TW201602716A - Resist layer with blank, method of manufacturing the same, mask blank and imprint mold blank, and transfer mask, imprint mold and method of manufacturing the same - Google Patents

Abstract

This resist-layer-equipped blank (10) is provided with a resist layer (7) which is formed upon a substrate (1), and which is configured from a positive resist material. The thickness of the resist layer (7) is not more than 200 nm. The rate of dissolution of an unexposed section of the resist layer (7) with respect to an aqueous developing solution is not more than 0.05 nm/sec. A development-acceleration layer (9), which serves to cause the aqueous development solution to spread all over at least an exposed section of the resist layer (7), is formed upon the resist layer (7). The water contact angle at the surface of the unexposed section of the resist layer may be 66 DEG or greater.

Description

Substrate of resistive layer, method for producing the same, mask base and imprint mold base, and transfer mask, imprint mold and manufacturing method thereof

The present invention relates to a substrate for a resist layer, a method for producing the same, a mask substrate, and a mold base for imprint, and a photomask for transfer, a mold for imprint, and a method for producing the same.

As a technique for forming a fine pattern on a semiconductor element or the like, a lithography technique using a transfer mask is known. Specifically, it is a technique of optically transferring the film pattern to a resist layer formed on a semiconductor substrate by a transfer mask having a film pattern formed on a glass substrate.

Further, as another technique for forming a fine pattern, a nanoimprint lithography can be cited. Specifically, it is a technique for forming an imprinting mold having a pattern having a concave-convex shape formed on a surface of a surface, and a material layer for forming a fine structure formed on a surface of a semiconductor substrate or the like to be subjected to microfabrication. Direct contact to transfer the uneven pattern.

Such a transfer mask or imprint mold is also manufactured by using a lithography technique, such as a light-shielding film and a phase shift mask, if it is a transfer mask. A specific design pattern is formed on the film, and a specific design pattern is formed on the glass substrate of the main mold if it is an imprint mold.

In the case of manufacturing a transmissive mask as a transfer mask, first, a resist layer is formed on a film formed on a light-transmissive substrate such as glass, and exposed and developed to form a resist pattern. Then, the film (and the desired substrate) is etched using the resist pattern as a mask to form a mask pattern (design pattern), thereby obtaining a transfer mask.

For the mask pattern, when the transmittance of exposure light (for example, an ArF excimer laser) used in the manufacture of a semiconductor element or the like is an optical density of 2.5 or more, a binary mask is obtained at a transmittance of 1 to 30%. In the case of the right and left, a halftone type phase shift mask is obtained (see Patent Document 1).

Further, when EUV (Extreme Ultra Violet) light is used as the exposure light used in the production of a semiconductor element or the like, a photomask substrate having a reflective layer, an absorbing layer, and a hard mask layer formed on the substrate is used. Reflective mask (refer to Patent Document 2).

Further, in the case of producing an imprint mold, a resist layer is formed on the hard mask layer formed on the surface of the glass substrate, and exposed and developed to form a resist pattern. Then, the hard mask layer and the substrate are etched using the resist pattern as a mask to form a specific pattern on the substrate, thereby obtaining an imprint mold (see Patent Document 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-304956

[Patent Document 2] International Publication No. 2012/105508

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-73305

In recent years, with the increase in the performance of information communication equipment and the increase in the capacity of storage media, the miniaturization of circuit patterns of semiconductor elements and concave and convex patterns of storage media has been progressing. In order to promote the miniaturization of the patterns, in addition to the short wavelength of the wavelength of the exposure light, it is also required to further reduce the design pattern formed on the transfer mask.

In the photolithography technique, since the design pattern formed on the photomask as the transfer mask is reduced and projected and transferred onto the wafer, the design pattern formed on the photomask is larger than the circuit pattern. However, if the size of the circuit pattern is very small compared to the wavelength of the exposure light (for example, 193 nm (ArF excimer laser)), there is a problem that the resolution of the pattern is lowered due to the interference of light, even if the design is to be designed. The pattern is transferred onto the wafer, and the design pattern is also inconsistent with the transferred circuit pattern. In order to solve such a problem, for example, an illuminating mask forms an auxiliary pattern. As such an auxiliary pattern, SRAF (Sub Resolution Assist Feature) which is not transferred onto a wafer and forms an auxiliary circuit pattern is known. Since the resolution of light is used to cancel the reduction in resolution due to interference of light, a line width of 40 nm or less is required as the size of the SRAF.

Further, in the nanoimprint lithography technique, the pattern formed on the imprint mold is directly transferred to the transfer target, but it is required to set the line width of the pattern (for example, the line and the gap pattern) formed in the mold. It is 30 nm or less.

In the transfer mask or the imprint mold, when the formed design pattern is made fine, the resist pattern used for forming the design pattern is required to be miniaturized. However, if the refinement of the resist pattern is advanced, there arises a problem that the line width of the resist pattern is designed to be different from the line width of the formed resist pattern, that is, the CD (Critical Dimension) shift. The amount has increased.

The reason for this is that in the case of a positive resist, when the resist layer composed of the resist material is developed, the side of the unexposed portion of the resist layer is dissolved by the developer. The unexposed portion of the resist layer is less likely to be dissolved in the developer, but is not completely insoluble. Therefore, when the unexposed portion of the resist layer is dissolved from the side surface direction by the developer, the line width of the resist pattern becomes small, and the resist pattern may be defective.

Further, when the thickness of the resist pattern with respect to the line width of the resist pattern is increased by the refinement of the resist pattern (if the aspect ratio of the resist pattern becomes large), the resist pattern collapses, etc. It becomes impossible to obtain the desired resist pattern. Therefore, in order to make the resist pattern fine The thickness of the resist layer must be made thin.

In addition to the above, since the dissolution of the unexposed portion due to the developer proceeds isotropically, the dissolution of the unexposed portion proceeds not only from the side direction but also in the thickness direction of the resist pattern. That is, there is a problem in that the thickness of the unexposed portion to be left is small and the contrast of the pattern is lowered. This is because when the resist pattern is used as a mask for dry etching or the like, the resist disappears before the pattern formation of the film to be etched or the like is completed. This problem is particularly remarkable in the case of advancing the refinement of the resist pattern.

Regarding the problem of an increase in the CD offset amount and a decrease in the thickness of the unexposed portion (resist pattern), it is considered that the unexposed portion of the resist layer is more difficult to dissolve in the developer. Thereby, the pattern can be made finer, but if the unexposed portion of the resist layer becomes less soluble, the developer becomes easily repelled by the resist layer, and the developer becomes less likely to contact or penetrate the resist layer. Department (the part that should be dissolved). As a result, there is a problem in that the exposed portion such as a hole or a gap is not dissolved in the developing solution, and no hole (a hole is missing) is formed, or a portion which is a gap portion at the end portion of the wire remains in a cross-sectional T shape. T-top shape) problem. In other words, the pattern to be formed is not formed, and the resolution of the resist pattern is deteriorated.

According to the above, there is a problem that the refinement of the resist pattern and the resolution of the resist pattern cannot be simultaneously achieved.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a substrate of a resist layer capable of achieving both the refinement of a specific pattern (line, gap, hole, etc.) formed and the resolution of the pattern, and a method of manufacturing the same . Further, the substrate of the resist layer may be applied to a transfer mask substrate or a stamp substrate, and an object thereof is to provide a production method using the transfer mask or the stamp.

The inventors of the present invention have tried to solve the above problems by first controlling the solubility of the unexposed portion of the resist layer in the developer. However, it has been found that if the refinement pattern is advanced, the solubility is not controlled and the resolving of the resist pattern and the resolution of the resist pattern cannot be achieved. problem.

Therefore, the present inventors have found that in order to promote the refinement of the resist pattern, the dissolution of the unexposed portion of the resist pattern from the side direction is suppressed, and on the other hand, the resist pattern is surely advanced in order to secure the resolution of the pattern. The exposure portion is dissolved from the thickness direction, whereby the above problems can be solved, thereby completing the present invention.

Specifically, the inventors first made the dissolution rate of the unexposed portion of the resist layer in the developer very small (or increased the contact angle of water on the surface of the unexposed portion of the resist layer). Thereby, the refinement pattern can be made finer, but the dissolution of the exposed portion of the resist pattern from the thickness direction is not performed. This is because the water repellency of the unexposed portion of the resist layer is increased (the water contact angle is increased), and the developing solution is less likely to come into contact with the exposed portion.

Therefore, the inventors formed a development promoting layer on the resist layer. The development promoting layer can positively contact the developer on the surface of the exposed portion of the resist layer (improving the wettability of the surface of the resist layer to cause the developer to stay on the exposed portion and deteriorate the surface of the resist layer The developer is allowed to easily penetrate the layer of the exposed portion or the like. In other words, the development promoting layer attracts the layer of the developer.

Thereby, the dissolution of the unexposed portion of the resist pattern due to the developer from the side surface direction can be suppressed, and the developer can be surely dried in the thickness direction by spreading the developer over the exposed portion of the resist pattern.

(Composition 1)

The composition of the present invention is a substrate of a resistive layer, characterized in that it has a substrate, and a resist layer formed of the positive resist material formed on the substrate, and the thickness of the resist layer 200 nm or less, the dissolution rate of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less, and at least the exposed portion of the resist layer is formed on the resist layer so as to extend the aqueous developing solution over the resist layer. The development promoting layer of the above cause.

In the present specification, the term "substrate of a resistive layer" means a substrate or a film formed on a substrate of a resist layer by using a resist pattern formed by photolithography as a mask. Specific examples of the substrate include a mask base substrate used in the production of a transfer mask, and an imprint mold base used in an imprint mold.

In addition, the "aqueous developing solution" means a developing solution using water as a main body of the solvent, and the component of the developed solute component is not particularly limited. Specific examples of the aqueous developing solution include an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide, and an organic alkaline aqueous solution such as a hydrogenated tetramethylammonium chloride solution (TMAH aqueous solution).

The positive type resist is obtained by applying a resist composition to the surface of a substrate, and then polymerizing the polymer component contained in the composition by baking treatment.

If the polymerization state of the resist layer is raised before exposure, the solubility of the resist layer in the developer becomes low. The surface and the side surface of the unexposed portion (the line portion of the resist pattern) of such a resist layer are not easily dissolved (eroded) by the developer. On the other hand, since the polarity of the surface of the resist layer which is polymerized becomes low, the wettability of the aqueous developing solution is deteriorated, and the developing solution is not easily infiltrated into the exposed portion which should be dissolved by the developing solution, and the resist residue is generated. In the case of the phenomenon of the gap portion of the pattern. In the case where a fine pattern is formed, penetration of the developer into the exposed portion becomes worse, and thus it becomes difficult.

In this configuration, since the development promoting layer is provided on the surface of the resist layer, the aqueous developing solution initially permeates the development promoting layer, and then wets the exposed portion of the resist layer to dissolve it.

Therefore, the exposed portion of the resist layer flows out by the developer, and is hardly dissolved in the aqueous developing solution, and the unexposed portion having a small dimensional change during development is surely left. As a result, for example, even a fine pattern having a pattern size of 40 nm or less can be formed in a pattern according to design.

(constituent 2)

Further, the constitution of the present invention is a substrate of a resistive layer, characterized in that it has a substrate and is formed on the substrate and is composed of a positive resist material. In the resist layer, and the thickness of the resist layer is 200 nm or less, the contact angle of the surface of the unexposed portion of the resist layer to water is 66° or more, and the aqueous developer is formed on the resist layer. a development promoting layer which is caused by at least the exposed portion of the resist layer.

The resist layer is formed by a polymerization treatment (baking treatment) or the like in the formation of the resist layer to increase the hydrophobicity of the surface of the resist and to lower the surface energy. It may be considered that the polarity of the surface of the resist layer is lowered by the polymerization of the resin component of the resist layer or the surface activity of the resist surface is lowered. In this case, the unexposed portion is less likely to come into contact with the aqueous developing solution, and the dissolution of the unexposed portion is suppressed. On the other hand, the developer which has been repelled by the unexposed portion does not reliably contact the exposed portion, but exhibits a region where the developer does not come into contact with the exposed portion.

According to this configuration, the contact between the unexposed portion and the developer is suppressed, and the development promoting layer causes the aqueous developer to wet the surface of the exposed portion. Therefore, the phenomenon in which the resist remains in the gap portion of the pattern can be effectively suppressed.

(constitution 3)

In the above configuration 1 or 2, it is preferred that the development accelerating layer is water-soluble.

If the development-promoting layer is water-soluble, it flows out by the aqueous developing solution at the time of development, so that it is not necessary to apply a step for removing the development-promoting layer.

(construction 4)

In any one of the above-described configurations 1 to 3, it is preferable that at least the surface of the exposed portion of the resist layer is deteriorated by the development promoting layer.

If the surface of the resist layer is deteriorated by the development promoting layer, the surface of the resist layer can be more reliably wetted during development.

(Constituent 5)

In any one of the above-mentioned configurations 1 to 4, it is preferable that the substrate has a film on the surface, and the resist layer is formed on the surface of the film.

(constituent 6)

In the above configuration 5, it is preferable that the film further has a hard mask film.

(constituent 7)

In the above-described configuration 5 or 6, it is preferable that the substrate of the resistive layer is a light-transmissive substrate having a light-transmitting property for light having a wavelength of 200 nm or less, and the film has a binary type of a light-shielding film. Photomask base.

(Composition 8)

Further, it is preferable that the substrate of the resistive layer is a translucent substrate having a light transmissive property to light having a wavelength of 200 nm or less, and the thin film has a semi-transmissive light semi-transmissive to light having a wavelength of 200 nm or less. The halftone phase of the film is phase shifted from the reticle substrate.

(constituent 9)

Moreover, it is preferable that the base of the resistive layer is a low-thermal expansion substrate, and the film has a reflective mask substrate having at least a multilayer reflective film and an absorber film.

(construction 10)

In any one of the above constitutions 1 to 6, it is preferable that the substrate of the above-mentioned resisting agent layer is a substrate for an imprinting mold.

(Structure 11)

Another configuration of the present invention is a transfer photomask which is produced by using the substrate of the above-mentioned resistive layer of any one of 7 to 9 and having a specific pattern formed on the film. .

(construction 12)

Another constitution of the present invention is an embossing mold which is produced by using the base of the resisting agent layer described in the above configuration 10, and a specific pattern is formed on the film of the substrate or the surface thereof. .

(construction 13)

Another constitution of the present invention is a method of manufacturing a substrate of a resistive layer, characterized in that And having a dissolution rate adjusting step for the resist layer formed on the substrate and composed of a positive resist material, and baking the resist layer to expose the unexposed portion of the resist layer The dissolution rate in the aqueous developing solution is 0.05 nm/sec or less; and the development accelerating layer forming step is formed on the resist layer to cause the aqueous developing solution to spread over at least the exposed portion of the resist layer. a development promoting layer; and the thickness of the above resist layer is 200 nm or less.

(construction 14)

Another constitution of the present invention is a method for manufacturing a substrate of a resistive layer, characterized by having a contact angle adjusting step for a resist layer formed on a substrate and composed of a positive resist material. The resist layer is baked to have a contact angle with respect to water of the surface of the unexposed portion of the resist layer of 66° or more; and a development promoting layer forming step formed on the resist layer a development promoting layer that causes the aqueous developing solution to spread over at least the exposed portion of the resist layer; and the thickness of the resist layer is 200 nm or less.

(construction 15)

In the above configuration 13 or 14, it is preferable that the substrate has a film, and the resist layer is formed on the surface of the film.

(construction 16)

According to still another aspect of the invention, there is provided a method of producing a photomask for transfer, comprising the step of forming a specific pattern on a substrate of the resistive layer produced by any one of the above-described compositions 13 to 15. .

(Construction 17)

Another constitution of the present invention is a method for producing an imprinting mold, comprising: a base of a resisting agent layer produced by any one of the above-mentioned constitutions 13 to 15; The step of forming the specific pattern on the substrate of the bottom.

(Composition 18)

A further embodiment of the present invention is a photomask substrate having a resistive layer, comprising: a substrate; and a resist layer formed on the substrate and formed of a positive resist material, and formed The thickness of the resist layer of the convex portion of the base of the specific concave-convex pattern is 200 nm or less, and the dissolution rate of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less, and the resist layer is formed on the resist layer. The development promoting layer is a cause of causing the aqueous developing solution to spread over at least the exposed portion of the resist layer.

(Composition 19)

Further, another configuration of the present invention is a photomask substrate having a resist layer, which is characterized in that it has a substrate, and a resist layer formed of the positive resist material formed on the substrate, and The thickness of the resist layer on the convex portion of the base on which the specific concave-convex pattern is formed is 200 nm or less, and the contact angle of the surface of the unexposed portion of the resist layer to water is 66° or more, and the resist layer is formed on the resist layer. The development promoting layer is a cause of causing the aqueous developing solution to spread over at least the exposed portion of the resist layer.

(construction 20)

Still another configuration of the present invention is a transfer mask, which is manufactured by using the above-described photomask substrate constituting the resistive layer of 18 or 19, and is formed on the film on the surface of the substrate. Specific pattern.

(construction 21)

Still another configuration of the present invention is a method of manufacturing a transfer reticle, characterized in that There is a dissolution rate adjustment step for the resist layer formed on the outermost surface of the substrate on which the specific concavo-convex pattern is formed and formed of a positive resist material, by baking the above-mentioned resist layer a dissolution rate of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less; and a development accelerating layer forming step of forming the aqueous developing solution over the resist layer at least on the resist layer a development promoting layer on the exposed portion; and a step of forming a second specific concave-convex pattern on the substrate on which the specific concave-convex pattern is formed by using the resist pattern formed of the resist layer as a mask; and the convex portion of the base The thickness of the above resist layer is 200 nm or less.

(construction 22)

Further, another aspect of the present invention provides a method of manufacturing a photomask for transfer, comprising: a contact angle adjusting step for forming a surface of a substrate on which a specific concavo-convex pattern is formed and having a positive resist a resist layer formed by the agent material, wherein the resist layer is baked, the contact angle of the surface of the unexposed portion of the resist layer to water is 66° or more; and the development promoting layer forming step is performed Forming a development promoting layer on the resist layer to cause the aqueous developing solution to spread over at least the exposed portion of the resist layer; and forming a resist pattern formed by the resist layer as a mask to form a specific unevenness The substrate of the pattern forms a second specific concavo-convex pattern; and the thickness of the resist layer of the convex portion of the base is 200 nm or less.

According to the present invention, it is possible to provide a substrate of a resist layer which can achieve both the miniaturization of the formed specific pattern (line, gap, hole, etc.) and the resolution of the pattern, and a method for producing the same. Moreover, the substrate of the resistive layer can be applied to the substrate for transfer or the substrate for imprinting, and a substrate can be provided. A method of manufacturing such a transfer mask or an imprint mold is used.

1‧‧‧Substrate

2‧‧‧film

2a‧‧‧Light semi-permeable membrane

2b‧‧‧Shade film

5‧‧‧Photomask base

7‧‧‧Resist layer

7a‧‧‧Exposure Department

7b‧‧‧Unexposed Department

7p‧‧‧resist pattern

7'‧‧‧2nd resist layer

7'p‧‧‧2nd resist pattern

8‧‧‧ Metamorphic layer

9‧‧‧Development promotion layer

10‧‧‧Photomask base with resistive layer

12‧‧‧Transfer mask

13‧‧‧ Imprinting mold

20‧‧‧Three-tone mask

21‧‧‧through area

22‧‧‧Halftone area

23‧‧‧ shading area

1(a) and 1(b) are schematic cross-sectional views showing a mask base and a transfer mask of the resist layer of the embodiment.

2(a)-(d) are schematic views for explaining a method of manufacturing a mask base of the resist layer of the present embodiment.

3(a) to 3(e) are schematic views for explaining a method of manufacturing the transfer mask of the embodiment using the mask base of the resist layer of the embodiment.

Fig. 4 is a schematic cross-sectional view showing an embossing die according to a modification of the embodiment.

Fig. 5 is a graph showing the relationship between the baking temperature at the time of formation of the resist layer and the water contact angle of the resist layer and the dissolution rate of the resist layer by the developer.

6(a) through 6(e) are schematic views for explaining a method of manufacturing a Levenson-type transfer photomask according to another embodiment.

7(a) through 7(c) are schematic views (No. 1) for explaining a method of manufacturing a three-tone type transfer photomask according to another embodiment.

8(a) through 8(d) are schematic views (2) for explaining a method of manufacturing a three-tone type transfer photomask according to another embodiment.

Fig. 9 (a) is a schematic plan view of a three-tone type transfer mask in the present embodiment, and Fig. 9 (b) is a schematic cross-sectional view.

[Embodiment 1]

In the present embodiment, the present invention will be described in detail based on the embodiments shown in the drawings.

1. The mask base with the resist layer

1-1. Photomask base

1-2. Resistive layer

1-3. Development promoting layer

2. Transfer mask

3. Method for manufacturing transfer mask

3-1. Mask base preparation steps

3-2. Resist layer formation step

3-3. Dissolution speed adjustment step

3-4. Development promoting layer forming step

3-5. Exposure step and development step

4. Effect of this embodiment

5. Variations, etc.

(1. Photomask base with resistive layer)

As shown in FIG. 1(a), the mask base 10 of the resistive layer of the present embodiment has a mask base 5 on which a film 2 is formed on at least one main surface of the substrate 1, a resist layer 7, and development promotion. In the layer 9, a resist layer 7 and a development promoting layer 9 are sequentially formed on the film 2. Hereinafter, each component will be described in detail.

(1-1. Photomask base)

The mask base of the present embodiment is not particularly limited as long as the film 2 is formed on at least one main surface of the substrate 1, and a known configuration can be employed. Hereinafter, some configurations of the reticle base will be described.

(1-1-1. Binary mask base)

The binary type reticle base is one of the transmissive reticle bases, and is a base of a transfer reticle for forming a fine pattern by photolithography. In the binary mask, a light shielding film that does not substantially transmit the exposure light is formed, and the exposure light is determined to be binary.

In the binary type photomask substrate, the substrate 1 is a light transmissive substrate, and the film 2 has a light shielding film. A known substrate may be used as the light-transmitting substrate, and it is only required to have light transmittance to light having a wavelength of 200 nm or less. In the present embodiment, for example, it is made of a transparent material such as synthetic quartz glass, soda lime glass, aluminosilicate glass, borosilicate glass or alkali-free glass. Therefore, the transfer photomask obtained by the binary type photomask substrate of the present embodiment can use ArF excimer laser (wavelength: 193 nm), F ₂ excimer laser (wavelength: 157 nm), or the like as exposure light.

The light-shielding film may have a light-shielding property for light having a wavelength of 200 nm or less, and may be composed of a known composition. Specifically, it may be composed of a material containing a transition metal element such as chromium, ruthenium, rhodium, tungsten, titanium, ruthenium, molybdenum, nickel, vanadium, zirconium, ruthenium, palladium or iridium or a compound thereof. For example, chromium or a chromium compound containing one or more elements selected from the group consisting of oxygen, nitrogen, carbon, and the like may be contained, and one or more selected from the group consisting of oxygen, nitrogen, and boron may be contained in the ruthenium. The elemental bismuth compound.

Further, the light-shielding film may be composed of a material containing a transition metal and a compound of a ruthenium (including a transition metal ruthenium, in particular, molybdenum telluride). In this case, the light-shielding film contains a material containing a transition metal and a compound of ruthenium, and examples thereof include a material containing a transition metal and ruthenium and oxygen and/or nitrogen as main constituent elements. Further, the light shielding film may be made of a material mainly composed of a transition metal and oxygen, nitrogen, and/or boron. The transition metal may be applied with molybdenum, niobium, tungsten, titanium, niobium, nickel, vanadium, zirconium, hafnium, palladium, iridium, iridium, chromium, and the like.

The light shielding film may include two layers of a light shielding layer and an anti-surface reflection layer, or may include three layers of an anti-back reflection layer formed between the light shielding layer and the substrate 10 in addition to the two layers. In the case where the light-shielding film is formed of a compound of molybdenum molybdenum, a two-layer structure of a light-shielding layer (such as MoSi) and an anti-surface reflection layer (such as MoSiON), or a light-shielding layer and a substrate 1 in the two-layer structure may be exemplified. A three-layer structure having an anti-back reflection layer (MoSiON or the like) is added between them.

Further, it is also possible to form a composition gradient film in which the composition of the light-shielding film in the film thickness direction is continuously or stepwise.

The film thickness of the light-shielding film is not particularly limited, and may be determined, for example, such that the optical density (OD: Optical Density) of the exposure light is 2.5 or more.

Further, the film 2 may have a hard mask film. The hard mask film is formed on the light shielding film and functions as an etching mask. Specifically, the hard mask film is covered by etching The etchant of the light film has a material composition of etching selectivity (having etching resistance). In the present embodiment, for example, it is preferably made of a material containing chromium or chromium as a chromium compound to which an element such as oxygen, nitrogen or carbon is added. At this time, by providing the hard mask film with an antireflection function, the transfer mask can be produced in a state in which the hard mask film remains on the light shielding film.

Further, the film 2 may have an etch stop layer. The etch stop layer is formed between the substrate and the light shielding film, and is made of a material having etching selectivity with both. In the present embodiment, for example, it is preferably made of a material containing chromium or chromium as a chromium compound to which an element such as oxygen, nitrogen or carbon is added. The etch stop layer can also be selected from materials that can be stripped simultaneously with the hard mask film.

(1-1-2. Halftone phase shift mask base)

The halftone phase shift mask base is a type of transmissive reticle base, and is a basis for a phase shift mask for forming a fine pattern by photolithography.

The halftone phase shift mask is formed by a light semi-transmissive portion that transmits light that does not substantially contribute to the intensity of exposure, and a light transmissive portion that transmits light that substantially contributes to the intensity of exposure. The phase of the light transmitted through the light semi-transmissive portion is substantially reversed with respect to the phase of the light transmitted through the light transmitting portion. The light in the vicinity of the boundary portion between the light semi-transmissive portion and the light transmitting portion is rewound to the other region. However, since the light that is circulated by the diffraction phenomenon is canceled by the above configuration, the light intensity of the boundary portion can be set. It is roughly zero. As a result, the contrast of the boundary portion, that is, the resolution can be improved.

In the halftone phase shift mask substrate, the substrate 1 is a light transmissive substrate, and the film 2 has a light semi-transmissive film. Similarly to the binary type photomask base, a known substrate may be used as the light-transmitting substrate, and it is only required to have light transmissivity to light having a wavelength of 200 nm or less. In the present embodiment, for example, it is made of a transparent material such as synthetic quartz glass, soda lime glass, aluminosilicate glass, borosilicate glass or alkali-free glass. Therefore, the transfer photomask obtained by the binary type photomask substrate of the present embodiment can use ArF excimer laser (wavelength: 193 nm), F ₂ excimer laser (wavelength: 157 nm), or the like as exposure light.

The light semi-transmissive film is such that light having a wavelength of 200 nm or less is substantially ineffective for exposure. The intensity (for example, 1% to 30% of the exposure light) is transmitted and has a specific phase difference (for example, 180°), and it may be constituted by a known composition. Specifically, a material containing a compound containing a transition metal and ruthenium (including a transition metal ruthenium compound) may, for example, be a material containing the transition metal and ruthenium and oxygen and/or nitrogen as main constituent elements. The transition metal may be applied with molybdenum, niobium, tungsten, titanium, niobium, nickel, vanadium, zirconium, hafnium, palladium, iridium, iridium, chromium, and the like.

Further, the film 2 may be formed by laminating one or more light semi-transmissive films and a light-shielding film to form a multi-step mask base. In this case, the material of the light semi-transmissive film may be a metal element or alloy containing chromium, tantalum, titanium, aluminum or the like in addition to the material of the light semi-transmissive film constituting the halftone phase shift mask base described above. Or materials of their compounds.

Further, when the light semi-transmissive film has a light-shielding film, the light semi-transmissive film is made of a material containing a transition metal and tantalum, and the light-shielding film preferably has a light-shielding film. A material composition that etches selectivity (with etch resistance). Specifically, a chromium compound in which an element such as oxygen, nitrogen or carbon is added to chromium or chromium can be exemplified.

The composition ratio or film thickness of the material constituting the light semi-transmissive film is adjusted so as to have a specific transmittance with respect to the exposure light. As the material constituting the light shielding film, a material constituting the light shielding film of the above-described binary type photomask substrate can also be applied. The composition or film thickness of the material constituting the light-shielding film is adjusted so as to have a specific light-shielding property (optical density) in the laminated structure of the light-transmissive film and the light-shielding film.

Further, similarly to the binary type photomask base, the film 2 may have a hard mask film. The hard mask film is formed on a light shielding film or a light semi-transmissive film, and functions as an etching mask.

(1-1-3. Reflective reticle base)

The reflective reticle base is one of the reticle bases and is the basis of a reflective reticle for forming a fine pattern by photolithography. In the reflective mask, for example, EUV (Extreme Ultra Violet) light having a wavelength of 13.5 nm is used as the exposure light. However, since the EUV light is easily absorbed by the substance, the transmissive mask using the refractive optical system as described above cannot be used. A reflective mask using a reflective optical system is used. Specifically, in reflection type In the photomask, a reflection film that reflects EUV light and an absorber film that absorbs EUV light are formed, and these form a mask pattern.

In the reflective reticle base, in order to suppress strain of the transferred pattern due to heat during exposure, the substrate 1 is a low thermal expansion substrate, and the film 2 has at least a reflection film and an absorber film. As the material constituting the low thermal expansion substrate, it is preferably used as a low thermal expansion coefficient in the range of about 0 ± 1.0 × 10 ^-7 / ° C, more preferably about 0 ± 0.3 × 10 ^-7 / ° C. A SiO ₂ -TiO ₂ -based glass of a glass material.

In the film 2, the reflective film is a multilayer reflective film, and the absorber film is formed in a pattern on the multilayer reflective film.

The multilayer reflective film is formed by alternately laminating a high refractive index layer and a low refractive index layer. The multilayer reflective film may be a Mo/Si periodic laminated film, a Ru/Si periodic multilayer film, a Mo/Be periodic multilayer film, a Mo compound/Si compound periodic multilayer in which a Mo film and a Si film are alternately laminated for about 40 cycles. A film, a Si/Nb periodic multilayer film, a Si/Mo/Ru periodic multilayer film, a Si/Mo/Ru/Mo periodic multilayer film, a Si/Ru/Mo/Ru periodic multilayer film, or the like. The material can be appropriately selected according to the wavelength of the exposure light.

Further, the absorber film has a function of absorbing EUV light, and a material such as tantalum (Ta) element or Ta as a main component can be preferably used. The crystal state of such an absorber film is preferably amorphous or has a crystallite structure in terms of smoothness and flatness.

Further, a hard mask film as an etching mask can be formed on the absorber film. Further, a protective film which functions as an etching stopper layer when patterning the absorber film can be formed on the multilayer reflective film.

(1-2. Resist layer)

In the above various mask substrates, a resist layer 7 is formed on the film 2. The resist layer 7 is formed of a material exposed by irradiation with an energy beam or the like, and the resist pattern obtained by exposing and developing the resist layer 7 corresponds to a fine pattern formed on the photomask. In the present embodiment, in order to correspond to a fine pattern of about several tens of nanometers, a positive type chemical amplification type resist is used. To form the material of the resist layer 7.

As the chemical amplification resist, a known one can be used, and for example, those containing at least a base polymer and a photoacid generator can be exemplified.

The base polymer is not particularly limited as long as it has a solubility in a developing solution (alkaline aqueous solution or the like) as the acid is generated. The photoacid generator is not particularly limited as long as it is known.

In the embodiment, the chemical amplification resist preferably contains a basic substance. The basic substance is preferably determined in consideration of a combination with a material (acid substance, alkaline substance, and the like) constituting the development promoting layer described below.

The chemically amplified resist may contain other components such as a surfactant, a sensitizer, a light absorber, and an antioxidant in addition to the above components.

In the present embodiment, the dissolution rate (hereinafter, also referred to as Rmin) of the unexposed portion of the resist layer 7 in the aqueous developing solution is 0.05 nm/sec or less, preferably 0.03 nm/sec or less, more preferably 0.01. Below nm/second. In other words, the unexposed portion of the resist layer 7 is preferably very insoluble in the developer. Thereby, dissolution of the unexposed portion of the resist layer 7 from the side surface direction and the thickness direction can be suppressed, and the narrowing and thinning of the resist pattern and the film reduction can be prevented. As a result, a fine pattern to be formed in the photomask is formed in accordance with the resist pattern, and the resolution is also ensured.

In the present specification, Rmin (unit: nm/sec) is defined as the dissolution rate of the unexposed portion in a 2.38% concentration of TMAH (tetramethylammonium hydroxide) at room temperature (23 ° C). Further, in the above regulation, TMAH is only used as an aqueous developing solution for specifying Rmin, and in the present invention, it is not intended to limit the aqueous developing solution to TMAH.

Further, in the present embodiment, the contact angle of water on the surface of the unexposed portion of the resist layer 7 is 66 or more, preferably 68 or more, and more preferably 70 or more. A large contact angle of water means that the water becomes less likely to come into contact with the unexposed portion of the resist layer 7 (for example, the wettability of water on the surface of the unexposed portion becomes small). Therefore, the aqueous developing solution also becomes less likely to come into contact with the unexposed portion, so that the dissolution of the unexposed portion is suppressed.

That is, in order to suppress the dissolution of the unexposed portion of the resist layer 7, the solubility of the resist layer 7 itself can be lowered by specifying the upper limit of Rmin, and the lower limit of the contact angle of water can be specified. The developer becomes less likely to come into contact with the resist layer 7.

The thickness of the resist layer 7 is preferably thin, and in the present embodiment, it is 200 nm or less, preferably 100 nm or less, more preferably 80 nm or less, still more preferably 50 nm or less. The reason for this is that the aspect ratio at the time of forming the resist pattern is reduced so as not to cause collapse of the resist pattern or the like. Specifically, the aspect ratio is preferably 2.5 or less, and particularly preferably less than 2. In the present embodiment, since the resist layer 7 has the above properties, even when the thickness of the resist layer 7 is within the above range, the film thickness of the resist pattern can be minimized, and sufficient. Ensure the contrast of the fine pattern that should be formed.

(1-3. Development promoting layer)

In the present embodiment, the development promoting layer 9 is formed on the resist layer 7. The development promoting layer 9 is a layer that causes the aqueous developing solution to spread over at least the exposed portion of the resist layer 7. Specifically, it is possible to maintain a state in which the solubility of the unexposed portion in the aqueous developing solution is extremely small, and the aqueous developing solution can sufficiently contact the exposed portion to reliably dissolve the exposed portion. In other words, a layer for attracting the developer is formed on the exposed portion where the developer usually does not easily reach. In the present embodiment, the layer for attracting the developer is formed by the two methods shown below, but the formation of the layer is not limited thereto. Also, the two methods can be combined.

The first method is a method of forming the water-soluble development promoting layer 9, and the second method is a method of deteriorating the surface layer portion of the resist layer 7 by the presence of the development promoting layer 9.

(1-3-1. Water-soluble development promoting layer)

Since the unexposed portion of the resist layer 7 has a very small solubility in the developer as described above and is hydrophobic, it tends to repel the developer, and even repels the development of the exposed portion to be present in the vicinity of the unexposed portion. liquid. As a result, there is a case where the developer does not easily come into contact with the exposed portion. However, it is necessary for the unexposed portion to easily repel the developer itself to suppress the narrowing and thinning of the pattern or the film reduction.

Therefore, in order to make the developing solution reliably contact the exposed portion, the development promoting layer 9 is formed into a water-soluble layer. Thereby, at the time of development, the aqueous developing solution first comes into contact with and penetrates the development promoting layer 9 to dissolve the development promoting layer 9. Since the development-promoting layer 9 is formed on the resist layer 7, the developer is likely to remain on the resist layer 7 after the entire development-promoting layer 9 is dissolved, and as a result, it is easy to easily contact the exposed portion. In other words, when the development-promoting layer 9 is not present, the developer is repelled due to the hydrophobicity of the unexposed portion, and it is difficult to reach the exposed portion. In contrast, the development-promoting layer 9 is provided to be water-soluble. The developer can be spread throughout the exposed portion via the dissolution of the development promoting layer 9. Therefore, the exposed portion is surely dissolved, and a specific resist pattern can be formed with good resolution without causing a defect in the resist pattern.

In the present embodiment, the material constituting the development promoting layer 9 is made of polyvinyl alcohol, polyvinylpyrrolidone, polyaniline or the like, whereby the development-promoting layer 9 can be made water-soluble.

(1-3-2. Deterioration of the surface of the resist layer by the development promoting layer)

The surface of the resist layer 7 can be deteriorated by the presence of the development promoting layer 9. Specifically, the development promoting layer 9 can be formed such that only the surface portion of the resist layer 7 is easily contacted and penetrates into the developer.

In the present embodiment, in order to form such a development promoting layer 9, a material containing an acidic substance and an alkaline substance is used as a material constituting the development promoting layer 9. Inside the development-promoting layer 9 containing the material, a salt is formed by reacting an acidic substance with a basic substance. The salt is allowed to permeate (transfer) to the surface portion of the resist layer 7. As a result, the component transferred from the development promoting layer 9 and the component originally contained in the resist layer 7 coexist in the surface layer portion of the salt-removing resist layer 7. Therefore, the surface layer portion of the resist layer 7 is deteriorated by the transfer component of the self-development promoting layer 9, and a new layer (deterioration) is formed between the development promoting layer 9 and the resist layer 7 as a layer different from the resist layer 7. Layer 8). That is, the altered layer 8 is a layer of a portion of the resist layer 7 before the development promoting layer 9 is formed on the resist layer 7.

The altered layer 8 is removed to some extent when the development promoting layer 9 is removed during development. The reason for this is that the altered layer 8 is composed of the component of the development promoting layer 9 and the resist layer 7. The coexistence is in a state of suspected exposure, and the solubility in the developer is improved to remove the altered layer 8.

The removal of the altered layer 8 means that the surface layer portion of the resist layer 7 is removed, so that the surface state of the resist layer 7 after the modified layer is removed changes (for example, the surface becomes rough), and the developer becomes easily contacted with the resist. The surface of the agent layer 7 (the wettability of the developer on the surface of the resist layer 7 is improved). As a result, the exposed portion can be reliably dissolved. In other words, by the formation and removal of the altered layer 8, the state in which the developer on the surface of the resist layer 7 does not easily reach the exposed portion is improved, so that the developer can be spread over the exposed portion. Further, the unexposed unexposed portion is maintained in a state where the dissolution rate in the developer is extremely high or the contact angle of water is large, so that it is hardly dissolved.

Further, even when a substance (for example, a surfactant) which prevents the developer from coming into contact with the exposed portion is present in the surface layer portion of the resist layer 7 due to the influence of the surface tension, the surface layer portion is changed to the deteriorated layer 8 When removed, the substance is also removed, so that the developer becomes easily contacted with the exposed portion of the resist layer 7.

Further, from the viewpoint of realizing the film formation of the resist layer 7 or ensuring the contrast of the resist pattern, it is necessary to suppress the film reduction of the resist pattern. Therefore, in the present embodiment, the thickness of the altered layer 8 is preferably 0.1 nm or more and 20 nm or less, and more preferably 10 nm or less. The thickness of the resist layer 7 is preferably 10% or less, more preferably 5% or less. By setting the thickness within the above range, the film due to the removal of the surface layer portion (deterioration layer 8) of the resist layer 7 can be minimized.

The method of calculating the thickness of the altered layer 8 can be determined by using a known composition analysis method (XPS (X-ray photoelectron spectroscopy) or the like) to determine the thickness of the altered layer 8, and can also be used. It is obtained by the "film reduction method" shown below.

The film-reduction method is a film-reducing amount (reduction amount of the resist layer 7 in the thickness direction) when the resist layer 7 is not developed in the case where the altered layer 8 is not provided, and a resisting agent in the case where the deteriorated layer 8 is provided. The difference in the amount of film reduction at the time of development of the layer 7 is determined as the thickness of the altered layer 8. As mentioned above, Since the salt of the development promoting layer 9 enters into the altered layer 8, the exposed portion and the unexposed portion are more easily dissolved in the developer. Therefore, the difference between the amount of film reduction in the case where the deteriorated layer 8 is provided and the case where the altered layer 8 is not provided corresponds to the amount of film reduction caused by removing the altered layer 8. That is, the difference between the amount of film reduction can be set to the thickness of the altered layer 8.

When the modified layer 8 is formed by the existence of the development promoting layer 9, it is preferable to make the combination of the resist layer 7 and the development promoting layer 9 appropriate. The present inventors are investigating the composition of the resist layer 7 and the development promoting layer 9 which the present inventors have grasped.

First, the resist layer 7 is preferably in a state containing a basic substance, and the volume of the alkaline substance of the development promoting layer 9 is larger than that of the resist layer 7. In addition, the "large volume" in the present specification means a state in which the structural unit at the end of the molecule is stereoscopically expanded by a strong substituent or the like to hinder the arrangement with other molecules or the rotational motion in the molecule. In addition, the "large volume" in the present specification specifically refers to a Van Der Waals volume of a substituent on the α carbon, and is not specified by a single molecular weight, and is, for example, a tertiary butyl group. The branch structure will increase the indicator.

As described above, the salt-based acidic substance which enters the self-development promoting layer 9 reacts with the basic substance to generate it. Therefore, the salt contains an alkaline substance. Therefore, if the volume of the alkaline substance of the development promoting layer 9 is larger than the alkaline substance of the resist layer 7, the salt containing the basic substance of the development promoting layer 9 can be prevented from entering the entirety of the resist layer 7.

When the entire resist layer 7 is the altered layer 8, the dissolution rate of the resist layer 7 in the developer, particularly the dissolution rate of the unexposed portion, is increased, and is out of the range of Rmin. As a result, at the time of development, the film of the resist pattern is reduced in size, and dissolution from the side direction is also performed, and the refinement and resolution of the resist pattern cannot be achieved. Therefore, it is preferable to provide a large volume of the alkaline substance as described above. Further, according to the above-described regulation of the large volume, it is possible to prevent the alkaline substance which is free from the development promoting layer 9 from entering the resist layer 7 at random without forming a salt.

Further, the large volume of the alkaline substance may be investigated by a known method, and for example, mass spectrometry such as secondary ion mass spectrometry (SIMS) or time-of-flight secondary ion mass spectrometry (TOF-SIMS) may be used. Method, or X-ray photoelectron spectroscopy (XPS).

Further, the resist layer 7 is preferably in a state containing a basic substance, and the molecules of the alkaline substance of the development promoting layer 9 are larger than the alkaline substance of the resist layer 7. The reason for this is that the same effects as those of the above-described large volume are exerted.

Furthermore, the term "larger molecule" as used herein refers to the size of the "molecular size" as described in the text. The size of the molecule can be specified using the well-known methods described above. Moreover, as an example of the simple method, the molecular weight of the basic substance is compared, and the substance with a large molecular weight can be regarded as "large molecule."

When a preferred example is exemplified, it is preferred that the basic substance of the resist layer 7 is a lower amine, and the basic substance of the development promoting layer 9 is a higher amine than the basic substance. In addition, when the total number of the substituents of the amine which is the basic substance of the development promoting layer 9 is larger than the amine which is the basic substance of the resist layer 7, it can be said that "the molecule is large".

Further, the acidic substance of the development promoting layer 9 is preferably an aromatic compound, and more preferably polyaniline. Further, the basic substance of the development promoting layer 9 is preferably an amine, and specifically, a tetraalkylammonium salt of a hydrogenated tetraalkylammonium group is preferable. Further, it is preferable that the development-promoting layer 9 contains polyaniline as an acidic substance and contains a quaternary ammonium salt as a basic substance. In this case, the development-promoting layer 9 is composed of a polyaniline-based resin as a main component. By this, since the development-promoting layer 9 is composed of a water-soluble polymer, the effect obtained when the development-promoting layer 9 is water-soluble as described in (1-3-1) can be obtained. In addition, the principal component here means the component which exists in the composition ratio more than 50 %.

(2. Transfer mask)

By using the mask substrate 10 of the resistive layer shown in FIG. 1(a), it is possible to achieve both the refinement of the specific resist pattern (line and gap, gap, hole, etc.) formed and the resist pattern. Resolution. And, the film 2 is etched by using the resist pattern as a mask, as shown in FIG. 1(b) The transfer photomask 12 of the present embodiment in which the fine pattern corresponding to the resist pattern is formed on the film 2 on the substrate 1 is shown.

(3. Method of manufacturing transfer mask)

Next, a method of manufacturing a transfer reticle will be described in detail. The above-described transfer mask is manufactured by first manufacturing a mask base of the above-mentioned resist layer, based on the mask base. Fig. 2 is an explanatory view showing a manufacturing procedure of a method of manufacturing a mask base of the resist layer of the embodiment.

(3-1. Mask base preparation steps)

First, the mask substrate 5 on which the film 2 is formed on the substrate 1 is prepared. The mask base is not particularly limited, and for example, the above various mask bases can be exemplified. In the present embodiment, as shown in Fig. 2(a), a mask base 5 on which a film 2 is formed on a substrate 1 containing synthetic quartz glass is prepared. As a method for forming the thin film 2 on the substrate 1, a known technique such as a sputtering method may be employed. Further, the composition of the film 2, the film formation conditions, and the like may be set to a known composition and conditions.

(3-2. Resist layer formation step)

Then, as shown in FIG. 2(b), a resist layer 7 composed of a positive-type chemically amplified resist material is formed on the film 2 of the mask substrate 5. Specifically, a resist liquid containing a component of a chemically amplified resist material is applied onto the film 2 by a known technique such as a spin coating method to form the resist layer 7. The solvent to be used in the preparation of the resist liquid is not particularly limited, and a known solvent can be used.

(3-3. Dissolution speed adjustment step)

Then, the resist layer 7 formed on the film 2 is adjusted to the dissolution rate (Rmin) in the developer. The dissolution rate of the resist layer 7 is mainly changed by the temperature (baking temperature) at the time of baking treatment, and when the baking temperature is high, the dissolution rate tends to decrease. An example of changing the Rmin value with a specific baking temperature is shown in FIG. Fig. 5 shows a chemically amplified resist (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.) which is a positive resist and is used for electron beam drawing on a glass substrate at a constant temperature of 120 ° C to 160 ° C The change in Rmin in the case of a 10-minute baking treatment. Furthermore, Rmin can also be adjusted by extending the baking time.

Further, the composition change of the chemically amplified resist material constituting the resist layer 7 can be adjusted by Rmin. In the present embodiment, the dissolution rate is adjusted by baking the resist layer 7. Therefore, the baking temperature may be controlled so that the dissolution rate in the developer becomes 0.05 nm/sec or less depending on the chemically amplified resist material to be used. Further, in the exposure step described below, the exposed resist layer 7 (exposure portion) is easily dissolved in the developer, and the dissolution rate of the unexposed resist layer 7 (unexposed portion) in the developer is maintained. The rate of dissolution adjusted in this step.

Further, by baking the resist layer 7, the contact angle of water on the surface of the unexposed portion also rises. The contact angle of water mainly changes by the temperature (baking temperature) at the time of baking treatment, and if the baking temperature becomes high, the contact angle tends to become large. The relationship of the water contact angle with respect to the baking temperature is shown in FIG. The baking conditions of the resist layer 7 in the graph of Fig. 5 are the same as described above. As shown in FIG. 5, when the baking temperature is raised, the water contact angle becomes large. When the resist layer 7 having a large water contact angle is formed, the aqueous developing solution is less likely to come into contact with the unexposed portion, so that the unexposed portion is less likely to be dissolved in the aqueous developing solution. When the water contact angle of the resist layer of the unexposed portion is 66° or more, preferably 68° or more, and more preferably 70° or more, the contact between the unexposed portion and the resist developing solution is suppressed.

Further, depending on the composition of the chemically amplified resist material constituting the resist layer 7, the contact angle of water on the surface of the unexposed portion is also different. Therefore, it is only necessary to control the baking temperature so that the contact angle of water becomes 66 or more depending on the chemically amplified resist material to be used.

(3-4. Development promoting layer forming step)

After the dissolution rate adjusting step, as shown in FIG. 2(c), the development promoting layer 9 is formed so as to cover the resist layer 7. Specifically, a coating liquid containing a component of the constituent material of the development promoting layer 9 may be applied onto the resist layer 7 to form the development promoting layer 9 by a known technique such as a spin coating method. After the development promoting layer 9 is formed, a baking treatment is performed. Development promoting layer 9 When the surface of the resist layer 7 is deteriorated, as shown in FIG. 2(d), the salt contained in the development promoting layer 9 is transferred to the baking treatment of the development promoting layer 9 or after the treatment. The resist layer 7 forms the above-described altered layer 8. The details are explained below.

The salt contained in the development-promoting layer 9 is formed by reacting an acidic substance existing inside the development-promoting layer 9 with a basic substance. In a specific example of the coating liquid containing the constituent material of the development-promoting layer 9, when the acidic substance is polyaniline and the basic substance is an amine, it is preferable to set 90% by mass or more of the coating liquid. water. Thereby, the salt is not excessively present in the development promoting layer 9, and the altered layer 8 having an appropriate thickness can be easily formed. In addition, even if the alkaline layer is contained in both of the resist layer 7 and the development promoting layer 9, 90% by mass or more of the coating liquid is used as water, and the resist layer 7 containing the chemically amplified resist is used. The concentration of the basic substance contained in the development promoting layer 9 formed by using the coating liquid can be made thinner than the alkaline substance contained. Further, by utilizing the concentration difference, the alkaline substance in the development promoting layer 9 can be prevented from penetrating the deteriorated layer 8 and the resist layer 7 therebelow.

Further, the mechanism for forming the altered layer 8 can be considered, for example, as follows.

When the basic substance contained in the resist layer 7 and the basic substance contained in the development promoting layer 9 are the same kind of compound (for example, both are amines), the two basic substances are easily mixed. However, when the concentration of the coating liquid containing the constituent material of the development promoting layer 9 is thinned as described above, the alkaline substance contained in the development promoting layer 9 does not penetrate to a certain depth or more due to the difference in concentration. That is, it becomes difficult to exceed the surface layer portion of the resist layer 7 to penetrate the resist layer 7 thereunder. As a result, a portion where the two basic substances are aggregated is formed between the resist layer 7 and the development promoting layer 9. Among them, the resist layer 7 absorbs the salt of the development promoting layer 9 (i.e., the salt of the amine bonded to the polyaniline). As a result, the surface layer portion of the resist layer 7 is changed to the altered layer 8.

The mask base 10 of the resistive layer of the present embodiment is produced as shown in Fig. 2(d) by the above steps and other processing such as washing.

(3-5. Exposure step and development step)

Next, as shown in FIG. 3, the resist substrate is used to form the resist layer, and the resist is used. The layer is patterned to thereby produce a transfer reticle. First, as shown in FIG. 3(a), the mask base 10 of the resist layer is formed on the resist layer 7 by using an electron beam plotter or the like to form a pattern to be formed on the transfer mask. The pattern is exposed in a way. After the exposure, the exposed resist layer 7 (exposure portion 7a) and the unexposed resist layer 7 (unexposed portion 7b) are formed.

Then, the mask substrate 10 of the exposed resist layer is developed using an aqueous developing solution (refer to FIG. 3(b)). The aqueous developing solution refers to a developing solution using water as a main body of the solvent. In the present embodiment, the aqueous developing solution is not particularly limited as long as it can dissolve the exposed portion 7a of the resist layer, and examples thereof include a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and TMAH (tetramethylammonium hydroxide). An alkaline aqueous solution.

At the time of development, the development promoting layer is first dissolved, and at least a part of the altered layer is also dissolved and removed. As a result, the developer contacts the resist layer 7 located directly below the altered layer. Further, as shown in FIG. 3(c), the exposed resist layer (exposure portion 7a) is dissolved and removed by the developer to form a resist pattern 7p. In this case, since the mask base 10 of the resist layer has the above configuration, the exposed portion 7a is reliably dissolved and removed, and the dissolution rate of the unexposed portion 7b is maintained to be extremely small. It hardly dissolves from the thickness direction without causing narrowing or thinning of the resist pattern 7p or film reduction.

Therefore, the film 2 is etched using the formed resist pattern 7p as a mask, whereby a transfer mask formed in a pattern according to design can be obtained (see FIGS. 3(d) and (e)).

(4. Effect of this embodiment)

In the present embodiment, in order to prevent the narrowing and thinning of the resist pattern when the fine resist pattern is formed, the unexposed portion of the resist layer is prevented from being easily dissolved in the developer, and the attractant layer is formed on the resist layer. The development promoting layer of the developer causes the developer to easily contact or penetrate the exposed portion. Thereby, the dissolution of the unexposed portion from the side surface direction and the thickness direction can be suppressed as much as possible, and the developer can surely contact the exposed portion, so that only the exposed portion can be reliably dissolved without substantially dissolving the unexposed portion.

Therefore, even if the formed resist pattern becomes fine, the resist pattern can be prevented from being changed. Since the narrowness is narrowed and the film is reduced, the defect of the resist pattern can be reduced, and the lack of a pattern due to the inability of the developer to contact the exposed portion can be prevented. In other words, it is possible to achieve both the miniaturization of the pattern and the resolution. Therefore, the contrast of the resist pattern can be ensured, and the thinning of the resist layer which is indispensable for miniaturization of the resist pattern can be easily achieved.

In order to achieve a state in which the unexposed portion of the resist layer is not easily dissolved in the developer, it is first considered that the unexposed portion of the resist layer itself is less likely to be dissolved in the developer. In this case, the dissolution rate (Rmin) of the unexposed portion in the developer is set to 0.05 nm/sec or less. As another method, it is considered that the developer is not easily contacted with the unexposed portion. In this case, since the developer is aqueous, the contact angle of water on the surface of the unexposed portion is set to 66° or more.

Further, in order to use the development promoting layer as a layer for attracting the developer, the development promoting layer is made water-soluble. Thereby, the aqueous developing solution easily comes into contact with the development promoting layer formed on the resist layer, and after the development promoting layer is dissolved, the remaining developing solution easily stays on the resist layer. As a result, the developer easily reaches the exposed portion of the resist layer, and the exposed portion can be surely dissolved to prevent the defect pattern from being deficient.

Further, the surface of the resist layer is deteriorated by the presence of the development promoting layer. Specifically, the salt generated in the reaction between the acidic substance and the basic substance contained in the material constituting the development promoting layer is transferred to the resist layer, and a surface layer of the resist layer is formed between the development promoting layer and the resist layer. The partially (unexposed portion and exposed portion) is deteriorated to form an altered layer. Since the altered layer is different from the resist layer and is easily contacted and dissolved in the developer, the developer sufficiently contacts the exposed portion of the resist layer present directly under the altered layer. As a result, the exposed portion is reliably dissolved to prevent the defect pattern from being deficient. Further, since the unexposed portion of the resist layer is deteriorated and becomes a part of the altered layer, it is easily dissolved by the developer, and since the Rmin is in the above range with respect to the unexposed portion, the unimproved portion is not easily maintained by the above. Since the developer is dissolved, the film of the resist pattern can be reduced to about the thickness of the substantially deteriorated layer. Therefore, there is no decrease in the contrast of the pattern due to the film reduction of the resist layer.

In the present embodiment, the Rmin of the unexposed portion of the resist layer is set as the above-mentioned standard. In the surrounding method, the resist layer is baked. The reason for this is that by raising the temperature at the time of the baking treatment, there is a tendency that the resist layer is baked and Rmin is lowered. In addition, the contact angle of water on the surface of the unexposed portion tends to increase as the baking treatment is performed. Therefore, when the contact angle is 66° or more, the baking treatment may be performed.

Further, in the mask base of the resist layer of the present embodiment, the composition of the resist layer and the development promoting layer can achieve both the refinement of the resist pattern and the resolution, and therefore the configuration of the mask base is not limited. Therefore, the configuration of the reticle base can be variously configured. For example, the reticle substrate may be a binary reticle substrate, a halftone phase shift reticle substrate, or a reflective reticle substrate.

(5. Variations)

In the above embodiment, the mask base of the resist layer and the transfer mask manufactured by the mask base are described. However, as long as the resist layer and the development promoting layer are provided, the resist is used. The layer and the development promoting layer may also be formed on other substrates. For example, the above-mentioned resist layer and development promoting layer may be formed on the imprint mold substrate.

The imprint mold substrate is, for example, a basis for an imprint mold for forming a fine pattern by a nanoimprint lithography method. The embossing mold contacts the transfer target (for example, a photocurable resin or a thermosetting resin), and transfers the fine pattern formed on the mold to the transfer target one-to-one.

In the stamping die, the substrate is made of a transparent material, and the film 2 has a hard mask film. As the transparent material, for example, quartz, sapphire or the like can be exemplified. Further, examples of the hard mask film include chromium or a compound containing chromium.

Further, by etching the film 2 and the substrate 1 with a resist pattern as a mask, as shown in FIG. 4, an imprint mold 13 having a fine pattern formed on the surface 1a of the substrate 1 is obtained.

(Coordination of constituent materials of the resist layer and constituent materials of the development promoting layer)

In the above embodiment, the resist layer has a basic substance, and the degree of entry of the salt in the development promoting layer is defined in accordance with the large volume or size of the basic substance in the development promoting layer. Of course However, as an example, there is a possibility that the entry of the salt is determined by other substances without depending on the alkaline substance. In addition, when an altered layer can be formed, a compound other than the above compound can be used as the acidic substance and the basic substance contained in the development promoting layer.

The basic substance which is a development-promoting layer is an amine-based compound which is soluble in water and has a relatively large volume. The number of carbon atoms contained in the molecule of the amine compound is preferably from 1 to 30. Specifically, it can be exemplified: , Porphyrin, amylamine, dipropylamine, ethylenediamine, 2-heptylamine, 2-aminopyridine, 2-aminoethanol, cyclohexylamine, diisopropylamine, 4-dimethylamino Pyridine, 2-dimethylaminoethanol, N,N-diethylethylenediamine, N-isopropylethylenediamine, 3-dimethylaminopropionitrile, N,N-dimethylcyclohexyl Amine, N,N-dimethyl-n-dodecylamine, (S)-(+)-2-amino-1-butanol, N,N-dimethyl-1,3-propanediamine, 2-Amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, N,N,N',N'-tetramethylethylenediamine, N , N, N', N'-tetramethyl-1,3-propanediamine and the like.

Further, in the case where the basic substance is a quaternary amine, ammonium hydride is preferred. For example, an ammonium hydroxide compound represented by the following formula (1) is preferred. In the formula (1), examples of R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group having 1 to 7 carbon atoms, an alcohol group, and an aryl group. Specifically, tetramethylammonium hydride, ethyltrimethylammonium hydride, tetraethylammonium hydride, triethylbutylammonium hydride, tributylethylammonium hydride, tetra-n-butylammonium hydride, Four second butyl ammonium hydride, tetra-tert-butyl ammonium hydride, and the like.

Moreover, as the acidic substance of the development-promoting layer, an organic acid having an acidic group such as a carboxyl group or a sulfo group is preferable, and both aromatic and aliphatic may be used. As an acidic substance having a carboxyl group, Examples thereof include saturated fatty acids, unsaturated fatty acids, and aromatic fatty acids. Further, examples of the organic acid having a sulfonic group include benzenesulfonic acid, alkylbenzenesulfonic acid, aminobenzenesulfonic acid, and alkyl-substituted aminobenzenesulfonic acid.

[Embodiment 2]

In the above embodiment, the case of the binary type photomask base (and the halftone type phase shift mask base or the reflective type mask base) is exemplified. On the other hand, the reticle substrate of the present invention can be applied to the formation of other types of transfer reticle. For example, the Levenson-type transfer photomask 12 can be formed by forming a phase shifting portion by forming a phase shifting portion by forming a phase shifting portion by etching the film 1 or the thin film 2 formed on the substrate 1 by etching or the like. Or a three-tone type transfer photomask 12.

In the case of producing the Levenson-type transfer photomask 12 or the three-tone type transfer photomask 12, and the case of producing the transfer photomask 12 of the binary type or the like described in the above embodiment, Both of them can be produced from the mask base 5 shown in the above embodiment. However, as shown in FIG. 6 below, for example, when the Levenson-type transfer mask 12 is produced, the mask base 5 shown in the above embodiment is recessed to form a (first) specific uneven pattern. Further, a resist layer (second resist layer 7') is formed on the mask substrate 5. The features described in detail in the above embodiments can also be applied at the time of forming the second resist layer 7'. The following is explained.

A method of manufacturing the Levenson-type transfer photomask 12 will be described. Hereinafter, the case where it is not particularly described is the same as that of the above embodiment.

The mask substrate 5 shown in the above embodiment is prepared, and the mask substrate 5 is processed until the stage of Fig. 3(e). In this case, of course, the water-soluble development promoting layer 9 (and hence the modified layer 8) is previously provided on the resist layer 7.

Thereafter, as shown in FIG. 6(a), the light-transmitting substrate is etched using the film 2 as a mask.

Further, in this example, as shown in FIG. 6(b), the second resist layer 7' is formed on the light-transmitting substrate in the state in which the film 2 is present. In addition, the material, formation conditions, and the like of the second resist layer 7' may be the same as those of the above embodiment. Moreover, in this case, the water-soluble development promoting layer 9 can also be The altered layer 8) is previously disposed on the second resist layer 7'. Further, in FIG. 6(b), the reason why the concave portion is formed on the outermost surface of the water-soluble development-promoting layer 9 is to roughly show that the influence of the depression of the light-transmitting substrate affects the shape of the outermost surface more or less. .

Next, as shown in FIG. 6(c), the second resist layer 7' is exposed and developed. As a result, the second resist pattern 7'p is formed.

Further, in this state, as shown in FIG. 6(d), the film 2 is removed by using the second resist pattern 7'p as a mask. The second specific uneven pattern is formed in this manner.

Finally, as shown in FIG. 6(e), the second resist pattern 7'p is removed to complete the Levenson-type transfer mask.

Next, a method of manufacturing a three-tone type transfer mask will be described.

The reticle base shown in the above embodiment was prepared. The film 2 in the mask base of the present example includes a light semi-transmissive film 2a (for example, MoSiON) and a light shielding film 2b (for example, CrON or TaN) from the light-transmitting substrate side as shown in FIG. 7(a). . In this case, of course, the water-soluble development promoting layer 9 (and hence the altered layer 8) is previously provided on the resist layer 7.

As shown in Fig. 7 (b) and (c), the mask substrate 7 is etched by using the resist pattern 7p as a mask to remove the resist pattern 7p.

Thereafter, as shown in FIG. 7(d), the light shielding film 2b is etched. In this manner, the (first) specific concave-convex pattern is formed in advance.

Further, in this example, as shown in FIG. 8(a), the second resist layer 7' is formed on the light-transmitting substrate in a state in which the light semi-transmissive film 2a is formed. In addition, the material, formation conditions, and the like of the second resist layer 7' may be the same as those of the above embodiment. Moreover, in this case, the water-soluble development promoting layer 9 (and further the modified layer 8) is also provided in advance on the second resist layer 7'. Further, the reason why the concave portion is formed on the outermost surface of the water-soluble development-promoting layer 9 in Fig. 8(a) is that the effect of the depression of the light-transmitting substrate is more or less reflected to the shape of the outermost surface. .

Next, as shown in FIG. 8(b), the second resist layer 7' is exposed and developed. As a result, the second resist pattern 7'p is formed.

In this state, as shown in FIG. 8(c), the light-transmissive film 2a is removed by using the second resist pattern 7'p as a mask to expose the substrate 1.

Thereafter, as shown in FIG. 8(d), the second resist pattern 7'p is removed. The second specific uneven pattern is formed in this manner, and the three-tone transfer mask is completed.

As described above, the base of the resistive layer in the middle of the production of the resistive layer in the middle of the production of the Levenson type transfer mask (Fig. 6(b)) or the three-tone type transfer mask (Fig. 8 (a)), the water-soluble development promoting layer 9 (and hence the modified layer 8) is formed on the second resist layer 7' in the same manner as in the above embodiment. Therefore, the technical idea of the present invention can also be applied to the present embodiment.

The configuration of this embodiment is summarized as follows.

A substrate for a resistive layer characterized by having a substrate and a resist layer formed on the substrate and composed of a positive resist material. The thickness of the above-mentioned resist layer of "the convex portion of the base having the specific concave-convex pattern formed is 200 nm or less, The dissolution rate of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less. a development promoting layer that causes the aqueous developing solution to spread over at least the exposed portion of the resist layer on the resist layer.

The above regulations are focused on the second resist layer 7' described above. Specifically, when the second resist layer 7' is formed, for example, in the case of the base of the resistive layer in the middle of the production of the Levenson-type transfer mask 12, as shown in FIG. 6(c), The thickness of the second resist layer 7' is measured in the recessed portion (concave portion) of the light-transmitting substrate to have an appropriate thickness. In the case of the three-tone type, it is also the same as shown in Fig. 8(b).

However, in the above embodiment, the reason why the thickness of the resist layer 7 is set to 200 nm or less is to reduce the aspect ratio in forming the resist pattern so as not to cause collapse of the resist pattern or the like. Looking at FIG. 6(c) or FIG. 8(b), it can be seen that the recessed portion of the light transmissive substrate such as the Levenson type, or In the second resist layer 7' formed by the recessed portion of the semi-transmissive film of the three-tone type, there is almost no fear of collapse of the resist pattern. It can be said that the collapse of the resist pattern or the like depends on the thickness of the second resist layer 7' on the outermost surface of the convex portion of the substrate on which the substrate or film of the specific pattern is formed. Therefore, in the above specification, the thickness of the resist layer of the "protruding portion of the base" is set to 200 nm or less. Thereby, it is naturally possible to obtain the same effects as those of the above embodiment in the present embodiment. Therefore, even without the above-mentioned additional explanation, it is possible to singularly grasp that the thickness of the so-called resist layer means the thickness of the resist layer which is the farthest from the lower surface of the substrate and the uppermost surface of the substrate.

The embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit and scope of the invention. For example, the contents of [Embodiment 1] and the contents of [Embodiment 2] can be combined as appropriate, and various changes can be made in various combinations.

[Examples]

Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to the examples.

(Example 1) (Photomask substrate preparation step)

In the present embodiment, a light semi-transmissive film and a light-shielding film are sequentially formed on the substrate as a phase shift mask base.

First, a single-layer MoSiN film having a film thickness of 69 nm was formed as a light semi-transmissive film on a substrate containing transmissive quartz glass and having a light transmissive property using a monolithic DC sputtering apparatus. The conditions at this time are as follows.

Sputtering target, molybdenum (Mo) and silicon (Si) of the mixed target (atomic% ratio of Mo: Si = 10: 90) , argon (Ar), nitrogen (N _2), and helium (He) of a mixed gas (At a gas pressure of 0.3 Pa and a gas flow rate ratio of Ar:N ₂ :He=5:49:46), the power of the DC power source was set to 2.8 kW, and reactive sputtering (DC sputtering) was performed. After the sputtering, heat treatment (annealing treatment) was performed at 250 ° C for 5 minutes.

Further, the light semi-transmissive film is also a phase shift film for an ArF excimer laser (wavelength 193 nm). Further, in the phase shift film, the ArF excimer laser (wavelength: 193 nm) had a transmittance of 5.24% and a phase difference of 173.85 degrees.

Thereafter, a light-shielding film was formed on the semi-transmissive film using a monolithic DC sputtering apparatus. The light-shielding film is a three-layer structure as follows.

First, as the first light-shielding film, a CrOCN layer having a film thickness of 30 nm was formed. The conditions at this time are as follows.

The sputtering target uses a chromium target in a mixed gas atmosphere of argon, carbon dioxide, nitrogen, and helium (pressure: 0.2 Pa, gas flow ratio: Ar:CO ₂ :N ₂ :He=22:39:6:33), DC The power of the power source was set to 1.7 kW, and reactive sputtering was performed.

Next, as the second light-shielding film, a CrN layer having a film thickness of 4 nm was formed. The conditions at this time are as follows.

In the mixed gas atmosphere of argon and nitrogen (pressure: 0.1 Pa, gas flow ratio: Ar: N ₂ = 83: 17), a chromium target was used, and the power of the DC power source was set to 1.7 kW to carry out reactive sputtering.

Finally, as a third light-shielding film, a CrOCN layer having a film thickness of 14 nm was formed. The conditions at this time are as follows.

Using a chromium target, the power of the DC power source is used in a mixed gas atmosphere of argon, carbon dioxide, nitrogen, and helium (pressure: 0.2 Pa, gas flow ratio Ar: CO ₂ : N ₂ : He = 21: 37: 11: 31) It was set to 1.8 kW and reactive sputtering was performed.

A light-shielding film having a total film thickness of 48 nm was formed by the above procedure. Further, the optical density (O.D.) at a wavelength of 193 nm in the laminated structure of the light-shielding film and the phase-shift film was 3.1.

Thus, the reticle substrate in this embodiment was fabricated.

(resist layer formation step)

The light shielding film of the reticle base is implemented under specific conditions Treatment with HMDS (hexamethyldisilazane, hexamethyldiamine). Thereafter, a chemically amplified resist (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.) which is a positive resist and used for electron beam drawing was spin-coated on a light-shielding film.

(dissolution speed adjustment step)

Thereafter, the baking treatment was carried out at 135 ° C for 10 minutes using a heating and drying device. The film thickness of the resist layer was set to 100 nm. The dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.05 nm/second. Further, the water contact angle is approximately 66.8°.

(developing promoting layer forming step)

Then, a coating liquid containing a component of a constituent material of the development promoting layer is spin-coated on the resist layer. Further, as a solvent in the coating liquid, water and isopropyl alcohol are used. The mass ratio is set to water: IPA = 90:10. As the solute in the coating liquid, Aqua Save (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd. was used. At this time, the mass ratio of the solute to the solvent is determined to be a solute: solvent = 1 to 3: 97 to 99. Thereafter, a specific heat drying treatment (baking treatment) is performed using a heating and drying device. The film thickness of the development promoting layer was set to 20 nm. The salt of the development promoting layer enters the surface layer portion of the resist layer by the baking treatment in the development promoting layer forming step, whereby the altered layer is formed. Further, the thickness of the altered layer was determined by a film-reduction method, and as a result, the thickness of the altered layer was 5 nm.

Through the above steps, the reticle substrate of the resistive layer in the present embodiment is produced.

(resolution evaluation)

The mask substrate of the obtained resist layer was subjected to pattern exposure using an electron beam of 50 kV, and then baked at 120 ° C (PEB: Post Exposure Bake). In the pattern exposure treatment, hole patterns having a line pattern of 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, and 80 nm and apertures of 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, and 80 nm, respectively, were formed. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern. Further, the development promoting layer is peeled off by the developer.

Next, the formed resist pattern was evaluated.

As a line pattern, a line of 80 to 50 nm is formed. In the line pattern of 40 nm, the line portion was confirmed to be thin, and in the line of 30 nm and the gap pattern, the line collapse was confirmed in a part.

Further, as the hole pattern, a hole pattern of 80 to 40 nm was formed. In the pattern in which the diameter of the hole was set to 30 nm, there was a region where the pore diameter was significantly enlarged, and a region connected to a part of the adjacent hole was confirmed.

From this, it is considered that a resist pattern having a pattern size of about 50 nm can be formed by using the mask substrate of the resist layer of the embodiment. Moreover, by correcting the drawing conditions and the like, it is expected to improve the thinning of the line portion at the time of development, and it is possible to form a resist pattern having a pattern size of about 40 nm.

Further, according to the configuration of the present embodiment, even in the fine pore pattern of 30 nm, the exposed portion of the aqueous developing solution can be dissolved, so that the development time can be shortened.

(production of transfer mask)

Then, the mask base of the resist layer which was produced in the same manner as the development promoting layer formation step described above was subjected to pattern exposure using an electron beam of 50 kV, and then baked at 120 ° C (PEB: Post Exposure Bake) ). As the resist pattern, the line and gap pattern were such that the width of the convex portion (line) of the pattern was 40 nm, and the width of the concave portion (gap) of the pattern was 40 nm. Furthermore, based on the above evaluation, the correction of the amount of DOSE at the time of drawing exposure is performed. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

By using the resist pattern as a mask to etch the light-shielding film and the light semi-transmissive film to form a phase shift mask, the phase shift mask is patterned with a transfer precision excellent in shape with respect to the resist pattern.

(Example 2)

In the present embodiment, the buffing treatment temperature in the dissolution rate adjusting step in the first embodiment was set to a condition of 140 ° C to 10 minutes, and a mask base of the resist layer was produced by the same method. Furthermore, the resist layer after baking treatment is in a developing solution (2.38% TMAH) The dissolution rate was 0.03 nm/sec, the water contact angle was about 67.2°, and the thickness of the altered layer formed on the surface of the resist layer was 3 nm.

Then, the resolution was evaluated in the same manner as in Example 1. As a result, a line having a size of 80 to 40 nm was formed as a line pattern. In the line pattern of 30 nm, it was confirmed that the line portion was tapered.

Further, as the hole pattern, a hole pattern of 80 to 40 nm was formed. In the pattern of the hole having a diameter of 30 nm, there is a region where the aperture is enlarged.

From this, it is considered that a resist pattern having a pattern size of about 40 nm can be formed by using the mask substrate of the resist layer of the embodiment. Further, it is considered that a resist pattern having a pattern size of less than 40 nm can be formed by performing correction of drawing conditions and the like.

Then, the mask substrate on which the resist layer of the development promoting layer was formed was subjected to pattern exposure using an electron beam of 50 kV, and then baked at 120 ° C (PEB: Post Exposure Bake). As the resist pattern, the line and gap pattern were such that the width of the convex portion (line) of the pattern was 40 nm, and the width of the concave portion (gap) of the pattern was 40 nm. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size of the line portion was measured at a plurality of points, and as a result, the average was 37.3 nm, and the narrowing and thinning of the line portion was suppressed to 7% or less. From this, it can be seen that a resist pattern having a higher dimensional accuracy can be formed by a slight change in the drawing conditions.

Further, the film reduction amount of the resist pattern is 5 nm or less.

By using the resist pattern as a mask to etch the light-shielding film and the light semi-transmissive film to form a phase shift mask, the phase shift mask is patterned with a transfer precision excellent in shape with respect to the resist pattern.

(Example 3)

In the present embodiment, the reticle substrate having the resist layer was produced in the same manner except that the baking treatment temperature in the dissolution rate adjusting step in the first embodiment was set to 155 ° C to 10 minutes. Furthermore, the resist layer after baking treatment is in a developing solution (2.38% TMAH). The dissolution rate was 0.01 nm/sec, and the water contact angle was 72.3. Further, the thickness of the altered layer formed on the surface of the resist layer was 1 nm.

Then, the resolution was evaluated in the same manner as in Example 1. As a result, a line was formed in all of the line patterns of 80 nm to 30 nm.

Further, the hole pattern forms a hole pattern of all of 80 nm to 30 nm.

From this, it is considered that a resist pattern having a pattern size of 30 nm or less can be formed by using the mask substrate of the resist layer of the embodiment.

Then, the mask substrate to which the resist layer was formed in the same manner as in the development promoting layer forming step of the present embodiment was subjected to pattern exposure using an electron beam of 50 kV, and then baked at 120 ° C (PEB: Post). Exposure Bake). As the resist pattern, the line and gap pattern were such that the width of the convex portion (line) of the pattern was 40 nm, and the width of the concave portion (gap) of the pattern was 40 nm. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

Next, the size of the line portion of the resist pattern was measured at a plurality of points, and as a result, the average was 39.3 nm, and the narrowing and thinning of the line portion was suppressed to 2% or less. From this, it can be seen that a resist pattern having a higher dimensional accuracy can be formed by a slight change in the drawing conditions.

Further, the film reduction amount of the resist pattern is 2 nm or less.

By using the resist pattern as a mask to etch the light-shielding film and the light semi-transmissive film to form a phase shift mask, the phase shift mask is formed into a thin film pattern with excellent transfer precision with respect to the shape of the resist pattern.

(Example 4)

In the present embodiment, a hard mask film was formed on the light-shielding film of the mask base produced in Example 2 as a phase shift mask base. First, on the light-shielding film of the reticle base of the first embodiment, a hard mask film having a thickness of 5 nm as an etch mask is formed by using a monolithic DC sputtering apparatus, and a resist layer is formed on the hard mask film. The resist layer in this example was produced in the same manner as in Example 2 except that the thickness of the resist layer was 50 nm. The reticle base. The dissolution rate of the resist layer after baking treatment in the developer (2.38% TMAH) was 0.03 nm/second.

Furthermore, the hard mask film uses a Si target in a mixed gas atmosphere of Ar (Ar), Nitrogen (N ₂ ), and Oxygen (O ₂ ) (Ar:N ₂ :O ₂ =20:57:23 [volume In %]), reactive sputtering was carried out to thereby form SiON having a film thickness of 5 [nm].

Next, the mask substrate on which the resist layer of the development promoting layer was formed in the same manner as in Example 1 was subjected to pattern exposure using an electron beam of 50 kV. As the resist pattern, the line and gap pattern were such that the width of the convex portion (line) of the pattern was 40 nm, and the width of the concave portion (gap) of the pattern was 40 nm.

Thereafter, baking treatment (PEB: Post Exposure Bake) was carried out at 120 °C. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size of the line portion was measured at a plurality of points, and as a result, the average was 37.2 nm, and the narrowing and thinning of the line portion was suppressed to 7% or less. From this, it can be seen that a resist pattern having a higher dimensional accuracy can be formed by a slight change in the drawing conditions.

Further, the film reduction amount of the resist pattern is 5 nm or less.

Then, the hard mask film is etched using the resist pattern as a mask, and the etched hard mask film is used as a mask to etch the light shielding film and the light semi-transmissive film to form a phase shift mask. The phase shift mask is patterned in a transfer precision superior to the shape of the resist pattern.

(Example 5)

In the present embodiment, a light-shielding film and a hard mask film are sequentially formed on the substrate as a binary mask base.

First, a single-layer MoSiN film having a film thickness of 50 nm was formed as a light-shielding film on a substrate containing transmissive quartz glass and having light transmissivity using a monolithic DC sputtering apparatus. The conditions at this time are as follows.

The sputtering target uses a mixed target of molybdenum (Mo) and bismuth (Si) (atomic % ratio Mo: Si = 21:79) in a mixed gas atmosphere of argon (Ar), nitrogen (N ₂ ), and helium (He). (gas pressure 0.3 Pa, the gas flow ratio _{Ar: N 2: He = 5} : 49: 46) , the power of the DC power source is set to 2.1kW, a reactive sputtering (DC sputtering). After the sputtering, heat treatment (annealing treatment) was performed at 250 ° C for 5 minutes.

Thereafter, a hard photomask film containing CrOCN was formed on the light-shielding film using a monolithic DC sputtering apparatus. Specifically, the sputtering target of chromium (Cr) target is assumed argon (Ar), carbon dioxide (CO _2), nitrogen (N _2), and helium (He) of the mixed gas atmosphere (gas pressure 0.2Pa, a gas flow rate ratio Ar: CO ₂ : N ₂ : He = 22: 39: 6: 33), the power of the DC power source was set to 1.7 kW, and a CrOCN layer having a film thickness of 10 nm was formed by reactive sputtering (DC sputtering).

The reticle substrate in this embodiment was fabricated by the above steps.

A mask layer having a thickness of 50 nm was formed on the hard mask film of the obtained mask base using the same positive resist as in Example 1, and a mask substrate of the resist layer in the present embodiment was produced. Further, the baking treatment at the time of forming the resist layer was set to 155 ° C for 10 minutes. Further, the dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.01 nm/second.

Next, the mask substrate on which the resist layer of the development promoting layer was formed in the same manner as in Example 1 was subjected to pattern exposure using an electron beam of 50 kV. As the resist pattern, the line and gap pattern were such that the width of the convex portion (line) of the pattern was 40 nm, and the width of the concave portion (gap) of the pattern was 40 nm.

Thereafter, baking treatment (PEB: Post Exposure Bake) was carried out at 120 °C. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size of the line portion was measured at a plurality of points, and as a result, the average was 39.2 nm, and the narrowing and thinning of the line portion was suppressed to 2% or less. From this, it is understood that according to the configuration of the present embodiment, a highly accurate resist pattern can be formed without changing the conditions such as drawing. Further, it is considered that a resist pattern having a higher dimensional accuracy can be formed by slightly changing the drawing conditions and the like.

Further, the film reduction amount of the resist pattern is 2 nm or less.

Then, the hard mask film is etched using the resist pattern as a mask, and the mask is formed by etching the light-shielding film using the etched hard mask film as a mask. As a result, the shape is excellent with respect to the shape of the resist pattern. The printing precision forms a pattern.

(Example 6)

In the present embodiment, a light-shielding film and an anti-surface reflection film were formed on the substrate as a binary type mask substrate.

First, a single-layer TaN film having a film thickness of 42 nm was formed as a light-shielding film on a substrate containing transmissive quartz glass and having a light transmissive property using a monolithic DC sputtering apparatus. The conditions at this time are as follows.

Sputtering target containing tantalum (Ta) of the target, in xenon (Xe) and nitrogen (N ₂₎ of a mixed gas environment (gas pressure 0.3 Pa, gas flow rate ratio _{Xe:: N 2 = 42 58} ), the DC power source The power was set to 2.8 kW and reactive sputtering (DC sputtering) was performed.

Thereafter, a TaO film having a film thickness of 9 nm was formed as an anti-surface reflection film on a light-shielding film containing a TaN film using a monolithic DC sputtering apparatus. The composition of the TaO film was set to Ta: 48 atom%, and O: 52 atom%. Further, the conditions for forming the TaO film are as follows. The sputtering target uses a target containing tantalum (Ta) and is a mixed gas atmosphere of argon (Ar) and oxygen (O ₂ ) (gas pressure 0.3 Pa, gas flow ratio Ar: O ₂ = 64: 36), and the DC power source is used. The power is set to 3.0 kW.

The reticle substrate in this embodiment was fabricated by the above steps.

A mask substrate having the same resisting agent as that of Example 1 was formed on the antireflection film of the obtained mask base to form a resist layer having a thickness of 80 nm to form the resist layer of the present embodiment. Further, the baking treatment at the time of forming the resist layer was set to 140 ° C for 10 minutes. Further, the dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.03 nm/second.

Next, the mask substrate on which the resist layer of the development promoting layer was formed in the same manner as in Example 1 was subjected to pattern exposure using an electron beam of 50 kV. As the resist pattern, the line and gap pattern is such that the width of the convex portion (line) of the pattern is 40 nm, and the width of the concave portion (gap) of the pattern is wide. The degree becomes 40 nm.

Thereafter, baking treatment (PEB: Post Exposure Bake) was carried out at 120 °C. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size of the line portion was measured at a plurality of points, and as a result, the average was 37.3 nm, and the narrowing and thinning of the line portion was suppressed to 7% or less. From this, it can be seen that a resist pattern having a higher dimensional accuracy can be formed by a slight change in the drawing conditions.

Further, the film reduction amount of the resist pattern is 5 nm or less.

Then, the resist pattern is used as a mask to etch the surface reflective film, and the etched anti-surface reflection film is used as a mask to etch the light-shielding film to form a mask. As a result, the transfer is excellent in shape relative to the resist pattern. The precision forms a pattern.

(Example 7)

In the present embodiment, a hard mask film was formed on the anti-surface reflection film of the reticle substrate produced in Example 6 as a binary reticle substrate.

On the anti-surface reflection film of the reticle substrate of Example 6, a single-chip DC sputtering apparatus was used to form a hard mask film having a film thickness of 4 nm as an etch mask, and a resist layer was formed on the hard mask film. The resistive layer of the present embodiment was produced in the same manner as in Example 6 except that the thickness of the resist layer was set to 50 nm and the baking temperature before the exposure drawing was set to 155 ° C to 10 minutes. Photomask base. The dissolution rate of the resist layer after baking treatment in the developer (2.38% TMAH) was 0.03 nm/second.

Further, the composition of the hard mask film was set to Cr: 79 atom%, and N: 21 atom%. Moreover, the conditions at the time of forming a hard mask film are as follows. The sputtering target uses a target containing chromium (Cr) and is a mixed gas atmosphere of argon (Ar) and nitrogen (N ₂ ) (gas pressure 0.1 Pa, gas flow ratio Ar: N ₂ = 83: 17), and the DC power source is used. The power is set to 1.7 kW.

Next, the mask substrate on which the resist layer of the development promoting layer was formed in the same manner as in Example 1 was subjected to pattern exposure using an electron beam of 50 kV. As the resist pattern, the line and gap pattern is such that the width of the convex portion (line) of the pattern is 40 nm, and the width of the concave portion (gap) of the pattern is wide. The degree becomes 40 nm.

Thereafter, baking treatment (PEB: Post Exposure Bake) was carried out at 120 °C. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size of the line portion was measured at a plurality of points, and as a result, the average was 37.4 nm, and the narrowing and thinning of the line portion was suppressed to 7% or less. From this, it can be seen that a resist pattern having a higher dimensional accuracy can be formed by a slight change in the drawing conditions.

Further, the film of the resist pattern is reduced to 5 nm or less.

Then, the resist pattern is used as a mask to etch the hard mask film, and the etched hard mask film is used as a mask to etch the light-shielding film and the anti-surface reflection film to form a mask, and the mask is formed in accordance with the mask. Design pattern.

(Example 8)

In the present embodiment, a multilayer reflective film, a protective film, an absorber film, and a low-reflection film were sequentially formed on a substrate as a reflective mask substrate.

First, on a substrate comprising the SiO ₂ -TiO ₂ glass, using an ion beam sputtering apparatus, there are formed alternately laminating Mo film and the total thickness of the Si film of the multilayer reflective film 280nm. The conditions at this time are as follows.

A multilayer reflective film is formed on the glass substrate by ion beam sputtering. Specifically, a Si target-formed Si layer was used as a low-refractive-index layer, and a Mo target-formed Mo layer was used as a high-refractive-index layer, and this was set to one cycle and laminated for 40 cycles. Also, a Si layer was finally formed using a Si target as a low refractive index layer.

Thereafter, a protective film was formed on the multilayer reflective film by DC magnetron sputtering. Specifically, a Ru film was formed using an Ru target in an atmosphere of argon (Ar).

Next, an absorber film was formed by sequentially laminating the absorber layer and the low reflection layer on the protective film by DC magnetron sputtering to produce a reflective mask substrate. Specifically, a TaB alloy layer is used to form a TaBN layer of the absorber layer in a mixed gas atmosphere of xenon (Xe) and nitrogen (N ₂ ), and secondly, a mixed gas of argon (Ar) and oxygen gas (O ₂ ). The TaBO layer of the film-forming low-reflection layer under the environment.

The reticle substrate in this embodiment was fabricated by the above steps.

A mask substrate having the same resisting agent as that of Example 1 was used to form a resist layer having a thickness of 50 nm on the surface of the obtained reflective mask substrate to prepare a resist layer of the resist layer in the present embodiment. Further, the baking treatment at the time of forming the resist layer was set to 155 ° C for 10 minutes. Further, the dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.01 nm/second.

The mask substrate on which the resist layer of the development promoting layer was formed in the same manner as in Example 1 was subjected to pattern exposure by an electron beam of 50 kV, and then baked at 120 ° C (PEB: Post Exposure Bake). As the resist pattern, the line and gap pattern was such that the width of the convex portion (line) of the pattern was 30 nm, and the width of the concave portion (gap) of the pattern was 30 nm. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size of the line portion was measured at a plurality of points, and as a result, the average value was 29.1 nm, and the narrowing and thinning of the line portion was suppressed to 3% or less.

From this, it is understood that according to the present embodiment, a highly accurate resist pattern can be formed without changing the conditions such as drawing. Further, it is considered that a resist pattern having a higher dimensional accuracy can be formed by slightly changing the drawing conditions and the like.

Further, the film of the resist pattern is reduced to 2 nm or less.

Then, the low-reflection film is etched using the resist pattern as a mask, and the absorber film is etched using the etched low-reflection film as a mask to produce a reflective mask. In the reflective reticle produced, an absorber film pattern having good dimensional accuracy was formed.

(Example 9)

In the present embodiment, a hard mask film is formed on a substrate as a substrate for imprinting.

First, a hard mask film is formed on a substrate including synthetic quartz glass and having light transmissivity using a monolithic DC sputtering apparatus. The composition of the hard mask film was set to Cr: 79 atom%, and N: 21 atom%. Moreover, the conditions at the time of forming a hard mask film are as follows. The sputtering target uses a target containing chromium (Cr) and is a mixed gas atmosphere of argon (Ar) and nitrogen (N ₂ ) (gas pressure 0.1 Pa, gas flow ratio Ar: N ₂ = 83: 17), and the DC power source is used. The power is set to 1.7 kW.

The mold base in this embodiment was produced by the above steps.

A resist layer having a thickness of 50 nm was formed on the hard mask film of the obtained mold base using the same positive resist as in Example 1, and a mold base of the resist layer in the present embodiment was produced. Further, the baking treatment at the time of forming the resist layer was set to 155 ° C for 10 minutes. Further, the dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.01 nm/second.

Thereafter, exposure and development were carried out under the same conditions as in Example 1 to form a resist pattern. The formed resist pattern was evaluated, and the narrowing and thinning of the resist pattern or film reduction was suppressed.

Then, the hard mask film is etched using the resist pattern as a mask, and the etched hard mask film is used as a mask to etch the substrate to form a mold. As a result, the mold is excellent in shape with respect to the resist pattern. The printing precision forms a pattern.

(Embodiment 10)

In the present embodiment, a three-tone type transfer photomask 12 was produced using the phase shift mask substrate also employed in the first embodiment. The specific configuration of the transfer mask 12 is shown in Fig. 9 . Fig. 9(a) is a schematic plan view of a three-tone type transfer photomask 12 (three-tone mask 20) in the present embodiment, and Fig. 9(b) is a schematic cross-sectional view of the three-tone mask 20. Furthermore, this embodiment is the same as the above-described FIGS. 7(a) to (d) and FIG. 8(a).

The three-tone mask 20 of the present embodiment has a transmissive region 21 in which the surface of the translucent substrate is exposed, a halftone region 22 including an exposed portion of the semi-transmissive film, and a light semi-transmissive film and a light-shielding film. The shading area of the area 23.

In the three-tone mask 20 of the present embodiment, as shown in FIG. 9(a), a pattern in which the transmission regions 21 are formed at a pitch of 150 nm and arranged in a lattice shape of 3 × 3 is formed. The shape of the transmission region 21 is set to a square pattern of 50 nm × 50 nm. The transmission region 21 is formed in the halftone region 22 The inside, in other words, the halftone region 22 is a pattern that surrounds the shape of the periphery of the transmission region 21. The halftone region 22 is a square pattern having an outer shape of 100 nm × 100 nm.

The three-tone mask 20 of the present embodiment is first formed by forming the light-shielding region 23 by the outside of the halftone region 22, and then forming the halftone region 22 and the transmission region 21.

<Formation of shading area 22>

First, the surface of the light-shielding film of the phase shift mask substrate which was also used in Example 1 was spin-coated as a positive resist and a chemical amplification resist for electron beam drawing (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.).

Next, in the dissolution rate adjusting step, the baking treatment temperature was set to 155 ° C for 10 minutes to produce a mask base of the resist layer. Further, the dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.01 nm/second.

A development promoting layer similar to that of Example 1 was formed on the surface of the above resist layer, and the mask base of the resist layer was subjected to pattern exposure using an electron beam of 50 kV. Thereafter, baking treatment (PEB: Post Exposure Bake) was carried out at 120 °C. As a resist pattern, a square pattern of 100 nm × 100 nm was formed at intervals of 50 nm in three rows of three sides in a row and a total of nine places. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size (the size of the line portion) of the light-shielding region 23 between the adjacent halftone patterns 22 is measured, and as a result, the average is 49.2 nm, and the narrowing and thinning of the line portion can be suppressed to 2% or less. The film reduction amount of the resist pattern is 2 nm or less.

The light-shielding film is etched by using the resist pattern as a mask to form a halftone region 22, and a light-shielding region 23 is formed.

<Formation of the transmission region 21 pattern and the halftone region 22 pattern>

Next, on the surface of the mask base on which the light-shielding region 23 is formed, the film is coated with a positive resist on the surface so that the film thickness on the light-shielding film region 23 is 100 nm, and the chemical amplification resist for electron beam drawing ( PRL009: manufactured by FUJIFILM Electronics Materials).

Next, the resist layer was formed under the conditions of a baking treatment temperature in the dissolution rate adjusting step of 155 ° C to 10 minutes. The dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.01 nm/second.

Further, a development promoting layer similar to that of Example 1 was formed on the surface of the above-mentioned resist layer, and the mask base of the resist layer was subjected to pattern exposure using an electron beam of 50 kV. Thereafter, the reticle substrate after the exposure of the drawing was subjected to a baking treatment (PEB: Post Exposure Bake) at 120 °C. As the resist pattern, a square pattern of 50 nm × 50 nm was formed in the same manner as the center inside the outer shape of the halftone region 22 formed as described above. Then, using 2.38% TMAH as a developing solution, development was carried out for 60 seconds to form a resist pattern.

The size of one side of the square of the gap portion (portion portion of the transmission region 21) of the formed resist pattern is an average of 50.9 nm, and the gap portion can be formed with the correct size. The resist pattern is used as a mask, and the light semi-transmissive film is dry-etched by a fluorine-based gas to form a transmissive region 21 and a halftone region 22.

When the positional accuracy of the three-tone mask 20 produced by the above method was confirmed, the displacement between the transmission region 21 and the center of the outer shape of the halftone region 22 was 1 nm or less, and the three-tone mask 20 excellent in positional accuracy was produced.

(Comparative Example 1)

In Comparative Example 1, the phase shift mask substrate produced in Example 1 was used. The HIDS treatment is performed on the light-shielding film of the reticle base under specific conditions. Thereafter, a chemically amplified resist (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.) which is a positive resist and used for electron beam drawing was spin-coated on a light-shielding film.

Thereafter, baking treatment was carried out at 125 ° C for 10 minutes using a heating and drying device. The film thickness of the resist layer was set to 100 nm. Through the above steps, the mask substrate of the resistive layer in Comparative Example 1 was produced. Further, the dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.12 nm/second.

Thereafter, the resolution was evaluated in the same manner as in Example 1, and as a result, as a line pattern, A line having a size of at most 50 nm was formed, and it was confirmed that it was clearly tapered. Further, in the line pattern of 40 nm, collapse was observed, and in the line pattern of 30 nm, there was a portion which disappeared.

Further, in the hole pattern, in the hole pattern having a pore diameter of 30 nm and 40 nm, the defect of the hole was confirmed. Further, in the hole pattern having a hole diameter of 70 nm and 80 nm, a portion connected to the adjacent pattern was confirmed.

Then, the mask base of the resistive layer of the comparative example was exposed and developed such that the width of the convex portion (line) of the pattern was 40 nm, and the width of the concave portion (gap) of the pattern was 40 nm. Since the resist pattern is formed, since the vertical and horizontal directions are relatively large, the line and gap patterns collapse, and a specific resist pattern cannot be formed.

(Comparative Example 2)

In Comparative Example 2, the phase shift mask substrate produced in Example 1 was used. The HIDS treatment is performed on the light-shielding film of the reticle base under specific conditions. Thereafter, a chemically amplified resist (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.) which is a positive resist and used for electron beam drawing was spin-coated on a light-shielding film.

Thereafter, baking treatment was carried out at 125 ° C for 10 minutes using a heating and drying device. The film thickness of the resist layer was set to 80 nm. The dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.12 nm/second.

Through the above steps, the mask substrate of the resistive layer in Comparative Example 2 was produced.

Thereafter, exposure and development were carried out to form a resist pattern by forming a line having a width of 40 nm, a gap pattern, a gap pattern, and a hole pattern having a hole diameter of 40 nm. At this time, the collapse of the line and the gap pattern is suppressed, but the dissolution of the resist pattern of the developer is performed. Therefore, when the light shielding film is etched, the resist pattern of the mask should be eliminated, and the mask should be used as a mask. Etching, the thickness of the light-shielding film is reduced, and the specific performance cannot be exhibited.

(Comparative Example 3)

In Comparative Example 3, the phase shift mask substrate produced in Example 3 was used. The HIDS treatment is performed on the light-shielding film of the reticle base under specific conditions. Will be positive A chemically amplified resist (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.) for resisting and electron beam drawing was spin-coated on a light-shielding film.

Thereafter, baking treatment was carried out at 155 ° C for 10 minutes using a heating and drying device. The film thickness of the resist layer was set to 80 nm. The dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.01 nm/second.

Through the above steps, the mask substrate of the resistive layer in Comparative Example 3 was produced.

Thereafter, exposure and development were carried out so as to form a line having a width of 40 nm, a gap pattern, a gap pattern, and a hole pattern, thereby forming a resist pattern. At this time, the dissolution of the resist pattern is suppressed, and the T-top shape is visible in the gap pattern and the hole pattern. As a result, etching was inhibited during the etching of the light-shielding film, and the pattern of the light-shielding film was not resolved.

(Comparative Example 4)

In Comparative Example 4, the phase shift mask substrate produced in Example 1 was used. The HIDS treatment is performed on the light-shielding film of the reticle base under specific conditions. Thereafter, a chemically amplified resist (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.) which is a positive resist and used for electron beam drawing was spin-coated on a light-shielding film.

Thereafter, baking treatment was carried out at 125 ° C for 10 minutes using a heating and drying device. The film thickness of the resist layer was set to 50 nm. The dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.12 nm/second.

Then, a development promoting layer was formed in the same manner as in Example 1. At this time, a metamorphic layer is also formed. Through the above steps, the mask substrate of the resistive layer in Comparative Example 4 was produced.

Thereafter, exposure and development were carried out so as to form a line having a width of 40 nm, a gap pattern, a gap pattern, and a hole pattern having a hole diameter of 40 nm to form a resist pattern. In this case, since the resist pattern of the developer is dissolved and thinned, the resist pattern of the mask is lost during the etching of the light-shielding film, and the light-shielding film to be used as the mask is etched, and the light-shielding film disappears. The gap pattern is not resolved.

(Comparative Example 5)

In Comparative Example 5, the imprint mold substrate produced in Example 9 was used.

The hard mask film of the obtained mold base was subjected to HMDS treatment under specific conditions. Thereafter, a chemically amplified resist (PRL009: manufactured by FUJIFILM Electronics Materials Co., Ltd.) which is a positive resist and used for electron beam drawing was spin-coated on a light-shielding film.

Thereafter, the baking treatment was carried out at 135 ° C for 10 minutes using a heating and drying device. The film thickness of the resist layer was set to 30 nm. The dissolution rate of the resist layer after the baking treatment in the developer (2.38% TMAH) was 0.05 nm/second.

Then, a development promoting layer was formed in the same manner as in Example 1. At this time, a metamorphic layer is also formed. Through the above steps, an imprint mold substrate of the resist layer in Comparative Example 5 was produced.

Thereafter, exposure and development were carried out so as to form a line and a gap of 30 nm width to form a resist pattern. At this time, the dissolution of the resist pattern of the developer is performed. Therefore, when the hard mask film is etched, the resist pattern of the mask should be eliminated, and the hard mask film to be used as a mask should be etched, and the hard mask film should be etched. It disappears, and the line and gap patterns are not resolved in the etching of the substrate.

1‧‧‧Substrate

2‧‧‧film

5‧‧‧Photomask base

7‧‧‧Resist layer

9‧‧‧Development promotion layer

10‧‧‧Photomask base with resistive layer

12‧‧‧Transfer mask

Claims (22)

A substrate with a resist layer, comprising: a substrate; and a resist layer formed of the positive resist material formed on the substrate, wherein the resist layer has a thickness of 200 nm or less, The dissolution rate of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less, and development of the above-mentioned aqueous developing solution on at least the exposed portion of the resist layer is formed on the resist layer. Promotion layer. A substrate with a resist layer, comprising: a substrate; and a resist layer formed of the positive resist material formed on the substrate, wherein the resist layer has a thickness of 200 nm or less, The surface of the unexposed portion of the resist layer has a contact angle with respect to water of 66 or more, and a development promoting layer which causes the aqueous developing solution to spread over at least the exposed portion of the resist layer is formed on the resist layer. The substrate of the resistive layer of claim 1 or 2, wherein the development promoting layer is water-soluble. The substrate of the resistive layer according to any one of claims 1 to 3, wherein at least the surface of the exposed portion of the resist layer is deteriorated by the development promoting layer. The substrate of the resistive layer according to any one of claims 1 to 4, wherein the substrate has a film on a surface thereof, and the resist layer is formed on a surface of the film. The substrate of the resistive layer of claim 5, wherein the film further has a hard mask film. The substrate of the receptor layer of claim 5 or 6, wherein the substrate is a translucent substrate having a light transmissive property for light having a wavelength of 200 nm or less, and the film has a light-shielding film of a binary type photomask substrate. The substrate of the resistive layer according to claim 5 or 6, wherein the substrate is a light-transmitting substrate having light transmissivity to light having a wavelength of 200 nm or less, and the film has semi-transmissivity to light having a wavelength of 200 nm or less. The light half-transmissive film has a halftone phase shifting reticle substrate. The substrate of the resistive layer of claim 5 or 6, wherein the substrate is a low thermal expansion substrate, and the film has at least a reflective film and a reflective mask substrate of the absorber film. The substrate of the resistive layer of any one of claims 1 to 6, which is an imprinted mold substrate. A reticle for transfer, which is produced by using a reticle substrate of a resisting agent layer according to any one of claims 7 to 9, and a specific pattern is formed on the film. An imprint mold which is produced by using an imprint mold substrate as claimed in claim 10, and a specific pattern is formed on the film of the substrate or the surface thereof. A method for producing a substrate with a resist layer, comprising: a dissolution rate adjusting step for a resist layer formed on a substrate and composed of a positive resist material, by performing the resist layer a baking treatment process, wherein a rate of dissolution of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less; and a development promoting layer forming step of forming the aqueous developing solution on the resist layer a development promoting layer which is caused by at least the exposed portion of the resist layer; and the thickness of the resist layer is 200 nm or less. A method for manufacturing a substrate with a resist layer, comprising: a contact angle adjusting step for a resist layer formed on a substrate and composed of a positive resist material, by performing the resist layer Baking treatment so that the contact angle of water on the surface of the unexposed portion of the resist layer is 66° or more; A development promoting layer forming step of forming a development promoting layer on the resist layer to cause the aqueous developing solution to spread over at least the exposed portion of the resist layer; and the thickness of the resist layer is 200 nm or less. A method of producing a substrate of a resistive layer according to claim 13 or 14, wherein said substrate has a film on a surface thereof, and said resist layer is formed on a surface of said film. A method of producing a photomask for transfer, comprising the step of forming a specific pattern on a substrate of a resistive layer produced by the method of any one of claims 13 to 15, and the above-mentioned obstruction The substrate of the agent layer is a reticle substrate with a resist layer. A method of producing an embossing mold, characterized by having the step of forming a specific pattern on a substrate of a resistive layer produced by the method of any one of claims 13 to 15, and the above-mentioned resisting agent The substrate of the layer is an imprinting mold substrate with a resist layer. A reticle substrate with a resist layer, characterized in that it has a substrate, and a resist layer formed of the positive resist material formed on the substrate, and a base of a specific concave-convex pattern is formed. The thickness of the resist layer in the portion is 200 nm or less, and the dissolution rate of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less, and the resist layer is formed on the resist layer so that the aqueous developing solution is spread over the resist layer. a development promoting layer of at least the exposed portion of the resist layer. A reticle substrate with a resist layer, characterized in that it has a substrate, and a resist layer formed of the positive resist material formed on the substrate, and a base of a specific concave-convex pattern is formed. The thickness of the resist layer in the portion is 200 nm or less, and the contact angle of the surface of the unexposed portion of the resist layer to water is 66° or more. A development promoting layer that causes the aqueous developing solution to spread over at least the exposed portion of the resist layer is formed on the resist layer. A transfer photomask characterized in that it is produced using a photomask substrate as in the resistive layer of claim 18 or 19, and a specific pattern is formed on the film on the surface of the substrate. A method for producing a transfer mask, comprising: a dissolution rate adjustment step for a resist layer formed on a surface of a substrate on which a specific concavo-convex pattern is formed and formed of a positive resist material By baking the resist layer, the dissolution rate of the unexposed portion of the resist layer in the aqueous developing solution is 0.05 nm/sec or less; and the development promoting layer forming step is formed on the resist layer a development promoting layer that causes the aqueous developing solution to spread over at least the exposed portion of the resist layer; and a resist pattern formed of the resist layer as a mask to form the substrate on which the specific concave-convex pattern is formed a step of specifying a concave-convex pattern; and a thickness of the resist layer of the convex portion of the base is 200 nm or less. A method of manufacturing a transfer mask, comprising: a contact angle adjustment step for a resist layer formed on a surface of a substrate on which a specific concavo-convex pattern is formed and formed of a positive resist material By baking the resist layer, the contact angle of the surface of the unexposed portion of the resist layer with respect to water is 66° or more; and a development promoting layer forming step is formed on the resist layer to form a development promoting layer that causes the aqueous developing solution to pass over at least the exposed portion of the resist layer; and a resist pattern formed of the resist layer as a mask, and the second specific unevenness is formed on the substrate on which the specific concave-convex pattern is formed a pattern; and the thickness of the resist layer of the convex portion of the substrate is 200 nm or less.