JP3336740B2 - Method of forming microstructure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a fine structure, and more particularly to a method for easily and easily forming a fine structure having a fine line width and a large thickness and a high aspect ratio. And a method for forming a fine structure.

[0002]

2. Description of the Related Art In recent years, research on fine processing technology for forming an extremely fine structure by applying the manufacturing technology of a semiconductor integrated circuit device has been actively conducted.

In particular, LIGA (Lithograph Ga) for forming a fine structure having a high aspect ratio by using deep lithography using X-rays and electroplating.
lvanformung und Abformun
g) method is of particular interest (Nikkei
Mechanical 1990.11.26, p.
26 to p. 28).

The LIGA method can be used for manufacturing micromachines, optical elements, sensors or actuators, and has a very wide range of applications.

FIGS. 8 and 9 are process diagrams schematically showing an example of a basic process for the conventional LIGA method.

Referring to FIGS. 8 and 9, first, FIG.
In the step shown in (a), typically, a resist (photosensitive resin) layer 102 containing polymethyl methacrylate (PMMA) as a main component (base resin) is formed on a substrate with a desired thickness (several tens μm to several hundreds μm). It is formed on 101.

Next, in the step shown in FIG.
The resist layer 102 is irradiated with synchrotron radiation (SR light) through the line mask 100 to form the resist layer 102.
Then, a desired pattern 102p is exposed.

The X-ray mask 100 has an X-ray absorber 1 in which a desired pattern is formed of a metal having a high X-ray absorption rate.
00a, and a light transmitting film (mask membrane) 100b made of a material that easily transmits X-rays. In addition,
The light transmitting film (mask membrane) is also called a mask supporting film.

Next, in a step shown in FIG. 8C, the resist layer 102 on which the desired pattern 102p is exposed is developed to form a resist pattern (resist structure) 103.
To form

Next, in a step shown in FIG. 8D, based on the resist pattern 103, a metal structure 104 is formed.
To form

More specifically, the entire substrate 101 having the resist pattern 103 is immersed in a plating solution, and nickel (Ni), copper (Cu), gold (Au) or the like is resist-coated on the substrate 101 by electroplating. It is deposited in the valley 103v of the pattern 103.

Next, in a step shown in FIG. 8E, the metal structure 104 is obtained by removing the substrate 101 and the resist pattern 103.

The metal structure 104 may be used as an end product, or the metal structure 104 may be used as a mold for molding.

When the metal structure 104 is used as a mold for molding, the metal structure 104 is filled with a plastic material by, for example, an injection molding method in a step shown in FIG. Next, the metal structure 1
04 is removed to obtain a plastic structure 10.
Get 5.

The plastic structure 105 may be used as a final product, or the plastic structure 105 may be used as a mold for molding.

When the plastic structure 105 is used as a mold, a metal structure (not shown) is obtained by electroplating or electroforming using the plastic structure 105 as a mold. Is sintered in a plastic structure 105 to form a ceramic structure (not shown).

The steps shown in FIGS. 9B to 9E are process diagrams schematically showing an example of forming a metal structure based on the plastic structure 105.

First, in the step shown in FIG. 9B, a dielectric plastic structure is prepared as the plastic structure 105. Then, according to the plastic structure 105, the plastic mold 10 composed of the dielectric plastic 106 and the conductive plastic sheet 107 is formed.
8 is formed.

Next, in the step shown in FIG. 9C, the plastic structure 105 is separated, and a plastic mold 108 is prepared.

Next, in a step shown in FIG. 9D, a metal structure 109 is deposited on the valley 108v of the plastic mold 108 by electroforming or electroplating.

Next, in a step shown in FIG. 9E, the plastic mold 108 is removed, and a metal structure 110 is obtained.

The term “fine structure” used in the present specification is not particularly limited to the following cases. For example, the metal structure 104 formed in the step shown in FIG. 9A, and a metal structure (not shown) and a ceramic structure (not shown) formed based on the plastic structure 105 formed in the process shown in FIG. 9) and a metal structure 110 formed in the step shown in FIG.

As a technique for forming a fine structure, a two-dimensional miniaturization technique having a small thickness (1 μm to 3 μm) in a two-dimensional figure, such as a circuit component of a semiconductor integrated circuit, is simply used. Not a two-dimensional figure but the thickness (Equation 1)
A three-dimensional miniaturization technology having a size of 0 μm to several 100 μm) is required.

For example, when manufacturing a micromachine or the like, a component of the micromachine or the like may have a size of about 1 μm to
A line width dimension of about 10 μm and about 10 μm to about 100 μ
It is necessary to manufacture parts of various sizes having a thickness (height) of the order of m.

In a microstructure such as a macro machine, an optical element, a sensor or an actuator,
In some cases, a certain mechanical strength is required, and a method for forming a microstructure having a high aspect ratio has been desired for many years.

For example, in a microstructure used for a driving mechanism such as an actuator or a micro gear, it is necessary to form a microstructure having a high aspect ratio in order to obtain a constant driving force.

More specifically, for example, FIG.
Referring again to FIGS. 9A and 9E, as a line width dimension W, for example, a finely processed portion of about 1 μm to 10 μm and a thickness (height) H, for example, a number A microstructure having a high aspect ratio (H / W), including a portion having a dimension of 100 μm or more, with high accuracy.
There has been a long-felt need for a method for forming a microstructure that can be formed easily and easily.

In the method for forming a fine structure such as the LIGA method described above, since the fine structure is formed based on the resist pattern 103, the resist layer 102 is formed thick on the substrate 101, It is necessary to reduce the diffraction effect of light by using tron radiation light (SR light) and to perform deep exposure on the resist layer 102 formed on the substrate 101.

Conventionally, in a method of forming a fine structure such as the LIGA method, a thick resist layer is formed on a substrate by using a multi-spin coating method (Micro Elect).
roMechanical System'92 Tr
avemunde (Germany), February
y4-7, 1992, p. 93-p. 97).

The multi-spin coating method is a method in which the spin coating method is repeated many times. Hereinafter, a method of forming a thick resist layer containing polymethyl methacrylate (PMMA) as a main component (base resin) on a substrate by using a multi-spin coating method will be described.

First, a methyl methacrylate monomer (monomer) is placed as a starting material in a solvent such as toluene.

Next, using a crosslinking agent such as triethylene glycol dimethacrylate or ethylene glycol dimethacrylate in a solvent such as toluene, by a solution polymerization method,
A methyl methacrylate polymer (polymer) is produced by completely polymerizing a methyl methacrylate monomer (monomer).

Next, the methyl methacrylate polymer (polymer) in a solvent such as toluene is converted into
Allow to settle. Next, the obtained methyl methacrylate polymer (polymer) is purified. Next, a solution (resist solution) having a desired viscosity is prepared by dissolving the purified methyl methacrylate polymer (polymer) in a solvent such as ethyl cellosolve acetate (ECA).

The term "solvent" as used herein means a solvent (liquid) for dissolving the polymer, which is different from the starting material monomer, and is itself used when forming a resist layer. A material to be removed from the resist layer.

Next, a resist layer is formed on the substrate by spin coating using this solution (resist solution).

More specifically, a methyl methacrylate polymer (polymer) and ethyl cellosolve acetate (EC
A) A solution containing a solvent such as A) (resist solution) is dropped on a horizontal substrate, and the substrate is rotated using a spinner or the like, thereby using a centrifugal force to produce a methyl methacrylate polymer (polymer). And a solution layer containing a solvent such as ethyl cellosolve acetate (ECA) is formed on the substrate to a uniform thickness.

Next, the substrate having the solution layer is subjected to a heat treatment (so-called pre-baking) for the purpose of removing a residual solvent such as ethyl cellosolve acetate (ECA) contained in the solution layer formed on the substrate. A resist layer is formed thereon.

In the multi-spin coating method, a resist layer is further formed on the resist layer formed on the substrate by the above-mentioned spin coating method.

That is, in the multi-spin coating method, a solution (resist solution) containing a solvent such as methyl methacrylate polymer (polymer) and ethyl cellosolve acetate (ECA) is further formed on the resist layer formed on the substrate.
Is dropped, and the substrate is rotated using a spinner or the like, thereby using a methyl methacrylate polymer (polymer) and ethyl cellosolve acetate (ECA) using centrifugal force.
A solution layer containing a solvent or the like is formed to a uniform thickness on the resist layer formed on the substrate.

As described above, a method of forming two resist layers on a substrate is generally a double spin coating method (Dou).
ble spin coating)
A method of forming a plurality of resist layers on a substrate by a similar method is generally a multi-spin coating method (Multi-spin coating method).
It is called spin coating.

Conventionally, in a method for forming a fine structure such as the LIGA method, when forming a fine structure having a high aspect ratio, the substrate 1 is formed again with reference to FIG.
01 on the resist layer 1 using the multi-spin coating method.
02 was formed thick.

As a device for reducing the light diffraction effect, an electron storage ring (SR) of a synchrotron radiation device is used.
The synchrotron radiation emitted from the ring is converted to synchrotron radiation in a short wavelength region using an emission window of the synchrotron radiation or a light transmitting film (mask membrane) of an X-ray mask. A technique for selectively extracting synchrotron radiation having a wavelength component to be absorbed is known (solid state technology).
y / Japan version / November 1989, p. 33 ~
p. 41).

FIG. 10 is a view schematically showing a conventional exposure step in which a resist layer is irradiated with synchrotron radiation to expose a desired pattern to the resist layer while reducing the diffraction effect of light. It is.

Referring to FIG. 10, FIG. 10A is a view schematically showing a known X-ray exposure apparatus.
(B) schematically shows a conventional exposure step of irradiating a synchrotron radiation beam to a resist layer around a radiation window of the synchrotron radiation beam and an X-ray mask to expose a desired pattern on the resist layer. FIG.

Referring to FIGS. 10A and 10B, this X-ray exposure apparatus 201 includes a vacuum chamber 202.
And a sample table 203 accommodated in the vacuum chamber 202.

The sample table 203 on which the resist layer 102 is formed on the substrate 101 can be placed.

On the side wall 202a of the vacuum chamber 202,
A light inlet 205 is provided. An exhaust port 206 is provided on a side wall 202b of the vacuum chamber 202, and the inside of the vacuum chamber 202 can be evacuated by a vacuum pump (not shown) or the like.

The side wall 202c of the vacuum chamber 202
Is provided with an atmosphere gas introduction port 207. By opening and closing the valve V, an atmosphere gas such as helium (He) gas can be introduced into the vacuum chamber 202 as required. Has become. Sample 2
An X-ray mask 100 is provided on 04.

Since the structure of the X-ray mask 100 has already been described with reference to FIG. 8B, the same members are denoted by the same reference numerals, and description thereof will be omitted. The synchrotron radiation light (SR light) generated by the electron storage ring (SR ring) 209 of the synchrotron radiation device transmits through the synchrotron radiation light emission window 210 and then passes through the light inlet 205 to the vacuum chamber 202. And irradiates the resist layer 102 of the sample 204 placed on the sample stage 203 through the X-ray mask 100.

As the window material of the emission window 210 for the synchrotron radiation, for example, a window material made of beryllium (Be) is used.

Next, the principle of the exposure step in the method of forming a semiconductor integrated circuit having a finely processed portion having a line width of about 1 μm or a fine structure will be described in detail.

In order to reduce the light diffraction effect, synchrotron radiation (SR light) applied to the resist layer 102
It is necessary to use synchrotron radiation (SR light) in a short wavelength region, which is synchrotron radiation in a wavelength region absorbed by the resist layer.

More specifically, the resist material for X-rays is
Since it hardly absorbs light of short wavelength components of 3 mm or less,
In order to expose the resist layer while reducing the light diffraction effect, it is necessary to use synchrotron radiation in a wavelength region of 4 ° to 20 °.

FIG. 11 is a diagram showing the effects of the emission window 210 for synchrotron radiation and the light transmitting film (mask membrane) 100b of the X-ray mask 100.

Referring to FIG. 11, curve A _{1 in} FIG.
Indicates synchrotron radiation (SR light) generated by the electron storage ring (SR ring) 209. Note that, in FIG. 11, about 10
Fig. 5 shows a conventional example in which synchrotron radiation having a peak wavelength is generated.

In FIG. 11, a curve B ₁ shows the synchrotron radiation after passing through the emission window 210 of the synchrotron radiation, and a curve C ₁ further shows the light of the X-ray mask 100. The figure shows synchrotron radiation after transmission through a transmission film (mask membrane) 100b.

The curve D ₁ further corresponds to the X-ray mask 1
8 shows synchrotron radiation after passing through the X-ray absorber 100a of No. 00.

The synchrotron radiation C ₁ transmitted through the light transmitting film (mask membrane) 100 b of the X-ray mask 100 and the X-ray mask 100
Synchrotron radiation D transmitted through the light absorber 100a
_The desired pattern 102p is exposed due to the difference in contrast (light / dark) from ₁ .

As can be seen from FIG. 11, the angle of 4 ° or more is obtained through the emission window 210 for the synchrotron radiation and the light transmitting film (mask membrane) 100b of the X-ray mask 100.
The resist layer 102 is irradiated with synchrotron radiation in a wavelength region of 0 ° or less.

As described above, conventionally, in order to reduce the diffraction effect of light, the emission window 2 of the synchrotron radiation light has been conventionally used.
10 and the light transmitting film (mask membrane) 100b of the X-ray mask 100 has been used.

The light transmitting film (mask membrane) 10
Since the dimensional stability of the X-ray mask 100 is required as the material of Ob, for example, Si, SiN, SiC, S
Inorganic materials such as i ₃ N ₄ , BN, and Be are used.

The material of the X-ray absorber 100a is, for example, tungsten (W), tantalum (T
a), gold (Au) or the like is used.

[0063] The thickness d _100a of the X-ray absorber 100a of the conventional X-ray mask 100, at most, about 0.7 [mu] m ^t.

[0064]

The conventional multi-spin coating method has a disadvantage that when a thick resist layer is formed on a substrate, the spin coating method needs to be repeated many times, which is troublesome. Was.

More specifically, in the conventional multi-spin coating method, centrifugal force is used by rotating a substrate,
Since a solution layer containing a solvent is formed (coated) on the substrate or the resist layer to a uniform thickness, the thickness of the resist layer which can be formed by one spin coating operation is inevitable. It becomes thin.

For this reason, in the conventional multi-spin coating method, when forming a thick resist layer, it is necessary to repeat the spin coating operation many times.

[0067] Further, the conventional multi-spin coating, on a substrate, the film thickness of the resist layer which may be formed to a uniform thickness, the average thickness, at most, be up to about 45 [mu] m ^t, 45 [mu] m ^t There is a problem that it is difficult to form a resist layer having the above thickness on a substrate.

That is, in the conventional multi-spin coating method, as described above, after a solution containing a solvent is dropped on the resist layer, the substrate is rotated using a spinner or the like, so that the solvent is deposited on the resist layer. Is formed to form a solution layer containing

For this reason, since the already formed resist layer is soluble (soluble) in the solvent, a part or all of the already formed resist layer is placed on the solution layer side during the spin coating operation. Because it melts.

Further, polymethyl methacrylate (PMM)
The resist layer containing A) as a main component (base resin) has a problem of low sensitivity.

As a technique for solving such a problem, the present applicant discloses in Japanese Patent Application Laid-Open No. 5-159996 that a chemically amplified resist can be suitably used in a method for forming a fine structure. .

Further, the present inventors have disclosed a related art of particular interest in the present invention in Japanese Patent Application No. 5-66676, which discloses a method for forming a fine structure in the general formula.

[0073]

Embedded image

Wherein R ₁ is an alkyl group having 1 to 4 carbon atoms (the hydrogen atom of the alkyl group may be substituted with a halogen atom);

[0075]

Embedded image

Wherein X is a halogen atom or a hydroxyl group, and R ₂ is a hydrogen atom or a methyl group. A resist material containing, as a main component (base resin), a copolymer consisting of units represented by the formula: It discloses that it can be used.

The resist materials disclosed in JP-A-5-159996 and Japanese Patent Application No. 5-66676 have higher sensitivity than conventional polymethyl methacrylate (PMMA).

Therefore, if a resist material described in JP-A-5-159996 or Japanese Patent Application No. 5-66676 is used, a resist material containing polymethyl methacrylate (PMMA) as a main component (base resin) can be obtained. Compared to the case of using a resist pattern, a resist pattern having the same shape, more specifically, a resist pattern having the same height (thickness) d ₁₀₃ (height indicated by d ₁₀₃ in FIG. There is an effect that it can be formed by time exposure.

[0079] However, finding that the case of using any of the aforementioned resist material, the resist thickness of the pattern 103 (height) d ₁₀₃ that can be formed with high accuracy, there is a limit did.

More specifically, the thickness d of the resist layer 102
₁₀₂ (in FIG. 8 (a), the thickness indicated by d ₁₀₂₎ thick (e.g., about several 100 [mu] m) was formed, by using a synchrotron radiation (SR light), conventional exposure method shown in FIG. 10 When the resist layer 102 is deeply exposed, the solubility of the resist layer 102 in a developing solution is reduced in the upper layer portion or on the surface of the resist layer 102, and the resist pattern 103 becomes a tapered shape tapering downward, However, as the depth increases in the direction from the surface of the resist layer 102 toward the substrate 101, the line width becomes wider, or a portion which should be dissolved in the developing solution is not dissolved in the developing solution, and
No. 3 cannot be formed with high accuracy.

FIG. 12 shows such a resist pattern 1
It is sectional drawing which shows the phenomenon which arises in FIG. 03 typically.

Referring to FIG. 12, as shown in FIG. 8C, the resist pattern 103w has a sidewall 103s of the resist pattern which should be formed in the direction of the synchrotron radiation, There is a phenomenon that the portion 103p that should be dissolved in the developer does not dissolve in the developer.

FIG. 12 shows a phenomenon that occurs when a positive resist material is used as the resist material for ease of explanation. This is a phenomenon that occurs in common with both negative and negative resist materials.

Referring again to FIGS. 8 and 9, LIGA
In any of the methods for forming a fine structure such as the method, a fine structure is formed based on the resist pattern 103. Therefore, if a phenomenon shown in FIG. There is a problem that a structure cannot be obtained.

In a method for forming a fine structure such as the LIGA method, since the fine structure is formed based on the resist pattern, it is difficult for the resist pattern to lose its shape in the developing step. At
It is required that the resist pattern does not easily lose its shape.

In the conventional multi-spin coating method, since a solvent is used in the step of forming a resist layer on a substrate, the solvent may not be completely removed from the resist layer formed on the substrate. In the step of (1) and the step of electroplating, there is a problem that the resist pattern loses shape and a fine structure having a desired shape cannot be obtained.

Further, when the resist layer is formed thick by the conventional multi-spin coating method, the internal stress of the resist layer inevitably increases, causing cracks in the resist layer and peeling of the resist layer from the substrate. There was a problem of doing.

In the conventional method for forming a microstructure such as the LIGA method, it is difficult to form a microstructure having a high aspect ratio with high accuracy, easily and simply due to the above reasons. There was a problem that it was difficult.

The present invention has been made in order to solve the above-mentioned problems. In particular, the present invention has been made to improve a process of forming a resist layer on a substrate, and / or to radiate synchrotron radiation on a resist layer. By improving the exposure step of exposing a desired pattern to the resist layer by irradiating light, a fine structure having a high aspect ratio can be formed with high precision, easily and easily. It is an object of the present invention to provide a method for forming a film.

More specifically, referring to FIG. 8 (e), FIG. 9 (a) and FIG. 9 (e), as a line width dimension W, for example, a portion finely processed to about 1 μm to 10 μm;
As a height (thickness) H, a microstructure including a portion having a desired height (thickness) selected from several μm to several hundred μm, or as a line width dimension W, for example, 1 μm to
The part finely processed to about 10μm and the height (thickness)
It is an object of the present invention to provide a method for forming a fine structure capable of easily and easily forming a fine structure which may have a portion having a dimension of about several hundred μm or more as H.

[0091]

The inventor of the present invention has studied for a long time a method of forming a fine structure capable of easily and easily forming a fine structure having a high aspect ratio with high precision. I have continued.

As a result, it has been found that in order to easily and easily form a fine structure having a high aspect ratio with high accuracy, it is necessary to devise a device satisfying the following conditions.

(1) As compared with the conventional multi-spin coating method, it is necessary to devise a method capable of easily and easily forming a resist layer on a substrate with a uniform thickness and a large thickness.

(2) It is necessary to devise a technique that can completely remove the solvent from the resist layer formed thickly on the substrate.

As described above, if the solvent remains in the resist layer, the resist pattern loses its shape in the developing process and the electroplating process.

In a method for forming a fine structure such as the LIGA method, a fine structure is formed based on a resist pattern.
This is because a fine structure as designed cannot be obtained.

(3) It is necessary to take measures to reduce the internal stress of the resist layer formed thick on the substrate.

(4) It is necessary to prevent the resist layer from peeling off from the substrate. (5) In the exposure step of irradiating the resist layer with synchrotron radiation to expose a desired pattern to the resist layer and the developing step of developing the resist layer exposed to the desired pattern to form a resist pattern, ,
The following measures are required.

It is necessary to devise a device capable of exposing the resist layer to a fine line width with high accuracy by reducing the light diffraction effect.

In the developing step of developing the resist layer on which the desired pattern has been exposed to form a resist pattern, it is necessary to take measures to reduce the phenomenon shown in FIG.

The present inventor has shown that the resist pattern is
As shown in (1), as a result of research on the cause of the tapered shape tapering downward or the portion that should be originally dissolved in the developing solution does not dissolve in the developing solution, the following facts have been found.

FIG. 13 is a diagram schematically showing the energy absorbed by the resist material. In FIG. 13, for ease of explanation, a positive resist material, more specifically, polymethyl methacrylate (PMMA) is used as the resist material.
A resist material containing as a main component (base resin) will be described as an example.

Referring to FIG. 13, a curve A ₂ represents an electron storage link (SR ring) 20 of the synchrotron radiation device.
9 shows a synchrotron radiation having a peak wavelength at about 10 ° generated by FIG.

The curve B ₂ shows the synchrotron radiation after passing through the emission window 210 for the synchrotron radiation.

The curve C ₂ further shows the X-ray mask 1
10 shows the synchrotron radiation after passing through the light transmitting film (mask membrane) 100b of No. 00.

In FIG. 13, a curve I (curve I indicated by a broken line in FIG. 13) indicates energy absorbed per unit volume of the resist material.

[0107] Figure 13 As is clear, and the exit window 210 of the synchrotron radiation light, in synchrotron radiation (13 transmitted through the light-transmitting film (mask membrane) 100b of the X-ray mask 100, a curve C ₂ The light shown) is 2
In a wavelength region of 0 ° or less, the light is continuous light.

The light-transmitting film (mask membrane) made of an inorganic material such as Si or SiN described above.
100b absorbs most of the long-wavelength component light exceeding 15 °, and is excellent in light transmittance in the wavelength region of 5 ° to 15 °.

As is apparent from FIG. 13, the resist material easily absorbs light in the wavelength region of 5 ° to 15 °, in particular, in the wavelength region of 4 ° to 20 ° absorbed by the resist material.

Further, the present inventor has found that in the developing step,
In order to form a resist pattern of a desired shape with high accuracy without causing the phenomenon shown in FIG. 12, in the exposure step of exposing the resist layer, the exposure amount of the synchrotron radiation to irradiate the resist layer is I came to find that there is a certain range.

That is, in order to form a resist pattern having a desired shape with high accuracy without causing the phenomenon shown in FIG. 12 in the developing step, the resist layer is irradiated in the exposure step of exposing the resist layer. They have found that the irradiation amount of synchrotron radiation and the absorption energy density absorbed by the resist layer have a certain range.

More specifically, it has been found that the amount of synchrotron radiation applied to the resist layer has a lower limit of the amount of light and an upper limit of the amount of light. .

The term “lower limit of light irradiation amount” used in the present specification means that when the resist material constituting the resist layer is a positive resist material, the main chain of the resist material constituting the resist layer is light-emitting. By cutting, the resist material is decomposed, the molecular weight is reduced, and the minimum irradiation amount of light necessary for the resist layer to be soluble in a solvent such as a developer is meant.

The term “lower limit of light irradiation amount” used in the present specification means that when the resist material constituting the resist layer is a negative resist material, the main chain of the resist material constituting the resist layer is The cross-linking by light means that the resist material is polymerized, the molecular weight increases, and the minimum irradiation amount of light required for the resist layer to become insoluble in a solvent such as a developing solution.

The term “upper limit of light irradiation amount” used in this specification means that when the resist material constituting the resist layer is a positive resist material, the main chain of the resist material constituting the resist layer is After being cut by light, the resist material is once decomposed, the molecular weight is reduced, and after the resist layer becomes soluble in a solvent such as a developer,
The amount of irradiation of light that causes a decomposition product of the resist material by light to be polymerized again by light to make the resist layer insoluble in a solvent such as a developer.

The term “upper limit of light irradiation amount” used in the present specification means that when the resist material constituting the resist layer is a negative resist material, the main chain of the resist material constituting the resist layer is , By being cross-linked by light, once the resist material is polymerized, the molecular weight increases, and after the resist layer becomes insoluble in a solvent such as a developer,
This means the amount of light irradiation at which the polymer of the resist material due to light is decomposed again by light and the resist layer becomes soluble in a solvent such as a developer.

The absorbed energy density absorbed by the resist layer has an upper limit of the absorbed energy density and a lower limit of the absorbed energy density.

As used herein, the term “absorbed energy density” means the energy absorbed by a substance per unit volume, for example, a value specified in units of J / cm ³ .

The term “lower limit of absorbed energy density” used in this specification means that when the resist material constituting the resist layer is a positive resist material, the main chain of the resist material constituting the resist layer is: By being cut by light, the resist material is decomposed, the molecular weight is reduced,
It means the minimum absorbed energy density necessary for the resist layer to become soluble in a solvent such as a developer.

The term “lower limit of absorbed energy density” used in the present specification means that when the resist material constituting the resist layer is a negative resist material, the main chain of the resist material constituting the resist layer is: By being cross-linked by light, the resist material polymerizes and the molecular weight increases,
It means the minimum absorbed energy density required for the resist layer to become insoluble in a solvent such as a developer.

The term “upper limit of absorbed energy density” used in the present specification means that when the resist material constituting the resist layer is a positive resist material, the main chain of the resist material constituting the resist layer is: After being cut by light, the resist material is once decomposed, the molecular weight is reduced, and the resist layer becomes soluble in a solvent such as a developing solution. Means the absorption energy density of light that is polymerized again by light to make the resist layer insoluble in a solvent such as a developing solution.

The term “upper limit of the absorbed energy density” used in the present specification means that when the resist material constituting the resist layer is a negative resist material, the main chain of the resist material constituting the resist layer is: By being cross-linked by light, the resist material is polymerized once, the molecular weight is increased, and after the resist layer becomes insoluble in a solvent such as a developer, a polymerized product of the resist material by light becomes It means the absorption energy density of light that is decomposed again by light and makes the resist layer soluble in a solvent such as a developer.

The present inventor has found that the upper limit of the light absorption energy density and the lower limit of the light absorption energy density are as follows:
Regardless of the wavelength component of the light, the composition of the resist material
It has been found that some components have unique values.

More specifically, referring again to FIG.
The upper limit of the absorption energy density of the resist material is the absolute value (integral value) of the area surrounded by the curve I _max per unit volume.
A value is identified as, does not depend on the shape of the curve I _max.

[0125] Similarly, the lower limit value of the absorption energy density of the resist material is a value that is specified as an absolute value (integral value) of the area enclosed by the curve I _min per unit volume, the shape of the curve I _{mi n} I don't care.

Of the light in the wavelength region that is easily absorbed by the resist layer, the light in the wavelength region that is particularly easily absorbed by the resist layer, specifically, the light in the wavelength region of 5 ° to 15 ° is the upper part of the resist layer or Easily absorbed on the surface,
In the depth direction of the resist layer, only the light absorbed by the upper layer portion or the surface of the resist layer reaches as attenuated light.

[0127] Thus, in the development step, with high accuracy, the maximum value of the height d ₁₀₃ of the resist pattern can be formed into a desired shape (d ₁₀₃ shown in FIG. 8 (c)), an upper portion of the resist or When the absorption energy density reaches the upper limit value on the surface, it is uniquely determined by the distance from the position where the absorption energy density of the resist layer has the lower limit value in the depth direction of the resist layer.

Therefore, in the depth direction of the resist layer, the height (thickness) can be increased without causing the phenomenon shown in FIG.
To form a resist pattern 103 having d ₁₀₃ ,
While reducing the increase in the absorbed energy density at the upper layer or surface of the resist layer, the light in the wavelength region that is absorbed by the resist layer, and the light in the wavelength region that is easily absorbed by the upper layer or surface of the resist layer, Specifically, 5Å or more and 20
(4) Light that hardly attenuates in the depth direction of the resist layer from which some or all of the light components in the following wavelength regions have been removed may be used.

The present inventor has made intensive efforts on the technology satisfying the above conditions (1) to (5), and as a result, has completed the present invention.

That is, the first invention is to improve the exposure step of exposing a desired pattern to the resist layer by irradiating the resist layer with synchrotron radiation. , While reducing the increase in absorbed energy density at the upper layer or surface of the resist layer, and
The present invention relates to a method for forming a fine structure capable of irradiating synchrotron radiation having a small light attenuation effect in a depth direction of a resist layer.

That is, in the method for forming a fine structure according to the first invention, a step of forming a resist layer on a substrate and irradiating the resist layer with synchrotron radiation to expose a desired pattern to the resist layer An exposing step, a developing step of developing a resist layer on which a desired pattern is exposed to form a resist pattern, and a microstructure forming method for forming a microstructure based on the resist pattern; Is characterized in that the resist layer is exposed through a filter having substantially the same absorption spectrum as the resist layer.

Further, the second invention provides the above (1) to (5)
The present invention relates to a method for forming a fine structure that satisfies the condition of (1).

That is, in the method for forming a fine structure according to the second invention, a step of forming a resist layer on a substrate and irradiating the resist layer with synchrotron radiation to expose a desired pattern to the resist layer An exposure step, a development step of developing a resist layer on which a desired pattern is exposed, and a development step of forming a resist pattern, based on the resist pattern, a method of forming a fine structure based on the resist pattern, comprising: The step of forming a resist layer on the substrate,
A step of placing a frame material having a hollow portion, a step of filling a syrup containing a monomer and a polymer obtained by polymerizing the monomer in the hollow portion, a monomer, and a monomer And a polymerization completion step of completely polymerizing a syrup containing a polymer obtained by polymerization on the substrate, and the exposure step includes passing the resist layer through a filter having substantially the same absorption spectrum as the resist layer. Expose.

Further, in the first or second invention, preferably, the filter material constituting the filter is substantially the same as the material forming the resist layer.

Further, in the first or second invention, preferably, the filter material constituting the filter is polyimide. Polyimide is 20
材料 It is a material whose light absorption spectrum and absorption coefficient in the following wavelength range are similar to those of the resist material for X-rays, and is excellent in heat resistance and light resistance. This is because the material is excellent in radiation resistance, such as hardly being generated.

The term “filter having substantially the same absorption spectrum as the resist layer” used in the present specification may be specified as a filter having substantially the same absorption coefficient as the resist layer.

In the first or second aspect of the present invention, the resist material constituting the resist layer formed on the substrate may be a known X-ray resist material.

Examples of such X-ray resist materials include:
A positive resist material and a negative resist material can be used.

As such an X-ray resist material, a positive resist material containing polymethyl methacrylate (PMMA) as a main component (base resin) can be mentioned.

As such a resist material for X-rays, a general formula

[0141]

Embedded image

In the above formula, R ₁ is a unit represented by an alkyl group having 1 to 4 carbon atoms (the hydrogen atom of the alkyl group may be substituted by a halogen atom);

[0143]

Embedded image

[Wherein, X is a halogen atom or a hydroxyl group, and R ₂ is a hydrogen atom or a methyl group]. A combined resist material can be used.

More specifically, the copolymer resist material is
Methyl methacrylate (MMA) and methacrylic acid (MA
A positive copolymer resist material containing a copolymer with A) as a main component (base resin) is preferred.

As such a resist material for X-rays, a negative resist material containing poly (glycidyl methacrylate) as a main component (base resin) can be mentioned.

The resist material for X-rays contains, as a main component (base resin), a copolymer of glycidyl methacrylate and ethyl acrylate or a copolymer of glycidyl methacrylate and methyl methacrylate. A negative-type copolymer resist material can be used.

The resist material for X-rays is mainly composed of chloromethylated polystyrene, iodinated polystyrene, and polymethylstyrene chloride (base resin).
And a negative resist material.

[0149] The term "synchrotron radiation" used herein refers to an electromagnetic wave emitted when high-energy electrons near the speed of light are bent in orbit by a magnetic field in an accelerator.

Synchrotron radiation is light having a continuous spectrum over a wide wavelength range. More specifically, synchrotron radiation is light having a continuous spectrum of about 0.1 ° from hard X-rays to far infrared rays.

The term “peak wavelength” as used herein means a wavelength at which the amount of photons or the photon power of synchrotron radiation is maximized.

The peak wavelength can be controlled to a desired wavelength by changing the magnitude of the magnetic force of the electron storage ring (SR ring) of the synchrotron radiation device (light source).

The synchrotron radiation used in the first or second invention is preferably a synchrotron radiation having a peak wavelength of less than 10 °, more preferably a synchrotron radiation having a peak wavelength of not less than 4 ° and not more than 5 °. Synchrotron radiation having a peak wavelength of 5 °.

Further, in the first or second invention,
"The filter material constituting the filter is substantially the same material as the resist material constituting the resist layer."
Although not particularly limited to the following cases, for example,
When the resist layer formed on the substrate is made of an acrylic resist material, it means that the material constituting the filter is made of an acrylic resin. More preferably, for example, the resist layer formed on the substrate is made of polymethyl methacrylate (PMMA)
Is composed of a resist material containing as a main component (base resin), the material constituting the filter is composed of a resin containing polymethyl methacrylate (PMMA) as a main component, and the resist layer formed on the substrate is For example, methyl methacrylate (MMA) and methacrylic acid (M
In the case where the filter is composed of a resist material containing a copolymer of AA) as a main component (base resin), the material constituting the filter is a copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA) Or a relation equivalent to such a relation.

In the second invention, the monomer is preferably a methyl methacrylate monomer, and the polymer is polymethyl methacrylate.

Further, in the second invention, the monomer is represented by the following general formula:

[0157]

Embedded image

Wherein R ₁ is an alkyl group having 1 to 4 carbon atoms (a hydrogen atom of the alkyl group may be substituted with a halogen atom);

[0159]

Embedded image

Wherein X is a halogen atom or a hydroxyl group, and R ₂ is a hydrogen element or a methyl group. The polymer is exemplified by the following general formula. It is a copolymer that can be used.

[0161]

Embedded image

Wherein R ₁ is an alkyl group having 1 to 4 carbon atoms (the hydrogen atom of the alkyl group may be substituted with a halogen atom), X is a halogen atom or a hydroxyl group,
R ₂ is a hydrogen atom or a methyl group.] More specifically, examples of the monomer represented by Chemical Formula 5 include methyl methacrylate (methyl methacrylate), 2-fluoroethyl methacrylate, 2,2,2
-Trifluoroethyl methacrylate, tetrafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, 2-chloroethyl methacrylate, 2-
Bromoethyl methacrylate and the like can be mentioned, and as the monomer represented by the above formula 6, for example, methacrylic acid, methacryloyl halogenide, acrylic acid,
Acryloyl halogenide and the like can be mentioned.

In the second invention, the monomer is preferably a mixture of a methyl methacrylate (MMA) monomer and a methacrylic acid (MAA) monomer, and the polymer is methyl methacrylate (MMA) and methacrylic acid. Acid (M
AA).

In the second invention, the monomer is preferably a glycidyl methacrylate monomer,
The polymer is characterized by being polyglycidyl methacrylate.

Further, in the second invention, the monomer is preferably a mixture of a glycidyl methacrylate monomer and an ethyl acrylate monomer, and the polymer is a copolymer of glycidyl methacrylate and ethyl acrylate. Features.

In the second invention, the monomer is preferably a mixture of a glycidyl methacrylate monomer and a methyl methacrylate monomer, and the polymer is a copolymer of glycidyl methacrylate and methyl methacrylate. It is characterized by the following.

Further, in the second invention, the monomer is preferably a chloromethylated styrene monomer, and the polymer is chloromethylated polystyrene.

In the second invention, the monomer is preferably an iodinated styrene monomer, and the polymer is iodinated polystyrene.

Further, in the second invention, the monomer is preferably a methyl styrene chloride monomer, and the polymer is polymethyl styrene chloride.

As a method for preparing a syrup containing a monomer and a polymer obtained by polymerizing the monomer, a certain amount of the charged monomer (monomer) is polymerized, and Preparation by coexisting a part of the body (monomer) and the produced polymer (polymer) (hereinafter referred to as prepolymerization), or mixing the monomer and the polymer May be prepared.

In the second invention, the frame member is preferably made of a metal represented by stainless steel.

Further, the frame material used in the second invention is:
Preferably, at least the surface is covered with a resin having a releasing property represented by a fluororesin.

Examples of such a fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), Specific examples thereof include tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVdF), and polychlorotrifluoroethylene (PCTFE).

Further, in the second invention, the viscosity of a syrup containing a monomer and a polymer obtained by polymerizing the monomer is as follows:
Preferably, it is not less than 2.0 dPa · s (20 ° C.) and 10.0
dPa · s (20 ° C.) or less. More preferably, it is 2.0 dPa · s (20 ° C.) or more and 8.0 or more.
dPa · s (20 ° C.) or less.

When the viscosity of the syrup is 2.0 dPa · s (20
C)), the syrup leaks out of the hollow portion of the frame material, and the thickness of the formed resist layer becomes thin, which is not preferable. On the other hand, when the value exceeds the above upper limit, the syrup is formed in the hollow portion of the frame material. In the step of filling the syrup, it is not preferable because air bubbles caught in the syrup hardly come out of the syrup.

[0176]

As used herein, the term “monomer” or “monomer” has a function of dissolving a solute, more specifically, a polymer, and itself has reactivity,
A material that becomes a polymer when polymerized.

More specifically, “monomer” or “monomer” refers to a material having a polymerizable functional group such as a vinyl group in the molecule.

The term “lithography” used in this specification refers to an exposure step of exposing a resist layer and a development step of developing the resist layer.

Further, in this specification, when the term “electroplating” is simply used, electroplating is included in addition to literal electroplating.

The thickness of the filter used in the first or second invention depends on the thickness (height) of the pattern to be exposed with respect to the resist layer.

[0182]

[0183] Further, in the first or second invention, the average film thickness of the resist layer to be formed on the substrate, but are not limited especially in the case of less, the film thickness of more than 3 [mu] m ^t, more preferably more than 45 [mu] m ^t, more preferably, 100 [mu] m ^t or more, more preferably, 10
It is not less than 0 μm ^{t and not} more than 1 mm ^t .

The filter used in the first or second invention can be manufactured according to a known thin film forming method.

More specifically, a known production method such as a roll coater method can be used.

[0186]

The method for forming a microstructure according to the first invention is substantially the same as the resist layer in the exposing step of irradiating the resist layer with synchrotron radiation to expose a desired pattern to the resist layer. The resist layer is exposed through a filter having the following absorption spectrum.

Although the resist layer varies depending on the type of the resist material constituting the resist layer, generally, the X-ray resist material absorbs light in a wavelength range of 4 ° to 20 °.

In the first invention, in the exposure step of exposing a desired pattern to the resist layer, the resist layer is irradiated with synchrotron radiation through a filter having substantially the same absorption spectrum as the resist layer. ing.

A filter having an absorption spectrum substantially the same as that of the resist layer has a wavelength range of 4 to 20 ° which is absorbed by the resist layer. Light in the easy wavelength range, more specifically, light in the wavelength range of 5 ° to 20 ° is more absorbed.

Therefore, the synchrotron radiation transmitted through a filter having substantially the same absorption spectrum as that of the resist layer is the light in the wavelength range that is easily absorbed by the resist layer, out of the light in the wavelength range that is absorbed by the resist layer. All or part of the light is removed.

In the first invention, among the light in the wavelength region absorbed by the resist layer, the light in the wavelength region that is easily absorbed by the resist layer is irradiated with the synchrotron radiation attenuated in advance. In the upper layer portion or the surface of the resist layer, light components in the wavelength region to be absorbed are small.

Therefore, this light has a remarkably low light attenuation effect in the depth direction of the resist layer.

Therefore, in the first aspect, it is possible to perform deep exposure in the depth direction of the resist layer before the upper layer portion or surface of the resist layer reaches the upper limit of the absorbed energy density.

More specifically, before the upper layer portion or surface of the resist layer reaches the upper limit of the absorbed energy density, the position where the lower limit of the absorbed energy density of the resist layer is set is determined by the depth of the resist layer. In the direction, it can be formed at a deeper position.

Therefore, according to the first invention, FIG.
The height (see FIG. 2 (c)) without the phenomenon shown in FIG.
A resist pattern (resist structure) having d ₃ ) shown therein can be formed with high precision.

According to the first aspect of the invention, it is formed with high precision,
Further, a fine structure is formed based on a resist pattern having a height.

As a result, according to the first aspect, a fine structure having a fine line width and a large thickness and a large aspect ratio can be formed with high accuracy.

The method for forming a microstructure according to the second invention has the following configuration, particularly in the step of forming a resist layer on a substrate.

(1) A step of mounting a frame member having a hollow portion on a substrate is provided. (2) A step of filling the hollow portion with a syrup containing a monomer and a polymer obtained by polymerizing the monomer is provided.

(3) A polymerization completion step of completely polymerizing a syrup containing a monomer and a polymer obtained by polymerizing the monomer on a substrate is provided.

According to the method of forming a microstructure according to the second aspect, the resist layer is formed on the substrate by the steps (1) to (3).

That is, the thickness of the resist layer formed on the substrate depends on the height of the frame material. Therefore, in the step (1), the thickness of the resist layer can be easily and easily controlled only by changing the height of the frame material.

In the step (2), not the syrup containing the polymer and the solvent but the syrup containing the monomer and the polymer obtained by polymerizing the monomer is filled in the hollow portion. Further, in the step (3), the syrup containing the monomer and the polymer obtained by polymerizing the monomer is completely polymerized on the substrate, so that the syrup is formed according to the second invention. A solvent is not originally contained in the resist layer.

That is, the solvent is not originally contained in the resist layer formed according to the second invention.
When exposing the resist layer using synchrotron radiation and developing the exposed resist layer to form a resist pattern, the resist pattern does not lose its shape.

The resist pattern thus formed does not originally contain a solvent, so that the resist pattern does not lose its shape even in the electroplating step.

According to the second aspect of the present invention, the syrup containing the monomer and the polymer obtained by polymerizing the monomer is completely polymerized on the substrate. Excellent adhesion with

Further, the method for forming a fine structure according to the second invention comprises, in the exposure step of irradiating the resist layer with synchrotron radiation to expose a desired pattern on the resist layer, particularly including the following steps: Things.

(4) The exposing step is performed through a filter having substantially the same absorption spectrum as that of the resist layer.
Exposing the resist layer.

Therefore, according to the second invention, similarly to the first invention, the resist pattern having a height (d ₃ shown in FIG. 2C) can be obtained without causing the phenomenon shown in FIG. (Resist structure) can be formed with high precision.

According to the second aspect of the present invention, the wiring is formed with high precision.
And a resist pattern with a height (resist structure)
Further, in the development step and the electroplating step, a fine structure is formed based on a resist pattern (resist structure) that does not easily lose its shape.

As a result, according to the second aspect of the invention, a fine structure having a fine line width and a large thickness and a large aspect ratio can be formed easily and easily with high precision.

[0212]

The present invention will be described below with reference to preferred embodiments, but the present invention is not limited to the following embodiments.

FIGS. 1 and 2 are process diagrams schematically showing a manufacturing process as an example of a method for forming a fine structure according to the present invention.

Hereinafter, for ease of explanation, an embodiment will be described with reference to FIGS. 1 and 2.

Examples 1 to 3 and Reference Examples In Examples 1 to 3, a resist material containing a copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA) as a main component (base resin) was used as a resist material. Here, an example in which a fine structure is formed by using is shown.

Example 1 (1) Preparation of a syrup containing a monomer and a polymer obtained by polymerizing the monomer As a starting material, 95 g (0.95) of a methyl methacrylate (MMA) monomer (molecular weight: 100) was used. Mol) and 5 g of methacrylic acid (MAA) monomer (molecular weight 86).
(0.051 mol) is prepared as a mixed solution. Next, 2,2-
0.2 g of azoisobutyronitrile (about 0.2% by weight based on the mixed solution of the above monomers) was added, and preliminarily polymerized at 60 ° C. for 50 minutes by a bulk polymerization method in an N ₂ gas atmosphere. To prepare a copolymer syrup containing a copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA) as a main component.

The weight average molecular weight of this copolymer syrup was 400,000. In Example 1, the pre-polymerization conditions were set to 5 ° C. in a temperature range of 40 ° C. to 120 ° C.
Copolymer syrups having various viscosities were prepared in the same manner except that the syrup was changed in the range of minutes to 240 minutes.

(2) Formation of Resist Layer FIG. 1 is a process diagram schematically showing an embodiment of a process of forming a resist layer on a substrate.

Referring to FIG. 1, first, in the step shown in FIG. 1A, a hot plate (heating means) 11
For example, a substrate 1 such as a silicon (Si) substrate is placed.

Next, a frame member (spacer) 12 having a hollow portion 12m is placed on the substrate 1. In addition, as a constituent material of the frame member (spacer) 12, a metal material such as stainless steel, a glass material, a fluororesin, or the like can be given.

A stainless steel frame material (spacer)
When a frame material (spacer) made of glass is used, it is preferable that the surface thereof is coated with a fluororesin.

This is to improve the releasability of the frame material (spacer) and the resist layer in a later step.

The frame material (spacer) 12 controls the application area of the resist layer formed on the substrate 1 and the application area and the thickness of the resist layer.

More specifically, the application area of the resist layer is controlled by the size of the opening of the hollow portion 12m of the frame member (spacer) 12, and the application area of the resist layer is controlled by the shape of the opening of the hollow portion 3m. The thickness of the resist layer is controlled by the height 12h of the side wall 12s of the hollow portion 12m.

In the following description, for ease of explanation,
A description will be given mainly of an example in which the opening of the hollow portion 12m has a circular shape with a diameter of 25 mm and the height 12h of the side wall 12s uses a frame material (spacer) of 100 μm.

In the step shown in FIG. 1B, methyl methacrylate (MMA) prepared according to the above (1) was used.
A syrup (resist solution) S ₂ containing a monomer, a methacrylic acid (MAA) monomer, and a copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA) is placed in a hollow portion 12 m of a frame member (spacer) 12. Inside, it is dropped and filled.

Next, in the step shown in FIG. 1 (c), a Kapton sheet (release sheet) 13 is placed on a frame material (spacer) 12, and further a Kapton sheet (release sheet) 13 Then, the metal plate 14 is placed, and the weight 15 is placed on the metal plate 14.

"Kapton sheet" is a polyimide sheet, and "Kapton" is a trade name of DuPont.

In this embodiment, a stainless steel frame member (spacer) 12 is used. Further, Kapton sheet 13, a releasing property between the resist layer, Kapton sheet and syrup (resist liquid) between S ₂ of the surface, those used to makes it easier to prevent the gas from entering is there.

The Kapton sheet (release sheet) 13
And between the syrup (resist liquid) S ₂ of the surface, in order to prevent the gas from entering, in the step shown in FIG. 1 (b), the syrup (resist liquid) S _2, in the hollow portion 12m , by surface tension, than the upper portion of the hollow portion 12m, syrup (resist liquid) surface of S ₂ is preferably be filled as rise.

In consideration of the above, the viscosity of the syrup (resist liquid) S ₂ is 2.0 dPa · s (20
° C) or more and 10.0 dPa · s (20 ° C) or less. More preferably, 2.0 dPa · s (20
° C) or more and 8.0 dPa · s (20 ° C) or less.

That is, the syrup (resist liquid) to be filled in the hollow portion 12m of the frame member (spacer) 12 must be a liquid having a high viscosity.

[0233] More specifically, in the hollow portion 12m, in the step of filling the syrup (resist liquid) S _2, syrup (resist liquid) S _2, together with being held in the hollow portion 12m, the hollow portion in 12m, syrup (resist liquid) of S _2, because completely has to be filled.

Next, the syrup (resist liquid) S ₂ filled in the hollow portion 12 m is heated by the hot plate (heating means) 11, so that the syrup (resist liquid) S ₂ is completely on the substrate 1. After polymerization, room temperature (20
C) to form a resist layer 2.

The resist layer 2 formed on the substrate 1
Accumulates internal stress during solidification. In order to alleviate (reduce) the internal stress, it is preferable to appropriately perform a heat treatment, that is, a so-called annealing treatment.

[0236]

By appropriately performing such a heat treatment, it is possible to prevent the occurrence of cracks in the resist layer 2 formed on the substrate 1.

Next, in the step shown in FIG. 1D, the weight 15, the metal plate 14, the Kapton sheet (release sheet) 13
By removing the frame material (spacer) 12, the substrate 1 having the resist layer 2 is taken out.

In this manner, a film having a thickness of 100
A resist layer 2 having a uniform thickness of μm was formed.

Next, the height 1 of the side wall 12s of the hollow portion 12m
Various film thicknesses (several tens μm to several hundred μm) in the same manner as described above except that a frame material (spacer) having a different 2h is used.
A plurality of substrates 1 (hereinafter, referred to as samples) having a resist layer having

Next, the presence or absence of cracks in the resist layer and the presence or absence of peeling between the resist layer and the substrate were observed for a plurality of samples prepared as described above.

Presence or Absence of Cracks in the Resist Layer In any of the samples prepared as described above, cracks hardly occurred, and in the step of forming a resist pattern using lithography using synchrotron radiation,
It was confirmed that it was suitably used.

Presence or Absence of Peeling of Resist Layer from Substrate All samples having a resist layer thickness of 100 μm or less have good adhesion to the resist layer and the substrate. Almost never confirmed.

On the other hand, in the case of a sample having a resist layer thickness of more than 100 μm, peeling between the substrate and the resist layer, which is considered to have occurred in the step of removing the frame material (spacer) from the resist layer after forming the resist layer, was performed. Was observed.

The cause of the peeling of the resist layer from the substrate is that when the thickness of the resist layer exceeds 100 μm, the releasability between the frame material (spacer) and the resist layer is significantly deteriorated.

For the purpose of improving the releasability between the frame material (spacer) and the resist layer, a material obtained by coating the surface of the frame material (spacer) with a fluororesin is used. When a resist layer having a thickness exceeding 100 μm is formed on a substrate such as a silicon (Si) substrate, the adhesion of the resist layer to the substrate is improved, and the peeling between the resist layer and the substrate is almost eliminated. confirmed.

In order to improve the releasability between the frame material (spacer) and the resist layer, a silicon (Si) substrate or the like is used in the same manner as described above by using a frame material (spacer) made of fluororesin. When a resist layer having a thickness of more than 100 μm was formed on the substrate, it was confirmed that the adhesion of the resist to the substrate became good, and peeling between the resist layer and the substrate was almost eliminated.

(3) Formation of Fine Structure In this embodiment, for ease of explanation, a resist layer is formed as a fine structure on a substrate, and the resist layer is subjected to lithography using synchrotron radiation. An example in which a resist pattern is formed using the above method and a structure is deposited by electroplating according to the resist pattern will be described.

FIG. 2 is a process diagram schematically showing a step of forming a resist pattern on the resist layer by lithography using synchrotron radiation and a step of forming a fine structure by electroplating according to the resist pattern. It is.

Referring to FIGS. 2 and 8, FIGS.
In the step shown in FIG. 2E, the step shown in FIG. 2A is different from the step shown in FIG. 8A, and the step shown in FIG.
Are basically the same as the steps shown in FIGS. 8A to 8E except that the step shown in FIG. 8B is different from the step shown in FIG.

That is, in the method for forming a microstructure shown in this embodiment, the resist layer 2 formed in the above (1) and (2) is formed in the steps shown in FIGS. 2 (a) and 2 (b). Emission window 21 for synchrotron radiation
0, in addition to the X-ray mask 100, the synchrotron radiation is irradiated through a filter 50 having substantially the same absorption spectrum as the resist layer 2 to expose the resist layer 2. 8 (a) and FIG. 8 (b)
In the process shown in (2), the resist layer 102 formed by the conventional multi-spin coating method is passed through the synchrotron radiation light emission window 210 and the X-ray mask 100.
The method is particularly different from the conventional method for forming a fine structure in which the resist layer 102 is exposed by irradiating synchrotron radiation.

That is, referring to FIG. 2, first, FIG.
In the step shown in (a), the substrate 1 having the resist layer 2 formed in (1) and (2) above (hereinafter referred to as
"Sample 4") is prepared.

Next, in the step shown in FIG. 2B, the resist layer 2 is irradiated with synchrotron radiation (SR light) to expose the resist layer 2 with a desired pattern.

FIG. 3 is a diagram for explaining the step shown in FIG. 2B in more detail. Referring to FIG. 3, FIG.
FIG. 3 is a view schematically showing an X-ray exposure apparatus used in the present embodiment, and FIG. 3B is a view corresponding to FIG. 2B.

Referring to FIG. 3 (a) and FIG. 3 (b)
Since the X-ray exposure apparatus 61 has the same configuration as that of the X-ray exposure apparatus 201 shown in FIG. 10A, corresponding members are denoted by corresponding reference numerals, and description thereof will be omitted.

Next, the exposure step of irradiating the resist layer 2 with synchrotron radiation (SR light) to expose a desired pattern on the resist layer 2 will be described in detail.

First, a sample 4 having a resist layer 2 formed on a substrate 1 is placed on a sample table 203.

Next, an X-ray mask 100 is placed on the sample 4.
And a filter 50 having substantially the same absorption spectrum as the resist layer 2 is provided.

Next, the interior of the vacuum chamber 202 is evacuated to a desired vacuum state (10 ⁻³ To
rr to 10 ^-5 Torr).

If necessary, the vacuum chamber 202
Atmosphere gas such as helium (He) gas is introduced thereinto (~
760 Torr).

Next, the synchrotron radiation light (SR light) generated by the electron storage ring (SR ring) 209 of the synchrotron radiation light device is transmitted to the synchrotron radiation light emission window 210, the X-ray mask 100, and the filter 50. Then, the resist layer 2 of the sample 4 placed on the sample table 203 is irradiated.

[0262] In the present embodiment, as exit window 210 of the synchrotron radiation was used beryllium (Be) window made of the average thickness of 35 [mu] m ^t.

[0263] Further, as the light-transmitting film (mask membrane) 100b of the X-ray mask 100, S of the average film thickness 2 [mu] m ^t
A light transmitting film (mask membrane) made of iN was used.

Further, the light absorber 100 of the X-ray mask 100
As a, it was used gold (Au) made of a light absorber having an average thickness of 5 [mu] m ^t.

As the filter 50, an average film thickness of 5
A 0 μm ^t polyimide filter (trade name Kapton, manufactured by Toray Dupont) was used.

The polyimide is mainly composed of a copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA) in the wavelength range of 4 ° to 20 ° (base resin).
Has substantially the same absorption spectrum and substantially the same light absorption coefficient as the resist layer 2 containing

In the present embodiment, as the resist layer 2, 50
A resist layer having a thickness in the range of μm to 350 μm was used as a sample.

In this example, NIJI-III (DRI) was used as the synchrotron radiation device.

Then, the electron storage ring (SR ring) of the synchrotron radiation device (DENSO NIJI-III)
209, zero-order light of synchrotron radiation (SR light) having a peak wavelength at about 5 ° was generated.

The irradiation amount is the accumulated beam current value of 2
It was 0 mA · hour to 400 mA · hour.

Also, a light source (a synchrotron radiation device)
The distance between the sample and the sample was 10 m.

FIG. 4 shows an emission window 2 for synchrotron radiation.
FIG. 10 is a diagram illustrating the effects of a light transmission film (mask membrane) 100 b of the X-ray mask 100 and a filter 50.

Referring to FIG. 4, curve A in FIG. 4 shows synchrotron radiation (SR light) generated by electron storage ring (SR ring) 209.

In FIG. 4, curve B shows the synchrotron radiation after passing through the emission window 210 of the synchrotron radiation, and curve C shows the X-ray mask 1
8 shows the synchrotron radiation light after passing through the light transmitting film (mask membrane) 100b of No. 00.

The curve E ₁ further shows that the filter 5
2 shows synchrotron radiation after transmission through zero.

Next, in the step shown in FIG. 2C, the resist layer 2 exposed in the step shown in FIG. 2B is developed to form a resist pattern 3.

In this embodiment, the substrate 1 having the resist layer 2 exposed as described above is immersed in a stock solution of methyl isobutyl ketone (MIBK) at room temperature for about 2 minutes while the substrate 1 is still, did.

Next, the shape of the obtained resist pattern (resist structure) 3 was observed.

The height d ₃ of the resist pattern ₃ (FIG. 2)
In the group where d ₃ ) shown in (c) is 154 μm or less, FIG.
It has been found that the resist pattern 3 can be formed with high accuracy without the phenomenon shown in FIG.

On the other hand, among the resist patterns 3 formed from a plurality of samples, the height d ₃ of the resist patterns ₃ is
In the group exceeding 154 μm, a phenomenon as shown in FIG. 12 was observed.

Also, in any of the resist patterns 3 formed from a plurality of samples,
No trace of a part of the resist pattern being dissolved in the developer was observed.

[0282] Among the resist patterns 3 formed from a plurality of samples, the height d ₃ of the resist pattern ₃ is 154 µm.
As described above, it was found that the group of m or less did not lose its shape and had sufficient hardness.

Next, in the step shown in FIG. 2D, the substrate 1 having the resist pattern 3 is immersed in a plating solution, and the substrate 1 is electroformed or electroplated, for example, with Ni,
A metal structure 4 is formed by depositing Cu, Au, or the like in the valleys of the resist pattern 3 or the like.

Next, in the step shown in FIG. 2E, the resist material is removed, and a metal structure 4 is obtained.

In the present example, a nickel structure was manufactured according to the steps shown in FIGS. 2C and 2D for a group in which the height d ₃ of the resist pattern 3 was 154 μm or less.

With respect to the nickel structure obtained as described above, it was observed whether or not plating was performed on unnecessary portions.

As a result of the observation, it was revealed that unnecessary portions of the nickel structure were not plated, and the nickel structure had a fine structure substantially as designed.

Further, in the obtained nickel structure, no trace that the resist pattern 3 lost its shape in the electroforming or electroplating step was observed.

[0289] As Example 2 filter 50, the average thickness of 25 [mu] m ^t polyimide filter (trade name Kapton, DuPont-Toray Co., Ltd.) except for using The experiment was conducted in the same manner as in Example 1.

[0290] used in Example 2, out of the plurality of samples, the height d ₃ of the resist pattern 3, in the following groups 48 [mu] m ^t, without causing symptoms such as shown in FIG. 12, the resist pattern 3 It became clear that it could be formed.

The synchrotron radiation used in Example 2 is shown in FIG. 4 for reference. In FIG. 4, a curve E ₂ are,
Emission window 21 for synchrotron radiation used in Example 2.
0, light transmitting film of X-ray mask 100 (mask membrane)
100b shows the synchrotron radiation after passing through the filter 50 used in Example 2.

[0292] As Example 3 filter 50, except for using a filter to methyl methacrylate of average thickness 50 [mu] m ^t (MMA) as a main component a copolymer of methacrylic acid (MAA) (own work product), implemented The same experiment as in Example 1 was performed.

The [0293] Example 3, of the plurality of samples, the resist pattern height d _3, in the following groups 48 [mu] m ^t, without causing symptoms such as shown in FIG. 12, the resist pattern 3 with high precision It became clear that it could be formed.

REFERENCE EXAMPLE The resist layer 2 is exposed and developed using the synchrotron radiation emission window 210 and the synchrotron radiation transmitted through the X-ray mask 100 without using the filter 50 to form a resist pattern. Formed.

In the reference example, the height d _{3 of the} resist pattern
However, in the group of about 48 μm or more, a phenomenon as shown in FIG. 12 occurred.

FIGS. 5 and 6 are diagrams showing the effect of the present invention. Referring to FIG. 5, FIG. 5 shows absorption energy density of a resist material containing a copolymer of methyl methyl methacrylate (MMA) and methacrylic acid (MAA) as a main component (base resin), and FIG. The thickness (height) d _{3 of the} resist pattern ₃ (shown in FIG. 2 (c)) enables the resist pattern (resist structure) 3 to be formed with high precision in the developing step without such a phenomenon. d
It is a figure which shows the correlation with ₃ ).

In FIG. 5, a curve F is a curve showing the effect of Example 1 using the filter 50, and a curve G is a curve showing the effect of the reference example without using the filter 50.

Based on an experiment, the upper limit of the absorption energy density of a resist material containing a copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA) as a main component (base resin) used in this example. The value and the lower limit were calculated based on the following formula.

[0299]

(Equation 1)

In the formula, ΔP _R (λ) indicates the energy absorbed by the resist material, P _S (λ) indicates the spectrum of synchrotron radiation, and T _W (λ) indicates beryllium (Be) windows and, such as an exposure atmosphere gas, shows the transmittance at the components of the beam line until the X-ray mask or filter front, T _M (lambda), the light transmittance of the X-ray mask membrane and / or filter of the transmission Rate, e
xp (−μ (λ) z) represents attenuation in the depth direction of the resist layer at the depth z, and μ (λ) is an absorption coefficient of the resist material.

Λ indicates the wavelength. The main component (base resin) is a copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA) used in this example.
The upper limit value of the absorbed energy density of the resist material containing as above is 12 kJ / cm ³ and the lower limit value is 0.8 kJ / c.
m ³ .

Referring to curve G, in the reference example, when the upper layer or surface of resist layer 2 reaches the upper limit of the absorbed energy density, ie, 12 kJ / cm ³ , the lower limit of the absorbed energy density, ie, , 0.8k
The position of J / cm ³ is a position of 48.6 μm from the surface of the resist layer 2 in the depth direction.

On the other hand, referring to the curve F, in the first embodiment,
When the upper layer portion or the surface of the resist layer 2 reaches the upper limit of the absorbed energy density, that is, 12 kJ / cm ³ , the lower limit of the absorbed energy density, that is, 0.1.
The position of 8 kJ / cm ³ is a position of 154 μm in the depth direction from the surface of the resist layer 2.

That is, if the filter 50 is not used, the maximum value of the height of the resist pattern that can be formed into a desired shape with high precision in the developing step is about 48 μm. According to the first embodiment, when a polyimide filter 50 having substantially the same absorption spectrum as the resist layer 2 is used,
Light having a wavelength component that is easily absorbed by the upper layer portion or the surface of the resist layer 2 is absorbed by the filter 50. As a result, a resist pattern having a height of 154 μm can be formed with high accuracy.

Referring to FIG. 6, FIG. 6 shows a resist capable of forming a resist pattern (resist structure) with high precision in the developing step without causing the phenomenon shown in FIG. Pattern 3 thickness (height)
FIG. ₃ is a diagram showing a correlation between (d ₃ shown in FIG. 2C) and the dose of synchrotron radiation to the resist layer 2.

In FIG. 6, a straight line F indicated by a solid line indicates the effect of the first embodiment using the filter 50, and a straight line G indicated by a broken line indicates the effect of the reference example using no filter 50. It is a straight line shown.

The straight line F indicated by a solid line and the straight line G indicated by a broken line
With reference to, by using the filter 50, a resist pattern (resist structure) having a side wall formed perpendicular to the substrate 1 can be obtained in a short time.

Also, by using the filter 50, the depth (thickness) direction in the resist layer 2 can be reduced.
Since the attenuation of the absorbed energy density is small, in the development process, the development proceeds in the upper layer portion and the lower layer portion to the same extent, so that the resolution of the resist pattern (resist structure) is improved.

When the resist layer 2 is irradiated with the synchrotron radiation for a long time through the X-ray mask 100 in order to deeply expose the resist layer 2, the X-ray absorber 100a is irradiated with the synchrotron radiation. Penetrates through the resist layer 2 and exposes a portion of the resist layer 2 that does not need to be exposed, so that a desired resist pattern cannot be obtained.

[0310] In the present invention, in order to solve such a problem, the average thickness of the X-ray absorber 100a is, It may be noted that it is preferable to use an X-ray mask having a thickness of at least 5 [mu] m ^t .

The average thickness of the X-ray absorber was 5 μm.
A method for fabricating an X-ray mask having a thickness of at least m ^t is because it is described in detail in Japanese Patent Application No. 4-277266, and description thereof is omitted here.

Further, as a material for forming a light transmitting film (mask membrane) of an X-ray mask, X-ray using polyimide is used.
It is known that line masks exist. However, an X-ray mask using polyimide as a light transmitting film (mask membrane) uses light having a wavelength of about 40 °,
An X-ray mask used for exposing a desired pattern on a resist layer. From the viewpoint of dimensional stability and the like, an X-ray mask for exposing the resist layer to a desired pattern using light in a wavelength region of 20 ° or less. It is not used as an X-ray mask.

On the other hand, according to the present invention, when a desired pattern is exposed on a resist layer using synchrotron radiation in a wavelength range of 20 ° or less, a polyimide filter is used separately from an X-ray mask. There is a feature.

[0314] With a specific configuration using a polyimide filter, of the light in the wavelength range that is absorbed by the X-ray resist material, particularly, the light in the wavelength range that is easily absorbed by the X-ray resist material. , More specifically, 4Å
Of the light in the wavelength region of 20 ° or less, in particular, light in the wavelength region easily absorbed by the resist layer, specifically, all or a part of the light in the wavelength region of 5 ° to 15 ° can be removed, By irradiating the resist layer with synchrotron radiation light in which light in a wavelength region particularly easily absorbed is attenuated in advance, the resist pattern is not simply a resist pattern having a fine line width, but a thick resist pattern. It should be noted that, as far as the present inventor knows, the unique effect that can be formed into a desired shape with high accuracy is a technique that has not been known hitherto.

The disclosure relating to the above embodiments is merely a specific example of the present invention, and does not limit the technical scope of the present invention.

Referring again to FIG. 3, in the present embodiment, filter 50 is provided with an emission window 210 for synchrotron radiation.
And an example in which the filter 50 is provided between the X-ray mask 100 and the resist layer 2 with reference to FIG. It goes without saying that the same effect as in the example is achieved.

Further, in this embodiment, an example was described in which the synchrotron radiation generated by the electron storage ring (SR ring) of the synchrotron radiation device was irradiated through the synchrotron radiation light emission window 210. But,
It should be noted that the emission window 210 for synchrotron radiation is not necessarily an essential component. That is,
The synchrotron radiation light generated by the electron storage ring 209 of the synchrotron radiation device is directly radiated to the X-ray mask 100 or the filter 50 using a vacuum direct connection method without using the synchrotron radiation light emission window 210. Note that this may be done.

In this embodiment, an example was described in which a resist material containing a copolymer of methyl methacrylate and methacrylic acid as a main component (base resin) was used as the resist material constituting the resist layer 2. This is merely used for explanation, and the present invention uses a resist material containing a copolymer of methyl methacrylate and methacrylic acid as a main component (base resin).
It goes without saying that the present invention is not limited to the method for forming a fine structure.

It should be noted that, in principle, the present invention can provide the same effect as that of the present embodiment even if another known X-ray resist material is used.

In this embodiment, an example in which a polyimide filter is used as the filter 50 has been described. However, in principle, the filter 50 is made of a material having substantially the same absorption spectrum as the resist layer. It should be noted that a super engineering plastic material other than polyimide, more specifically, polyethylene terephthalate or the like is applicable.

Further, in this example, for the sake of simplicity, no particular mention was made of an adhesion aid or a cross-linking agent used in preparing a resist material, but the resist material used in the present invention was prepared. Needless to say, an adhesion aid or a cross-linking agent may be used in this case.

Preferred examples of such a crosslinking agent include ethylene glycol dimethacrylate and triethylene glycol dimethacrylate.

As the adhesion aid, various silane coupling agents can be used. Such adhesion aids include, for example, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyl Preferred specific examples thereof include triacetoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, and γ-chloropropylmethyldimethoxysilane.

[0324]

As described above, according to the present invention, a fine structure having a high aspect ratio can be formed with high precision.
It can be manufactured easily and easily.

More specifically, according to the first aspect, in the exposure step, the resist layer is irradiated with synchrotron radiation through a filter having substantially the same absorption spectrum as that of the resist layer. A high-precision resist pattern can be formed without forming a shape in which the line width increases as the depth increases from the surface of the resist layer 2 toward the substrate 1.
By forming a fine structure, a fine line width dimension,
A thick microstructure having a large aspect ratio can be easily formed easily with high precision.

According to the second invention, in particular, in the step of forming a resist layer on the substrate, the step of placing a frame member having a hollow portion on the substrate, and the step of And a step of filling a syrup containing a polymer obtained by polymerizing the monomer, and a syrup containing the monomer and the polymer obtained by polymerizing the monomer are completely polymerized on the substrate. As a result, the following effects are obtained.

(1) A resist layer can be formed uniformly thick on a substrate as compared with the conventional multi-spin coating method.

(2) Even if a thick resist layer is formed on a substrate, cracks are less likely to occur in the resist layer.

(3) Excellent adhesion between the substrate and the resist layer. (4) In the step of forming a resist pattern by development, the resist pattern is less likely to lose its shape.

(5) In the step of depositing a fine structure according to a resist pattern by electroplating,
The resist pattern is less likely to lose its shape.

(6) According to the second aspect of the present invention, in the exposing step, the resist layer is irradiated with synchrotron radiation through a filter having substantially the same absorption spectrum as the resist layer. In the development process, a good resist pattern can be formed. By forming a fine structure based on the resist pattern, a fine structure having a fine line width, a thickness, and a large aspect ratio can be formed with high precision. In addition, it can be formed easily and easily.

(7) According to the second invention, in the step of forming a resist layer on the substrate, as a result of using the bulk polymerization method, the resist layer formed on the substrate has
Originally contains no solvent.

For this reason, in the step of forming a microstructure by electroplating based on the resist pattern during the development and the resist pattern during development, the resist pattern is less likely to crack or lose its shape. Can be obtained.

[Brief description of the drawings]

FIG. 1 is a process diagram schematically showing an embodiment of a process of forming a resist layer on a substrate according to the present invention.

FIG. 2 shows a method for forming a microstructure according to the present invention.
In particular, the resist layer is irradiated with synchrotron radiation,
An exposure step of exposing a desired pattern to the resist layer, a developing step of developing the resist layer exposed to the desired pattern to form a resist pattern, and a step of forming a microstructure based on the resist pattern. FIG. 3 is a process chart schematically showing one embodiment.

FIG. 3 shows a method for forming a microstructure according to the present invention.
FIG. 4 is a process diagram schematically showing an exposure step of irradiating a synchrotron radiation beam to the resist layer to expose a desired pattern on the resist layer.

FIG. 4 shows an emission window 210 for synchrotron radiation and a light transmitting film (mask membrane) 100b of the X-ray mask 100.
FIG. 4 is a diagram showing the effect of a filter 50 having substantially the same absorption spectrum as the resist layer 2.

FIG. 5 is a diagram showing the effect of the present invention.

FIG. 6 is a diagram showing the effect of the present invention.

FIG. 7 shows a method for forming a microstructure according to the present invention.
FIG. 10 is a process chart schematically showing another example in the exposure step.

FIG. 8 is a process diagram schematically showing a basic process of a conventional LIGA method.

FIG. 9 is a process chart schematically showing the basic steps of the conventional LIGA method.

FIG. 10 is a process diagram schematically showing a conventional exposure process of exposing a resist layer to a desired pattern by irradiating synchrotron radiation to the resist layer in the conventional LIGA method.

FIG. 11 shows an emission window 210 for synchrotron radiation and X
Light transmitting film (mask membrane) 101 of line mask 100
It is a figure showing the effect of b.

FIG. 12 illustrates a step of exposing a resist layer to a desired pattern using an exposure step as shown in FIG. 10 and then developing the resist layer exposed to the desired pattern to form a resist pattern. FIG. 3 is a view schematically showing a phenomenon occurring in a resist pattern.

FIG. 13 is a diagram schematically showing energy absorbed by a resist material.

[Explanation of symbols]

 Reference Signs List 1 substrate 2 resist layer 2p pattern 3 resist pattern (resist structure) 3v valley 4 metal structure 11 hot plate (heating means) 12 frame material 12m hollow portion 12h frame material height 12s frame material side wall 13 Kapton sheet ( Release sheet) 14 Metal plate 15 Weight 50 Filter 100 X-ray mask 100a X-ray absorber 100b X-ray transmitting film (mask membrane) 210 Emission window for synchrotron radiation

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) H01L 21/027 G03F 7/20

Claims (4)

(57) [Claims] A step of forming a resist layer on a substrate; an exposing step of irradiating the resist layer with synchrotron radiation to expose a desired pattern on the resist layer; and exposing the desired pattern to light. Developing the formed resist layer to form a resist pattern; and forming a microstructure based on the resist pattern. The method for forming a microstructure, wherein the exposing step is substantially performed with the resist layer. And exposing the resist layer through a filter having the same absorption spectrum. 2. A step of forming a resist layer on a substrate; an exposing step of irradiating the resist layer with synchrotron radiation to expose a desired pattern on the resist layer; A developing step of developing the resist layer formed to form a resist pattern, and a method of forming a fine structure based on the resist pattern, wherein the resist layer is formed on the substrate. A step of placing a frame material having a hollow portion on the substrate; and a step of filling a syrup containing a monomer and a polymer obtained by polymerizing the monomer in the hollow portion. And a polymerization completion step of completely polymerizing a syrup containing the monomer and a polymer obtained by polymerizing the monomer on the substrate, wherein the exposing step is substantially performed with the resist layer. Same sucking Through a filter having a spectrum, exposing the resist layer, method of forming a fine structure. 3. The fine structure according to claim 1, wherein a filter material constituting the filter is substantially the same as a resist material constituting the resist layer. Forming method. 4. The method for forming a fine structure according to claim 1, wherein a filter material constituting the filter is polyimide.