layer of an alkali-soluble composition composed of a nitrene-based compound between the resist layers and forming a patterning layer having a multilayer structure,
The method is characterized by including a step of exposing the patterned layer having the multilayer structure and a step of developing with an alkali developing solution after the exposure.

[0014]

In the method of manufacturing a semiconductor device according to the first aspect of the present invention, the positive resist film is sequentially formed on the substrate from one having a faster dissolution rate to a developer at the same exposure amount to one having a slower dissolution rate. By forming a patterning layer having a multi-layered structure and exposing the multi-layered patterning layer with a developing solution to develop a resist pattern, the dissolution rate of the upper layer portion and the lower layer portion of the resist layer is approximated to develop. The subsequent resist pattern shape is made rectangular to improve the resolution.

Further, in the method of manufacturing a semiconductor device according to the second aspect, the positive type resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate. In addition, a barrier layer made of a soluble composition is formed between each positive resist layer to form a patterning layer having a multilayer structure, and the patterned layer having the multilayer structure is exposed and developed with a developing solution to form a resist pattern. As a result, an antireflection layer having optical transparency is formed between the resist layers by the alkali-soluble composition to reduce intra-film multiple reflection within each resist layer and reduce variations in sensitivity and resist finish size.

Further, in the method of manufacturing a semiconductor device according to the third aspect of the present invention, the positive type resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate. At the same time, a barrier layer made of a soluble composition is formed between each positive resist layer, and a barrier layer made of a soluble composition is formed on the uppermost layer of the positive resist film to form a patterning layer having a multilayer structure. By developing the resist pattern by developing with a developing solution after the exposure of the multi-layered patterning layer, the light intensity actually incident on the resist layer, that is, the contrast of the light intensity incident on the exposed and unexposed portions is increased. Make the pattern profile rectangular.

Further, in the method of manufacturing a semiconductor device according to a fourth aspect, a positive resist film is sequentially formed on the substrate from one having a high dissolution rate to an alkaline developer at the same exposure amount to one having a slow dissolution rate. At the same time, a barrier layer made of an alkali-soluble composition made of a nitrene-based compound is formed between the positive resist layers to form a patterning layer having a multilayer structure, and the patterning layer having the multilayer structure is exposed and then developed with an alkali developing solution. By forming a resist pattern with each of the positive resist layers, an antireflection layer against exposure light rays is formed between the positive resist layers, and a barrier layer made of a composition having optical transparency is easily formed to form a resist pattern in each resist layer. To reduce the multiple reflection in the film.

[0018]

【Example】

Example 1. The first embodiment of the present invention will be described below. 1A to 1C are cross-sectional views for explaining a method of forming a photoresist pattern according to the first embodiment in the order of steps. In the figure, 1 is a substrate to be processed, 2 is a resist A, 3 is a resist B, 4 is a resist C, 5 is a barrier layer formed of an alkali-soluble composition, and 6 is a resist layer exposed through a mask 7. , A resist pattern formed by development, and 7 represents a mask.

Here, each of the resists 2 to 4 used in Example 1 is composed of a resin soluble in an alkali developing solution, a photosensitive substance which is an ester compound having a quinonediazide moiety, and a solvent. A cresol novolac resin is used as the resin soluble in the alkaline developer. In addition, a different photosensitive material is used for each resist, which is a hydroxybenzophenone type and has a different esterification rate due to a naphthoquinonediazide group. However, the number of quinonediazide moieties in the photosensitive material used here is the same.

And, if the esterification rate is high,
There are three types of A, B, and C, and the resists 2 to 4 containing these photosensitive substances are referred to as resist A, resist B, and resist C. Further, the alkali-soluble composition forming the barrier layer 5 used in Example 1 is a nitrene-based compound having an in-film multiple reflection preventing effect and light transparency.

Next, a method of forming a resist pattern according to the first embodiment will be described with reference to FIG. One-third of the film thickness of the resist A2 normally applied on the substrate 1 to be processed
And the barrier layer 5 is formed thereon by several hundred liters. Next, the resist B3 is applied so as to have the same film thickness as the resist A2, and the barrier layer 5 is further formed thereon by several hundred liters. Finally, the resist C4 is applied so as to have the same film thickness as the resists A2 and A3, and the barrier layer 5 is formed again by several hundred Å. This barrier layer 5 forms a layer of three types of resists that suppress mixing between the resists (FIG. 1).
(See (a)).

Next, the resist layer is exposed through the mask 7. At this time, since the absorbed exposure amount decreases from the surface side of the resist layer to the substrate side, the amount of the photosensitizer decomposed in the order of the resists A, B, and C is reduced. Further, since the intra-film multiple reflection in each resist is suppressed by the barrier layer 5 between each resist, the difference between the maximum value and the minimum value of the exposure amount in each resist layer becomes small. Further, since the barrier layer 5 has light transparency, light sneaking into the unexposed portion is reduced (FIG. 1).
(See (b)), however, the dissolution rate is adjusted to be slightly faster on the substrate side, and when the exposed portion is removed, the profile of the resist pattern 6 becomes close to a rectangle. Further, it is possible to prevent the unexposed portion from being dissolved during development, and the above effect is enhanced (see FIG. 1C).

The effects of the semiconductor device manufactured as described above will be described below with reference to FIGS. FIG. 2 shows the dissolution rate of the resists A, B, and C with respect to the decomposition amount (exposure amount) of the photosensitizer. At the same dissolution rate, the decomposition amount of the photosensitizer increases in the order of the resists A, B, and C. As shown in FIG. 2, in consideration of the time of contact with the developing solution in the order of increasing the dissolution rate of each resist, the resist A,
By selecting B and C and determining the exposure dose suitable for the photosensitizer decomposition amount of each resist corresponding thereto, it is possible to reduce the variation of the exposure dose and the variation of the dissolution rate to reach each layer resist layer, and to obtain a good resist pattern 6 Profile can be obtained.

That is, by sequentially forming from a positive resist having a high dissolution rate to an alkaline developing solution at the same exposure amount to a positive resist having a slow dissolution rate, in other words, decomposition of a photosensitive group at the same dissolution rate. By forming a plurality of positive resists having different amounts in order from the resist having the smallest decomposition amount on the substrate 1 to be processed, the dissolution rates of the upper layer portion and the lower layer portion of the resist layers 2 to 4 are made close to each other, and development is performed. It is possible to improve the resolution by making the subsequent resist pattern shape rectangular.

FIG. 3 shows the variation of the resist finish dimension with respect to the variation of the resist film thickness when the barrier layer 5 is formed on the resist. As shown in FIG. By forming on top, the in-film multiple reflection effect in the resist layer is suppressed,
Variations in sensitivity and resist finish size are reduced.

FIG. 4 shows the contrast of the light intensity that actually reaches the resist layer after passing through the barrier layer 5 formed of the alkali-soluble composition through the mask 7 and is shown in FIG. As described above, by forming the barrier layer 5 on the resist, the contrast of the light intensity actually incident on the resist layer is increased, and the light sneak to the unexposed portion is also reduced.

Further, FIG. 5 shows the change of the dissolution rate depending on the position in the depth direction in the resist layer, and the regions surrounded by the broken line are the resists A, B and C from the surface side, respectively.
As shown in FIG. 5, the difference in dissolution rate between the substrate side and the resist surface side is small, and since the multiple reflection in the film is suppressed by the barrier layer 5 between the resist layers, the maximum value and the minimum value are reduced. The difference between is also small.

[0028]

As described above, according to the first aspect of the present invention, the positive resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate. Then, a patterning layer having a multi-layer structure is formed, and the resist layer is formed by exposing the patterning layer having the multi-layer structure after exposure and developing with a developing solution, so that the dissolution rates of the upper layer portion and the lower layer portion of the resist layer are close to each other. The resist pattern after development can be formed into a rectangular shape to improve the resolution, and the desired resist pattern can be obtained.

According to a second aspect of the present invention, the positive resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate, and each positive resist layer is formed. In addition, a barrier layer made of a soluble composition was formed to form a patterning layer having a multi-layer structure, and the patterning layer having the multi-layer structure was developed with a developer after exposure to form a resist pattern. The anti-reflection layer having light transparency is formed by the alkali-soluble composition, and it is possible to reduce in-film multiple reflection in each resist layer and reduce variations in sensitivity and resist finish dimension.

According to a third aspect of the present invention, the positive resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate, and each positive resist layer is formed. And forming a barrier layer of a soluble composition on the positive resist film, and forming a barrier layer of a soluble composition on the uppermost layer of the positive resist film to form a patterning layer having a multilayer structure, and exposing the patterning layer having the multilayer structure. Since the resist pattern is formed by developing with a post-developing solution, the contrast of the light intensity actually incident on the resist layer, that is, the light intensity incident on the exposed portion and the unexposed portion is increased to make the pattern profile rectangular. There is an effect that can be done.

Further, according to claim 4, a positive resist film is sequentially formed on the substrate from one having a high dissolution rate to an alkaline developing solution at the same exposure amount to one having a slow dissolution rate, and each positive resist film is formed. Between the layers, a barrier layer made of an alkali-soluble composition composed of a nitrene-based compound is formed to form a patterning layer having a multilayer structure, and after the patterning layer having the multilayer structure is exposed, it is developed with an alkali developing solution to form a resist pattern. Therefore, an anti-reflection layer for exposure light rays is formed between each positive resist layer, and a barrier layer made of a composition having optical transparency is easily formed, so that intra-layer multiple reflection in each resist layer is achieved. The effect of being able to reduce is produced.

[Brief description of drawings]

FIG. 1 is a process chart illustrating a resist pattern forming method according to a first embodiment of the present invention.

FIG. 2 is a characteristic diagram showing changes in the dissolution rate of an alkali developing solution with respect to the amount of photosensitizer decomposition of the resist according to Example 1.

FIG. 3 is a characteristic diagram showing a variation in resist finish dimension with respect to a resist film thickness according to Example 1.

FIG. 4 is a characteristic diagram showing the contrast of the light intensity that actually reaches the resist layer through the mask and the alkali-soluble composition according to Example 1.

5 is a characteristic diagram showing a change in dissolution rate of an alkali developing solution with respect to a depth in a resist layer according to Example 1. FIG.

FIG. 6 is a process diagram illustrating a resist pattern forming method according to a conventional example.

FIG. 7 is a characteristic diagram showing an exposure intensity distribution formed in a resist layer according to a conventional example.

FIG. 8 is a characteristic diagram showing variations in resist finish dimension with respect to resist film thickness according to a conventional example.

FIG. 9 is a characteristic diagram showing the contrast of the light intensity that actually reaches the resist layer through the mask according to the conventional example.

FIG. 10 is a characteristic diagram showing a change in dissolution rate of an alkali developing solution with respect to a depth in a resist layer according to a conventional example.

[Explanation of symbols]

1 substrate to be processed 2 resist A (slow dissolution rate for the same exposure amount) 3 resist B (faster dissolution rate for the same exposure amount than resist A) 4 resist C (faster dissolution rate for the same exposure amount than resist B) 5) Alkali-soluble composition 6 Resist pattern 7 Mask

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 22, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

By the way, FIG. 7 shows a distribution diagram of the exposure intensity formed in the resist layer 8, and the numbers in the horizontal row indicate the relative values of the exposure intensity in the resist layer 8 when a certain amount of light is incident. Shows. In FIG. 7 comparison, since it is the standing wave by the interaction of the light reflected on the light and the workpiece substrate 1 that is incident on the resist layer 8, exposure intensity in Les resist layer 8 is relatively large layer Small layers can be alternated,
As a result, it is shown that the upper layer portion of the resist layer 8 has a higher exposure intensity, while the lower layer portion has a relatively lower exposure intensity.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

Further, the layer multiple reflection effect in les resist layer 8, the sensitivity and resist the finished dimension variation increases, as shown in FIG. 8, the resist finished size varies greatly with variations in the thickness of the resist layer 8 At the same time, as shown in FIG. 9, the resist layer 8 is actually passed through the mask 7.
Regarding the contrast of the light incident on, the difference between the exposed portion and the unexposed portion does not clearly appear.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006] As a result, Te 10 odor which represents the change in the dissolution rate into the alkaline developer due to the depth direction of the position of the resist layer 8, exposure light intensity, better upper portion of the resist layer 8 (front side) , The resist layer is larger than the lower layer portion (substrate side), and with one type of resist, the higher the exposure intensity, the faster the dissolution rate with the alkaline developer, so the dissolution rate decreases from the surface side to the substrate side. . Further, it has a maximum value and a minimum value corresponding to the standing wave.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

Since the conventional method of forming a resist pattern is performed as described above, when exposed, the light intensity becomes stronger toward the upper layer portion of the resist layer 8 and, conversely, the lower layer. The light gets harder to reach and becomes weaker toward the part. For this reason, the amount of decomposition of the photosensitive group is different, and it becomes easier to dissolve toward the upper layer portion of the resist layer 8 during development, and the pattern profile deteriorates. Further, since the developing solution is in contact with the upper layer portion for a longer time, the development is accelerated.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

Further, in the method of manufacturing a semiconductor device according to the second aspect, the positive type resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate. In addition, a barrier layer made of a soluble composition is formed between each positive resist layer to form a patterning layer having a multilayer structure, and the patterned layer having the multilayer structure is exposed and developed with a developing solution to form a resist pattern. Accordingly, each resist layers are formed reflection-preventing layer that by the alkali-soluble composition, reduces the film multiple reflection within the resist layer, to reduce the variation of sensitivity and resist trim size.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

Further, in the method of manufacturing a semiconductor device according to the third aspect of the present invention, the positive type resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate. At the same time, a barrier layer made of a soluble composition is formed between each positive resist layer, and a barrier layer made of a soluble composition is formed on the uppermost layer of the positive resist film to form a patterning layer having a multilayer structure. form a resist pattern by developing with patterned after exposure layer developer multilayer structure.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Further, in the method of manufacturing a semiconductor device according to a fourth aspect, a positive resist film is sequentially formed on the substrate from one having a high dissolution rate to an alkaline developer at the same exposure amount to one having a slow dissolution rate. while, in the positive resist layer, a light transparency that such a nitrene compound lifting
Zur alkali with soluble composition to form a barrier layer to form a patterned layer by a multilayer structure, by forming a resist pattern by developing in exposed after the alkali developing solution of the patterning layer of the multilayer structure, each positive resist the layers forming the antireflection layer with respect to the exposure light beam, film multi
Reduces double reflection and enters both exposed and unexposed areas
Increased contrast of light intensity
Into a rectangle.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

[0018]

EXAMPLES Example 1. The first embodiment of the present invention will be described below. 1A to 1C are cross-sectional views for explaining a method of forming a photoresist pattern according to the first embodiment in the order of steps. In the figure, 1 is a substrate to be processed, 2 is a resist C , 3 is a resist B, 4 is a resist A , 5 is a barrier layer formed of an alkali-soluble composition, and 6 is a resist layer exposed through a mask 7. , A resist pattern formed by development, and 7 represents a mask.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

And, if the esterification rate is high,
There are three types of resists, A, B, and C, and the resists 2 to 4 containing these photosensitive substances are referred to as a resist C , a resist B, and a resist A. Further, the alkali-soluble composition forming the barrier layer 5 used in Example 1 is a nitrene-based compound having an in-film multiple reflection preventing effect and light transparency.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Next, a method of forming a resist pattern according to the first embodiment will be described with reference to FIG. One-third of the film thickness of the resist C 2 normally applied on the substrate 1 to be processed
And the barrier layer 5 is formed thereon by several hundred liters. Next, the resist B3 is applied so as to have the same film thickness as the resist C2 , and the barrier layer 5 is further formed thereon by several hundred liters. Finally, the resist A 4 resist C 2, was applied B 3 to be the same thickness as the said barrier layer 5 is again several hundred Å is formed. This barrier layer 5 forms a layer of three types of resists that suppress mixing between the resists (FIG. 1).
(See (a)).

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Next, the resist layer is exposed through the mask 7. At this time, since the exposure amount absorbed is reduced from the surface side of the resist layer to the substrate side, the amount of the photosensitizer decomposed in the order of the resists A, B, and C is reduced . Further, since the intra-film multiple reflection in each resist is suppressed by the barrier layer 5 between each resist, the difference between the maximum value and the minimum value of the exposure amount in each resist layer becomes small. Further, since the barrier layer 5 has light transparency, light sneaking into the unexposed portion is reduced (FIG. 1).
(See (b)), however, the dissolution rate is adjusted to be slightly faster on the substrate side, and when the exposed portion is removed, the profile of the resist pattern 6 becomes close to a rectangle. Further, it is possible to prevent the unexposed portion from being dissolved during development, and the above effect is enhanced (see FIG. 1C).

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

Further, FIG. 5 shows the change of the dissolution rate depending on the position in the depth direction in the resist layer, and the regions surrounded by the broken line are the resists A, B and C from the surface side, respectively.
As shown in FIG. 5, the difference in dissolution rate between the substrate side and the resist surface side is small, and the standing wave is suppressed by the barrier layer 5 between the resist layers. The difference becomes smaller.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

According to a second aspect of the present invention, the positive resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate, and each positive resist layer is formed. In addition, a barrier layer made of a soluble composition is formed to form a patterning layer having a multi-layered structure, and the patterning layer having the multi-layered structure is exposed and developed with a developing solution to form a resist pattern. , it is formed reflection-preventing layer that by the alkali-soluble composition, reduces the film multiple reflection within the resist layer, an effect that it is possible to reduce the variation in sensitivity and resist trim size.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

According to a third aspect of the present invention, the positive resist film is sequentially formed on the substrate from the one having a high dissolution rate to the developing solution at the same exposure amount to the one having a slow dissolution rate, and each positive resist layer is formed. And forming a barrier layer of a soluble composition on the positive resist film, and forming a barrier layer of a soluble composition on the uppermost layer of the positive resist film to form a patterning layer having a multilayer structure, and exposing the patterning layer having the multilayer structure. than was so developed to form a resist pattern in a subsequent developer, an effect that it is possible to make the pattern profile in rectangular.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

Further, according to claim 4, a positive resist film is sequentially formed on the substrate from one having a high dissolution rate to an alkaline developer at the same exposure amount to one having a slow dissolution rate, and each positive resist film is formed. between the layers, to form a barrier layer by a alkali-soluble composition having a light transparency that such a nitrene compound to form a patterned layer by a multilayer structure, developed by the exposure after the alkali developing solution of the patterning layer of the multilayer structure since so as to form a resist pattern Te, each positive resist layers, anti-reflection layer is formed to exposure light, that Sosu the effect that it is possible to reduce the film multiple reflection within the resist layer With the exposure unit
And increase the contrast of the light intensity incident on the
The effect that the turn profile can be rectangular
Play the fruit.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] Explanation of code

[Correction method] Change

[Correction content]

[Explanation of Codes] 1 substrate to be processed 2 resist C (having a slower dissolution rate for the same exposure amount) 3 resist B (having a faster dissolution rate for the same exposure amount than resist A) 4 resist A (same exposure amount than resist B) 5) Alkali-soluble composition 6 Resist pattern 7 Mask

[Procedure Amendment 17]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 1

[Correction method] Change

[Correction content]

[Figure 1]

Claims (4)

[Claims] 1. A method of manufacturing a semiconductor device, wherein a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and then the positive resist is developed to form a resist pattern. Forming a patterning layer having a multi-layer structure by sequentially forming the positive resist film on the substrate from one having a high dissolution rate in a developing solution at the same exposure amount to one having a slow dissolution rate in a developing solution; and patterning the multi-layer structure. A method of manufacturing a semiconductor device, comprising: a step of exposing a layer; and a step of developing with a developing solution after exposure. 2. A method of manufacturing a semiconductor device, wherein a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and then the positive resist is developed to form a resist pattern. The positive resist film is sequentially formed on the substrate from one having a high dissolution rate to a developing solution at the same exposure amount to one having a slow dissolution rate, and a barrier layer of a soluble composition is formed between the positive resist layers. And a step of forming a patterning layer having a multi-layered structure, exposing the patterning layer having the multi-layered structure, and developing with a developing solution after exposure. 3. A method of manufacturing a semiconductor device, wherein a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and then the positive resist is developed to form a resist pattern. The positive resist film is sequentially formed on the substrate from one having a high dissolution rate to a developing solution at the same exposure amount to one having a slow dissolution rate, and a barrier layer of a soluble composition is formed between the positive resist layers. And a step of forming a barrier layer of a soluble composition on the uppermost layer of the positive resist film to form a patterning layer of a multilayer structure, a step of exposing the patterning layer of the multilayer structure, and a post-exposure developing solution. And a step of developing with a semiconductor device. 4. A method of manufacturing a semiconductor device, wherein a positive resist film is formed on a substrate, a desired pattern is exposed on the resist film, and then the positive resist is developed to form a resist pattern. The positive resist film is sequentially formed on the substrate from one having a high dissolution rate to an alkaline developer at the same exposure amount to one having a slow dissolution rate, and an alkali-soluble alkali nitrite compound is formed between the positive resist layers. A semiconductor comprising: a step of forming a barrier layer of the composition to form a patterning layer having a multilayer structure; a step of exposing the patterning layer of the multilayer structure; and a step of developing with an alkaline developer after exposure. Device manufacturing method.