JP3264424B2 - Patterning method for photoresist layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for patterning a photoresist layer formed on a substrate.

[0002]

2. Description of the Related Art In a manufacturing process of a semiconductor device, as shown in FIG. 4, various substrates 1 such as a semiconductor substrate, an insulating substrate, and a substrate having an insulating film formed on a semiconductor substrate main body are formed. The layer 2 having a desired pattern may be formed as an intermediate layer or a final layer.

For such a case, that is, the substrate 1
In order to form a layer 2 having a desired pattern as an intermediate layer or a final layer thereon, a method for forming a layer having a desired pattern described below has been proposed with reference to FIG.

That is, a photoresist layer 3 having a composition containing a novolak resin and a photosensitive agent is formed on a substrate 1 (FIG. 5A).

Next, the photoresist layer 3 formed on the substrate 1 is patterned into a pattern having a window 3a 'having a pattern of a layer 2 having a desired pattern as an intermediate layer or a final layer. Then, a patterned photoresist layer 3 'is formed from the photoresist layer 3 (FIG. 5B).

Next, a layer 2 having a desired pattern as an intermediate layer or a final layer with respect to the substrate 1 using the patterned photoresist layer 3 'as a mask layer.
The region of the patterned photoresist layer 3 ′ as the mask layer of the substrate 1 facing the window 3 a, that is, the patterned photoresist as the mask layer of the substrate 1 is deposited by a material deposition process, for example, a deposition process. On the areas not masked by the layer 3 ', a layer 2 having the desired pattern as an intermediate or final layer is placed on the patterned photoresist layer 3' as a mask layer, as an intermediate or final layer. Along with the formation of the layer 2 'made of the material of the layer having the desired pattern, it is formed (FIG. 5).
C).

[0007] Next, the patterned photoresist layer 3 'as a mask layer is subjected to a leaching treatment on the patterned photoresist layer 3' as a mask layer.
Is removed from the substrate 1 together with a layer 2 'made of a material having a desired pattern as an intermediate layer or a final layer formed on the photoresist layer 3' (FIG. 5).
D, FIG. 4). The above is a method of forming a layer having a desired pattern that has been conventionally proposed.

Further, in the method of forming a layer having such a desired pattern, a photoresist layer 3 formed on the substrate 1 has a pattern of a layer 2 having a desired pattern as an intermediate layer or final layer Conventionally, a method of patterning a photoresist layer described below with reference to FIG. 6 has been proposed for patterning into a pattern having windows 3a '.

That is, the novo formed on the substrate 1
For a photoresist layer 3 having a composition including a rack resin and a photosensitive agent , a photomask 4 having a light-transmitting region 4a having a pattern of a layer 2 having a desired pattern was used.
An exposure process with ultraviolet rays 5 is performed, whereby the photoresist layer 3 is exposed to the regions 3L exposed by the ultraviolet rays 5
(FIG. 6A).

Next, on the surface of the photoresist layer 3 forming the exposed region 3L, a layer of such a modified liquid is made to exist by dropping a modified liquid having a composition containing chlorobenzene or bromobenzene. Thereby, a part of the photosensitizer and a part of the low molecular weight component of the novolak resin in the region 3b along the surface of the photoresist layer 3 are eluted into the layer 6 of the modifying liquid (FIG. 6B). Layer 6 of the reforming liquid
By removing from the surface of the photoresist layer 3 by spin-off or the like (FIG. 6C), the region 3b along the surface of the photoresist layer 3 is subjected to a modification treatment using a modification liquid, whereby The region 3b along the surface of the photoresist layer 3 is modified into a mode in which the dissolution rate by a developer described later is lower than that of the region below the region 3b along the surface of the photoresist layer 3.

Next, a developing solution having a composition containing phosphate or tetramethylammonium hydroxide is dropped on the surface of the photoresist layer 3 in which the exposed region 3L is formed and the region 3b along the surface is modified. Causes a layer 7 of such a developer to be present, thereby effecting a development action on the photoresist layer 3 by dissolving the area 3L exposed by the ultraviolet rays 5 with the developer (FIG. 6D),
Next, the developer layer 7 is removed from the photoresist layer 3 by rinsing with water, and then dried (FIG. 6).
E) Therefore, the photoresist layer 3 is subjected to a development process, whereby the window 3 having the pattern of the light-transmitting region 4 a of the photomask 4 is formed from the photoresist layer 3.
A photoresist layer 3 'patterned into a pattern having a' is formed (FIGS. 6E and 5B).

The above is a method of patterning a photoresist layer that has been conventionally proposed. According to such a conventional method of patterning a photoresist layer, the photoresist layer 3
After the step (FIG. 6A) of performing an exposure process using a photomask 4 on the photoresist layer 3 and before the step of performing a development process on the photoresist layer 3 (FIG. 6D), a modifying liquid is applied to a region along the surface of the photoresist layer 3. A step (FIGS. 6B and 6C) of performing the modification process used, and the region (3b) along the surface of the photoresist layer 3 is developed by the step of performing the modification process (FIGS. 6B and 6C). Is modified in such a manner that the solubility of the developer used in the step (FIG. 6D) is lower than that of the region below the region 3b along the surface.

For this reason, a step of performing a developing process (FIG. 6D)
In the region 3b along the surface of the photoresist layer 3
However, the solubility in the developing solution used in the step of performing the developing treatment (FIG. 6D) is lower than that in the region below the region 3b along the surface.

Thus, in the step of performing the developing process (FIG. 6D), the patterned photoresist layer 3 'is so-called overhanged from the photoresist layer 3, as shown in FIGS. 6E and 5B. It can be obtained in a cross-sectional pattern.

In the step of performing the developing process (FIG. 6D), if a patterned photoresist layer 3 'can be obtained from the photoresist layer 3 in an overhanging sectional pattern, The step of forming a patterned photoresist layer 3 'from the photoresist layer 3 in the method of patterning the photoresist layer shown in FIG. 6 and the method of forming a layer having a desired pattern shown in FIG. 4 (FIG. 5B) 4) by applying to FIG.
In the step of removing the photoresist layer 3 ′ from the substrate (FIG. 5D) in the formation method having the desired pattern shown in FIG. 5D, the photoresist layer 3 ′ is formed on the substrate 1 in the window 3 a ′ of the photoresist layer 3 ′. The layer 2 having the desired pattern can be removed without coming into contact with the layer 2 having the desired pattern, so that the layer 2 having the desired pattern can be formed with less "burr" and less fluctuation in width, and Can be obtained with a good smooth pattern.

Conventionally, in a method of forming a layer having a desired pattern shown in FIG. 4, a novola formed on a substrate 1 is formed similarly to the method of patterning a photoresist layer shown in FIG.
FIG. 7 is used to pattern a photoresist layer 3 having a composition having a rack resin and a photosensitive agent into a pattern having a window 3a ′ having a pattern of a layer 2 having a desired pattern as an intermediate layer or a final layer. A method of patterning a photoresist layer described below has also been proposed.

That is, the novo formed on the substrate 1
On the surface of the photoresist layer 3 having a composition having a rack resin and a photosensitizer, a modifying solution having a composition having chlorobenzene or bromobenzene is dropped on the surface of the photoresist layer 3 as in the method of patterning the photoresist layer shown in FIG. A layer 6 of such a modifying liquid is present, whereby a part of the photosensitizer and a part of the low molecular weight components of the novolak resin in the region 3b along the surface of the photoresist layer 3 are removed. 6
Then, the modified liquid layer 6 is removed from the surface of the photoresist layer 3 by spin-off or the like (FIG. 7B). The region 3b along the surface of the photoresist layer 3 is subjected to a modification treatment using a modification liquid, so that the region 3b along the surface of the photoresist layer 3 is dissolved along the surface of the photoresist layer 3 by a dissolution rate by a developer described later. Is modified so as to be lower than the region below the region 3b.

Next, as with the photoresist layer patterning method shown in FIG. 6, a layer 2 having a desired pattern is formed on the photoresist layer 3 in which the region 3b is modified along the surface. Using a photomask 4 having a light-transmitting region 4a having a pattern, an exposure process using ultraviolet rays 5 is performed.
To form an exposed area 3L (FIG. 7C).

Next, on the surface of the photoresist layer 3 in which the region 3b along the surface is modified and the exposure region 3L is formed, as in the case of the photoresist layer patterning method shown in FIG. By the addition of a developer having a composition comprising phosphate or tetramethylammonium hydroxide, a layer 7 of such a developer is present, whereby the developing action of dissolving the area 3L exposed by the ultraviolet rays 5 with the developer is carried out. (FIG. 7D), and then the developer layer 7 is removed from the photoresist layer 3 by rinsing with water, and then dried (FIG. 7E). 3 is subjected to a development process, whereby the photoresist layer 3 is patterned into a pattern having a window 3a having a pattern of the light-transmitting region 4a of the photomask 4. Forming a Torejisuto layer 3 '(Fig. 7E, Figure 5B).

The above is another method of patterning a photoresist layer conventionally proposed. According to such a conventional method of patterning a photoresist layer shown in FIG. 7, before the step of performing an exposure treatment (FIG. 7C), the patterning method of the conventional photoresist layer shown in FIG. Similarly, prior to the step of performing a developing process on the photoresist layer 3 (FIGS. 7D and E), a step of performing a modifying process using a modifying liquid on a region along the surface of the photoresist layer 3 (FIGS. 7B and 7C). ), Detailed description is omitted,
FIG. 7D is obtained by performing the developing process (FIGS. 6D and 6E).
E, As shown in FIG. 5B, the patterned photoresist layer 3 ′ is so-called overhanged from the photoresist layer 3 as in the case of the photoresist layer patterning method shown in FIG. It can be obtained in a cross-sectional pattern.

[0021]

In the case of the conventional photoresist layer patterning method shown in FIGS. 6 and 7, at the end of the step of performing the modification treatment (FIGS. 6B and C, FIGS. 7A and B), Step of removing the modifying liquid on the surface of photoresist layer 3 from the surface of photoresist layer 3 (FIGS. 6C and 7B)
When the steps of performing the modification process (FIGS. 6B and C, FIGS. 7A and B) are completed, the photoresist layer 3
It is undeniable that the amount of the modified liquid is present in the region 3b along the surface of the substrate with variation in the amount thereof. Therefore, in the step of performing the developing treatment (FIGS. 6D and E, FIGS. 7D and E), In the region 3b along the surface of the photoresist layer 3, it cannot be denied that the amount of the modified liquid is present with a variation in the amount. For this reason, the developing action of the developing solution on the photoresist layer 3 in the step of performing the developing process (FIGS. 6D and E, FIGS. 7D and E) is affected with the variation due to the remaining of the modifying solution.

As described above, in the conventional photoresist layer patterning method shown in FIGS. 6 and 7, the patterned photoresist layer 3 'is overhanged from the photoresist layer 3. Even if a cross-sectional pattern can be obtained, there is a drawback that the overhanging cross-sectional pattern cannot be obtained with good reproducibility in a cross-sectional pattern having no intended variation.

Thus, the present invention is free from the disadvantages mentioned above,
It is intended to propose a new photoresist layer patterning method.

[0024]

A photoresist layer patterning method according to the first invention of the present application is formed on a substrate in the same manner as the conventional photoresist layer patterning method shown in FIG. A set having a novolak resin and a photosensitive agent
To formation of the photoresist layer, and a step of performing exposure using a photomask, post-step of performing the exposure process, the region along the surface of the photoresist layer, Kurorobenzenma
Or a step of performing a reforming process using a reforming solution having a composition containing bromobenzene, and after the step of performing the reforming process, the photoresist layer is treated with phosphate or tetramethyl hydroxide.
Performing a development process using a developer having a composition containing ammonium .

However, the method of patterning a photoresist layer according to the first invention of the present application is a method of patterning a photoresist layer, which comprises the steps of: From the area along the surface of the resist layer, remove the residual modifier from
Or a step of removing using a reforming liquid removing liquid having a composition having Diflon .

The second aspect th patterning method of a photoresist layer according to the invention, like the patterned method of the conventional photoresist layer shown in FIG. 7, climb formed on a substrate
Chlorobenzene or bromobenzene in a region along the surface of a photoresist layer having a composition having a block resin and a photosensitizer.
A step of performing a reforming process using a reforming liquid having a composition having a zen, a process of performing an exposing process using a photomask on the photoresist layer after the process of performing the reforming process, and a process of performing the exposing process. after the step of subjecting, to a photoresist layer, phosphoric acid
Composition with salt or tetramethylammonium hydroxide
Performing a developing process using the developing solution .

However, the method of patterning a photoresist layer according to the second invention of the present application is a method of patterning a photoresist layer according to the second aspect of the present invention. from the area along the surface of the layer, the residual reforming liquid, phosphate or
Or a step of removing using a reforming liquid removing liquid having a composition having Diflon .

The method of patterning a photoresist layer according to the third invention of the present application differs from the method of patterning a conventional photoresist layer shown in FIG. 7 and the method of patterning a photoresist layer according to the second invention of the present application. Similarly, in a region along the surface of a photoresist layer having a composition including a novolak resin and a photosensitive agent formed on a substrate, chlorobenzene or the like is provided.
Or a step of performing a reforming process using a reforming solution having a composition having bromobenzene, and after the step of performing the reforming process, a step of performing an exposure process using a photomask on the photoresist layer, After the step of exposing, the photoresist layer is treated with phosphate or tetramethylammonium hydroxide.
Performing a development process using a developer having a composition having a system.

However, the method for patterning a photoresist layer according to the third invention of the present application is the same as the method for patterning a photoresist layer described above, except that after the step of performing the modification process and before the step of performing the exposure process, From the area along the surface of the resist layer, remove the residual modifier from
Or a step of removing using a reforming liquid removing liquid having a composition having Diflon .

[0030]

Embodiment 1 Next, an embodiment of a method for patterning a photoresist layer according to the first invention of the present application will be described with reference to FIG.

In FIG. 1, portions corresponding to those in FIG. 6 are denoted by the same reference numerals, and detailed description thereof will be omitted. The first application shown in FIG.
The method of patterning a photoresist layer according to the second invention comprises:
As with the patterning method of the conventional photoresist layer shown in FIG. 6, having a similar, novolac resin and a photosensitive agent
That step of performing exposure processing on the photoresist layer 3 having the composition (FIG. 1A), after the step (FIG. 1A) for performing the exposure process, the same, chlorobenzene region 3b along the surface of the photoresist layer 3 or With bromobenzene
Modifier-liquid reforming processes performed step using a composition (Fig. 1B and C), after the step (Fig. 1B and C) subjecting the reforming process, the same, also phosphate to the photoresist layer 3
Is development of a composition having tetramethylammonium hydroxide
A developing process using a liquid (FIGS. 1F and 1G), but after the process of applying the modifying process (FIGS. 1B and 1C) and before the process of applying the developing process (FIGS. 1F and 1G), Removal of such a modified liquid by dropping of a modified liquid removing liquid having a composition containing phosphate or diflon onto the surface of the photoresist layer 3 forming the 3L and the area 3b along the surface is modified. A layer of liquid 8 is present, whereby
In the modified liquid removing liquid layer 8, the residual modified liquid existing in the region 3b along the surface of the photoresist layer 3 is eluted (FIG. 1D). The layer 8 is removed from the photoresist layer 3 by rinsing with water, and then dried by spin-off or the like (FIG. 1E), so that the region 3b along the surface of the photoresist layer 3
From the residue of the reforming fluid, with phosphate or diflon
A step of removing (Figure 1D and E) using a modified liquid remover composition that.

The above is an embodiment of the method for patterning a photoresist layer according to the first invention of the present application. According to such an embodiment of the method for patterning a photoresist layer according to the first invention of the present application, after the step of performing a modification process (FIGS. 1B and 1C), the step of performing a development process (FIGS. 1F and 1G). ), The step of removing the residual reforming liquid (FIG. 1)
Since the method is the same as the conventional method of patterning a photoresist layer shown in FIG. 6 except for having D and E), detailed description is omitted, but the method of patterning a conventional photoresist layer shown in FIG. As in the case of (1), in the step of performing the developing process (FIGS. 1F and 1G), the region 3b along the surface of the photoresist layer 3 has a solubility in the developing solution used in the step of performing the developing process (FIGS. As a result, the area is lower than the area below the area 3b along the surface, and thus, the light-transmitting area 4a of the photomask 4 is removed from the photoresist layer 3 by the step of performing the exposure treatment (FIGS. 1F and 1G). A photoresist layer 3 'patterned into a pattern having a window 3a' having the pattern shown in FIG. 1G and FIG. 5B can be obtained with a so-called overhanging cross-sectional pattern.

However, in the case of the method of patterning a photoresist layer according to the present invention shown in FIG. 1, after the step of performing the modification (FIGS. 1B and 1C), the step of performing the development (FIG. 1F)
And G) before the step of removing the residue of the reforming liquid (FIGS. 1D and 1E), and performing the reforming process by the step of removing the residue of the reforming liquid (FIGS. 1D and 1E). When the steps (FIGS. 1D and 1E) are completed, the photoresist layer 3
Even if the amount of the reforming liquid remains in the region 3b along the surface of the substrate with variation in the amount, the residue of the reforming liquid can be removed.
The developing action of the developing solution on the photoresist layer 3 in F and G) can be prevented from being affected by the remaining of the modifying solution.

Therefore, the patterned photoresist layer 3 ′ can be obtained from the photoresist layer 3 with good reproducibility in a cross-sectional pattern that is overhang and has no intended variation.

[0035]

Embodiment 2 Next, an embodiment of a method for patterning a photoresist layer according to the second invention of the present application will be described with reference to FIG.

In FIG. 2, parts corresponding to those in FIGS. 1 and 7 are denoted by the same reference numerals, and detailed description is omitted. Patterning method of the photoresist layer according to the present second th invention shown in FIG. 2, as in the case of patterning method of the conventional photoresist layer shown in FIG. 7, the same, a novolak resin and a photosensitive agent
Having chlorobenzene or bromobenzene in a region 3b along the surface of the photoresist layer 3 having the composition
A similar exposure process is performed on the photoresist layer 3 after the step of performing the reforming process using the composition reforming liquid (FIGS. 2A and 2B) and the process of performing the reforming process (FIGS. 2A and 2B). 2C and a step of performing the exposure process (FIG. 2C).
After C), similar, phosphorus respect photoresist layer 3
With acid salts or tetramethylammonium hydroxide
And a step of performing a development process using a developing solution (FIGS. 2F and 2G). After the step of performing an exposure process (FIG. 2C),
Before the step of performing the developing treatment (FIGS. 2F and 2G), FIG.
In the same manner as in the embodiment of the method for patterning a photoresist layer according to the first invention shown in FIG.
Removal of such a modified liquid by dropping a modified liquid removing liquid having a composition containing phosphate or diflon onto the surface of the photoresist layer 3 where L is formed and the region 3b along the surface is modified. A layer of liquid 8 is present, whereby the residue of the modifying liquid present in the region 3b along the surface of the photoresist layer 3 is eluted in the layer 8 of modifying liquid removing liquid (FIG. 2D). Next, the layer 8 of the modified liquid removing liquid is removed from the photoresist layer 3 by rinsing with water,
Then, drying is performed by spin-off or the like (FIG. 2E), so that the remaining of the reforming liquid is changed from the region 3b along the surface of the photoresist layer 3 to phosphate or diflon.
There is a step of removing using a modified liquid removing liquid having a composition (FIGS. 2D and 2E).

The above is an embodiment of the method for patterning a photoresist layer according to the second invention of the present application. According to such an embodiment of the method for patterning a photoresist layer according to the second invention of the present application, after the step of performing the exposure processing (FIG. 2C), the step of performing the development processing (FIGS. 2F and 2G).
The method is the same as the conventional method of patterning a photoresist layer shown in FIG. 7 except that before the step of removing the residue of the modified liquid (FIGS. 2D and E), the detailed description is omitted. In the same manner as in the conventional photoresist layer patterning method shown in FIG. 7, the patterned photoresist layer 3 'is removed from the photoresist layer 3 in FIG.
As shown in FIG. 5B, a so-called overhanging cross-sectional pattern can be obtained.

However, in the method of patterning a photoresist layer according to the present invention shown in FIG. 2, after the step of performing the exposure treatment (FIG. 2C), and before the step of performing the development treatment (FIGS. 2F and 2G), For removing the residue (FIG. 2D)
And E), and the surface of the photoresist layer 3 at the end of the step of performing the modification treatment (FIGS. 2D and E) by the step of removing the residual of the modification liquid (FIGS. 2D and E). Even if there is a residue of the reforming liquid in the region 3b along the line, the residue of the reforming liquid can be removed.
As in the case of the photoresist layer patterning method according to the first invention of the present application shown in FIG. 1, the developing action of the developing solution on the photoresist layer 3 in the step of performing the developing treatment (FIGS. 2F and 2G) is modified. It can be unaffected by residual liquid.

Therefore, as in the case of the method of patterning a photoresist layer according to the first invention of the present application shown in FIG.
From the photoresist layer 3, the patterned photoresist layer 3 ′ can be obtained with good reproducibility in a cross-sectional pattern that is overhanged and has no intended variation.

[0040]

Third Embodiment Next, with reference to FIG. 3, an embodiment of a method of patterning a photoresist layer according to the third invention of the present application will be described.

In FIG. 3, portions corresponding to those in FIGS. 1, 2 and 7 are denoted by the same reference numerals, and detailed description thereof will be omitted. FIG.
Patterning method of the photoresist layer according to the present second th invention shown in, as in the case of the patterning method of the conventional photoresist layer shown in FIG. 7, the same, the novolak resin
Chlorobenzene or bromobenzene is applied to a region 3b along the surface of the photoresist layer 3 having a composition having a photosensitive agent.
Step of performing a reforming treatment using a reforming liquid having a composition having
A and B) and a similar step of performing an exposure process on the photoresist layer 3 (FIG. 3E) after the step of performing the modification process (FIGS. 2A and B) and a step of performing the exposure process (FIG. 3E). 3E) A similar photoresist layer 3 after
Phosphate or tetramethylammonium hydroxide
Step of performing development processing using a developer having a composition having
F and G), but performing a reforming process (FIG. 3A).
And B) before the step of performing the exposure treatment (FIG. 3E), removing the modified liquid having a composition having a phosphate or diflon on the surface of the photoresist layer 3 in which the region 3b along the surface is modified. The dripping of the liquid causes such a layer of modified liquid removing liquid 8 to be present, whereby the layer 8 of modified liquid removing liquid is present in the region 3 b along the surface of the photoresist layer 3. The remaining of the reforming liquid is eluted (Fig. 3
C) Next, the layer 8 of the modified liquid removing liquid is removed from the photoresist layer 3 by rinsing with water, and then dried by spin-off or the like (FIG. 3D). There is a step (FIGS. 1D and 1E) of removing the residual reforming liquid from the region 3b along the surface of the layer 3 using a reforming liquid removing liquid having a composition containing phosphate or diflon .

The above is an embodiment of the method of patterning a photoresist layer according to the third invention of the present application. According to such an embodiment of the method of patterning a photoresist layer according to the third invention of the present application, after the step of performing the modification processing (FIGS. 3A and 3B), the step of performing the exposure processing (FIG. 3E).
The method is the same as the conventional method of patterning a photoresist layer shown in FIG. 7 except that before the step of removing the residue of the modified liquid (FIGS. 3C and 3D), the detailed description is omitted. 7, the patterned photoresist layer 3 'is removed from the photoresist layer 3 in the same manner as in the conventional photoresist layer patterning method shown in FIG.
As shown in FIG. 5B, a so-called overhanging cross-sectional pattern can be obtained.

However, in the case of the method of patterning a photoresist layer according to the present invention shown in FIG. 3, after the step of performing a modification process (FIGS. 3A and 3B), a step of performing an exposure process (FIG.
E) Before removing the residual reforming liquid (FIG. 3C)
And D), and when the step of performing the modification process (FIGS. 3A and 3B) is completed by the step of removing the residue of the modification liquid (FIGS. 3C and 3D), the photoresist layer 3
Even if there is a residue of the reforming liquid in the region 3b along the surface of the photoresist, the residue of the reforming liquid can be removed, so that the pattern of the photoresist layer according to the first invention shown in FIG. As in the case of the chemical conversion method, the developing action of the developing solution on the photoresist layer 3 in the step of performing the developing treatment (FIGS. 3F and 3G) can be prevented from being affected by the remaining of the modifying solution.

Accordingly, as in the case of the method for patterning a photoresist layer according to the first invention of the present application shown in FIG.
From the photoresist layer 3, the patterned photoresist layer 3 ′ can be obtained with good reproducibility in a cross-sectional pattern that is overhanged and has no intended variation.

[0045]

According to the method of patterning a photoresist layer according to the present invention, as in the case of the conventional method of patterning a photoresist layer, a combination comprising a novolak resin and a photosensitizer is used.
Before the step of subjecting the formed photoresist layer to a development treatment, a region along the surface of the photoresist layer is cleaned.
A step of performing a reforming process using a reforming solution having a composition having lorobenzene or bromobenzene; and, by performing the reforming process, a region along the surface of the photoresist layer is subjected to a developing process. Phosphates used in the process
Has been modified in such a manner that the solubility in a developer having a composition having tetramethylammonium hydroxide is lower than that in the region below the region along the surface, so that in the step of performing the developing treatment, The region along the surface of the resist layer has a lower solubility than the region below the region along the surface, due to the solubility of the developing solution used in the step of performing the developing process. From the photoresist layer, the patterned photoresist layer can be obtained in a so-called overhanging cross-sectional pattern.

However, in the case of the method of patterning a photoresist layer according to the present invention, after the step of applying the modifying treatment and before the step of applying the developing treatment, the residue of the modifying liquid is reduced to phosphate or the like.
Or a step of removing using a reforming liquid removing liquid having a composition having Diflon , and the step of removing the residual reforming liquid has completed the step of performing the reforming treatment. sometimes,
Even if the amount of the modified liquid remaining in the region along the surface of the photoresist layer varies, the residual of the modified liquid can be removed. The developing action of the developing solution on the resist layer can be prevented from being affected by the remaining of the modifying solution.

Therefore, the patterned photoresist layer can be obtained from the photoresist layer in a reproducible manner with a cross-sectional pattern that is overhang and has no intended variation.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing sequential steps showing an embodiment of a method for patterning a photoresist layer according to the first invention of the present application.

FIG. 2 is a schematic diagram showing an embodiment of a method for patterning a photoresist layer according to a second invention of the present application, in sequential steps.

FIG. 3 is a schematic diagram showing an embodiment of a method for patterning a photoresist layer according to a third invention of the present application, in sequential steps.

FIG. 4 is a schematic cross-sectional view showing a state in which a layer having a desired pattern is formed on a substrate, for describing a method of patterning a photoresist layer according to the present invention and a method of patterning a conventional photoresist layer. FIG.

FIG. 5 is a schematic diagram showing a method of forming a layer having a desired pattern, which is used for describing a method of patterning a photoresist layer according to the present invention and a method of patterning a conventional photoresist layer. is there.

FIG. 6 is a schematic diagram showing a conventional method of patterning a photoresist layer in sequential steps.

FIG. 7 is a schematic diagram showing a conventional method of patterning another photoresist layer in sequential steps.

[Explanation of symbols]

Reference Signs List 1 substrate 2 layer having desired pattern 2 'layer formed simultaneously with layer having desired pattern 3 photoresist layer 3L exposed area 3' patterned photoresist layer 3a window 4 photomask 4a translucent Area 5 Ultraviolet rays 6 Reforming liquid layer 7 Developer liquid layer 8 Reforming liquid removing liquid layer

Continuation of front page (56) References JP-A-4-296860 (JP, A) JP-A-61-272931 (JP, A) JP-A-7-168368 (JP, A) JP-A-60-43654 (JP) , A) JP-A-2-10364 (JP, A) JP-A-8-202050 (JP, A) JP-A-4-206625 (JP, A) JP-A-63-104422 (JP, A) 63-114127 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03F 7/38 G03F 7/26 H01L 21/027

Claims (3)

(57) [Claims] 1. A photosensitizer comprising: a novolak resin formed on a substrate;
Exposing a photoresist layer having a composition having a chemical agent to a photoresist layer using a photomask. After the exposing step, chlorobenzene or brombenzene is added to a region along the surface of the photoresist layer.
Applying a modifying treatment using a modifying liquid having a composition having a phosphoric acid , and after the applying the modifying treatment, the photoresist layer contains phosphate or tetramethylammonium hydroxide.
Performing a developing process using a developing solution having a composition having the following composition: a photoresist layer patterning method, wherein after the modifying process, before the developing process, the surface of the photoresist layer Yes from along regions, the residual of the modifier-liquid, a phosphate or Daifuron
A method for patterning a photoresist layer, comprising a step of removing using a modified liquid removing liquid having a composition to be performed. 2. A photosensitizer comprising a novolak resin formed on a substrate.
Having chlorobenzene or bromobenzene in a region along the surface of a photoresist layer having a composition having
A step of performing a modification process using a modified liquid, a step of performing an exposure process using a photomask on the photoresist layer after the step of performing the modification process, and a process of performing the exposure process using a photomask. Then, phosphate or tetramethylammonium hydroxide is added to the photoresist layer.
Performing a developing process using a developing solution having a composition having the following composition. In the method of patterning a photoresist layer, after the step of performing the exposure process, and before the step of performing the developing process, the photoresist layer is formed along the surface of the photoresist layer. The remaining of the above-mentioned reforming liquid is
A method for patterning a photoresist layer, comprising a step of removing using a modified liquid removing liquid having a composition to be performed. 3. A photosensitive composition comprising a novolak resin formed on a substrate and photosensitive resin.
Having chlorobenzene or bromobenzene in a region along the surface of a photoresist layer having a composition having
A step of performing a modification process using a modified liquid, a step of performing an exposure process using a photomask on the photoresist layer after the step of performing the modification process, and a process of performing the exposure process using a photomask. Then, phosphate or tetramethylammonium hydroxide is added to the photoresist layer.
Performing a developing process using a developing solution having a composition having the following composition: a photoresist layer patterning method, wherein after the modifying process, before the exposing process, the surface of the photoresist layer Yes from along regions, the residual of the modifier-liquid, a phosphate or Daifuron
A method for patterning a photoresist layer, comprising a step of removing using a modified liquid removing liquid having a composition to be performed.