TWI597182B - Liquid ejection device, nanoimprinting apparatus, nanoimprinting liquid storage tank, method of manufacturing cured product pattern, method of manufacturing optical component, method of manufacturing circuit board, and method of manufacturing imprinting - Google Patents

Description

Liquid discharge device, nanoimprinting device, nanoimprinting liquid storage bucket, method of manufacturing hardened product pattern, method of manufacturing optical component, method of manufacturing circuit board, and method of manufacturing imprinting mold

The invention relates to a liquid discharge device for discharging a nanoimprint liquid, a nanoimprinting device, a nanoimprint liquid storage bucket, a method for manufacturing a hardened product pattern using the liquid discharge device, a method for manufacturing an optical component, and a circuit board for manufacturing the same Method, and method of making an imprint mold.

In semiconductor devices, microelectromechanical systems (MEMSs) and the like, the demand for micromachining has been increasing. In particular, photon imprinting technology is attracting attention.

In the photon imprinting technique, a photohardenable component (resist) is attached to a substrate having a surface having a fine irregular pattern and pressed against a substrate coated with the photohardenable component (crystal Hardened in the state of the circle). this will The irregular pattern of the mold is transferred to the hardened product of the photohardenable component, whereby the irregular pattern is formed on the substrate. The photon nanoimprint technique is capable of forming a fine structure (hardened product pattern) on the order of several nanometers.

In the photon imprint technique, a photohardenable component is applied to a pattern forming region of the substrate (placement step). Next, the photohardenable component is molded using a patterned mold (mold contact step). The photohardenable component is hardened by irradiating the photohardenable component with light (light irradiation step), and then being demolded (release step). Performing these steps allows a resin pattern (photohardenable film) having a predetermined shape to be formed on the substrate (see PTL 1).

In the placing step of the photon nanoimprint technique, a liquid discharge device including a liquid discharge head (hereinafter simply referred to as a "head") can be used as a means for applying the photohardenable component to the substrate. PTL 2 describes a liquid discharge device for discharging a common liquid such as ink, that is, the liquid discharge device includes a fully enclosed outer casing, a storage tub placed in the outer casing, and a head communicating with the storage tub. The liquid (ink) to be discharged is stored in a storage space in the storage tub. The liquid (ink) stored in the tub is supplied to the head and then discharged from the head.

In the photon imprint technique, molding is performed by pressing a mold against a nanoimprinting liquid, such as a photohardenable component applied in the step of disposing. Therefore, when, for example, gelled or solid foreign particles having a diameter of several nanometers to several micrometers (hereinafter referred to as "fine particles") are present in the nanoimprint liquid applied in the configuration step, the mold The damaged or formed pattern has defects. Therefore, the concentration of the nano-imprinted liquid particles The degree is preferably low.

Alternatively, when metal impurities such as metal ions or fine metal particles are present in the nanoimprint liquid, the treated substrate is contaminated with the metal impurities, and thus the semiconductor properties of the semiconductor device are affected. As such, the concentration of metal impurities in the nanoimprinted liquid is preferably low.

When a water system is present in the nanoimprinting liquid, properties such as hardening properties of the nanoimprinting liquid can be reduced as much as possible. Therefore, the concentration of water in the nanoimprinted liquid is preferably low.

The liquid discharge device described in PTL 2 is applied to a nanoimprinting device and the case where the nanoimprint liquid is stored in a storage section due to various components of the liquid discharge device, particles, metal impurities, or The concentration of water can be increased as much as possible over time. Therefore, there is a problem in which the nanoimprint liquid is stored in the storage section to increase the concentration of particles, metal impurities, or water in the nanoimprint liquid over time.

In the present invention, the concentration of particles, metal impurities, or water in the nanoimprint liquid stored in the storage section is suppressed with time.

[reference list] [Patent Document]

[PTL1]

PCT Japan Interpretation Patent Notice No. 2005-533393

[PTL2]

Japanese Patent Laid-Open Application No. 2006-192785

As one aspect of the present invention, the liquid discharge device includes a storage section for storing the nanoimprint liquid, and also includes a discharge port communicating with the storage section and discharging the nanoimprint liquid. The storage section contains a sorption medium that adsorbs or absorbs at least one selected from the group consisting of microparticles, metal ions, and water. When the nanoimprint liquid is discharged from the discharge port, the absorbing medium is not discharged from the discharge port.

Further features of the present invention will become apparent from the following description of exemplary embodiments.

1‧‧‧Liquid discharge device

2‧‧‧floor

3‧‧‧ head

4‧‧‧Liquid storage unit

5‧‧‧Transfer member

6‧‧‧Substrate

7‧‧‧Storage section

8‧‧‧storage bag

9‧‧‧Light nanoimprinting liquid

10‧‧‧Exhaust port

11‧‧‧Liquid packing

12‧‧‧ Pressure Regulator

13‧‧‧Communication

14‧‧‧ Valve

15‧‧‧ valve

16‧‧‧Connectors

17‧‧‧ buffer

18‧‧‧ Pressure Sensor

19‧‧‧ pump

20‧‧‧ valve

21‧‧‧ storage bucket

22‧‧‧ Controller

23‧‧‧Sucking media

70‧‧‧ storage bucket

80‧‧‧Storage section

103‧‧‧ Positioning marks

104‧‧‧Mold

105‧‧‧ Positioning marks

106‧‧‧ coated film

107‧‧‧ illuminating light

108‧‧‧ hardened products

109‧‧‧ hardened film

110‧‧‧ hardened product pattern

111‧‧‧Area

112‧‧‧Circuit structure

201‧‧‧ container

203‧‧‧Communication

204‧‧‧ pump

205‧‧‧Party counter

206‧‧‧Particle filter

207‧‧‧Metal impurity removal filter

600‧‧‧ nano imprinting equipment

610‧‧‧Mold head

611‧‧‧Structural Ontology

612‧‧‧Light source

613‧‧‧Lighting optical system

616‧‧‧Substrate chuck

618‧‧‧Control section

701‧‧‧ storage bucket

801‧‧‧Storage section

1 is a schematic view of a liquid discharge device in accordance with an embodiment of the present invention.

Figure 2 is a diagram showing a method of displaying a sorbent medium sealed in a wash liquid storage unit.

Figure 3A is an illustration of a pressure regulator used in an embodiment of the invention.

Fig. 3B is a view showing a state in which the storage bag is contracted by the state shown in Fig. 3A.

Figure 4 is a flow chart showing how the pressure of the liquid fill is controlled.

Figure 5A is a schematic cross-sectional view showing a method of making a hardened product pattern in accordance with an embodiment of the present invention.

Fig. 5B is a schematic cross-sectional view showing a method of manufacturing the hardened product pattern.

Fig. 5C is a schematic cross-sectional view showing a method of manufacturing the hardened product pattern.

Fig. 5D is a schematic cross-sectional view showing a method of manufacturing the hardened product pattern.

Fig. 5E is a schematic cross-sectional view showing a method of manufacturing the hardened product pattern.

Fig. 5F is a schematic cross-sectional view showing a method of manufacturing the hardened product pattern.

Fig. 5G is a schematic cross-sectional view showing a method of manufacturing the hardened product pattern.

Figure 6 is a schematic view of a nanoimprinting apparatus in accordance with an embodiment of the present invention.

Figure 7A is a schematic view of a nanoimprinted liquid storage tank in accordance with an embodiment of the present invention.

Figure 7B is a schematic view of a nanoimprinted liquid storage tank modified by the nanoimprinted liquid storage tank shown in Figure 7A.

Embodiments of the invention are described in detail below with reference to the accompanying drawings. The invention is not limited to the embodiments. Various modifications and improvements can be made to the embodiments based on the knowledge of those skilled in the art without departing from the spirit of the invention. Such modifications and improvements are within the scope of the invention.

[Microparticles, metal impurities, or water in a liquid imprinted liquid]

In the case of producing a hardened product pattern by a photon nanoimprinting process, the presence of particles in the photon imprinting liquid 9 (hereinafter referred to as "liquid 9") may cause damage to the mold or such as A failure to form a defect in the pattern. When the mold is pressed against the liquid 9 on the substrate, for example, the concave portion of the pattern formed on the surface of the mold is unfolded, and thus the mold can be damaged as much as possible. Alternatively, the particles are caught in the recessed portion of the mold surface, and thus the mold can be broken as much as possible.

As used herein, the term "microparticle" means finely foreign particles. The microparticles are gelled or solid particulate materials having a diameter of from several nanometers to several micrometers. The microparticles include gelled or solid organic microparticles produced by topical polymerization of a nanoimprinted liquid, and inorganic microparticles such as fine metal microparticles underneath.

The number of particles in the liquid 9 is preferably as small as possible. The concentration of the particles having a diameter of 0.1 μm or more in the liquid 9 is preferably 1 or less per ml, or preferably 0.1 or less per ml.

During the preparation of the liquid 9, in order to minimize the number of particles in the liquid 9, it is preferred that the purification including filtration be sufficiently performed. Even if the liquid 9 is prepared by sufficiently performing purification so as to have a reduced particle concentration, the concentration of the particles in the liquid 9 can be gradually increased as much as possible as time elapses with the liquid 9 stored in the tub or the like. . Therefore, it is necessary to suppress the concentration of the particles in the liquid 9 to increase with time. plus.

In the case of fabricating a semiconductor device by the photon nanoimprint process, when the metal impurities are present in the liquid 9, by applying the liquid 9 to the processed substrate, the processed substrate is Contaminated by the metal impurities. As a result, the semiconductor properties of the semiconductor device can be affected as much as possible. The term "metal impurities" as used herein means metal-containing fine particles or metal ions, and especially means sodium, calcium, iron, potassium, zinc, aluminum, magnesium, nickel, chromium, copper, lead. Fine particles or ions of manganese, lithium, tin, palladium, rhodium, cobalt, or ruthenium.

The concentration of the metal impurities in the liquid 9 is preferably low. The concentration of each of the metal impurity elements in the liquid 9 is preferably 100 ppb (100 ng/g) or less and more preferably 1 ppb (1 ng/g) or less. As used herein, the term "metal impurity element" means sodium, calcium, iron, potassium, zinc, aluminum, magnesium, nickel, chromium, copper, lead, manganese, lithium, tin, palladium, iridium, cobalt. And 锶. Adjusting the concentration of these elements in the liquid 9 within the above range enables the effect of the liquid 9 to be reduced in the semiconductor properties of the semiconductor device.

Thus, during the preparation of the liquid 9, in order to minimize the concentration of the metal impurities in the liquid 9, it is preferred that the purification including filtration be sufficiently performed. Even if the liquid 9 is prepared by sufficiently performing purification so as to have a reduced metal impurity concentration, the concentration of the metal impurities in the liquid 9 can be gradually increased as time elapses with the liquid 9 stored in the barrel or the like. Increase in land. Therefore, it is necessary to suppress an increase in the concentration of the metal impurities in the liquid 9 stored in the tub over time.

Further, when a water system is present in the liquid 9, properties such as the hardening property of the liquid 9 can be reduced as much as possible. When the water system is present in a photohardenable component such as that hardened by ultraviolet light, the sensitivity of the photohardenable component to light can be minimized.

Therefore, the concentration of water in the liquid 9 is preferably minimized during the preparation of the liquid 9. When the time 9 elapses with the liquid 9 stored in the tub or the like, the moisture in the ambient air for pressure adjustment or the water contained in the liquid filler, containing water, may penetrate the compartment as much as possible. In the case where water enters the liquid 9 from the outside, properties such as hardening properties may be reduced as much as possible, and the liquid 9 may be contaminated as much as possible by metal ions from the outside. Therefore, it is necessary to suppress the concentration of water in the liquid 9 from increasing with time.

[Liquid storage unit]

The liquid storage unit 4 (hereinafter referred to as the "unit 4") according to an embodiment of the present invention includes a storage bag 8 storing the liquid 9 and a sorption medium 23 placed in the storage bag 8. That is, the unit 4 stores the sorption medium 23 and the liquid 9 in the storage bag 8. The storage bag 8 is placed in a storage section (outer casing 7) in which the liquid 9 is stored.

The sorption medium 23 adsorbs or absorbs at least one selected from the group consisting of the particles, the metal ions, and water. As used herein, the term "sorption" means adsorption and/or absorption.

[sucking media]

The unit 4 includes the sorption medium 23 that adsorbs or absorbs at least one selected from the group consisting of particles, metal ions, and water contained in the liquid 9, and is placed in the storage of the liquid. 9 in the storage bag 8. The sorption medium 23 is constructed such that when the liquid 9 is discharged from the discharge port 10 of the head 3, the absorbing medium 23 is not discharged by the discharge port 10.

The absorbing medium 23 and the liquid 9 are in contact with each other, and thus the particles, metal ions, and/or water contained in the liquid 9 can be adsorbed on the absorbing medium 23 or absorbed in the absorbing medium 23. And can be retained. Thus, even if impurities such as the particles, the metal ions, or water are generated in the storage bag 8 or into the liquid 9 in the storage bag 8, the concentration of the impurities in the liquid 9 can be increased with time. It is suppressed because the impurities are retained by the sorption medium 23.

Since the sorption medium 23 is constructed such that when the liquid 9 is discharged from the head 3, the absorbing medium 23 is not discharged by the discharge port 10, the particles, the metal impurities, or the water It is prevented from being discharged from the discharge port 10. Therefore, the yield of the photon nanoimprint process can be increased, and various devices such as semiconductor devices can be manufactured with high yield.

The sorbent medium 23 is preferably a multi-hole medium. When the sorption medium 23 is a plurality of small holes, the ability of the sorption medium 23 to adsorb or absorb the particles can be increased. In the case where the sorption medium 23 has an ion exchange group on its surface as described below, when the sorption medium 23 is a small aperture, the specific surface area of the sorption medium 23 can be made large. And thus the ability of the sorption medium 23 to adsorb the metal impurities can be increased. to In the case where the sorbent medium 23 contains a desiccant as described below, when the sorbent medium 23 is a small aperture, the specific surface area of the sorption medium 23 can be made large, and thus the sorption medium The adsorption capacity or absorption capacity of 23 can be increased.

The sorption medium 23 has pores. The pores preferably have an average diameter of from 0.001 micron to 0.5 micron, more preferably from 0.001 micron to 0.1 micron, and particularly preferably from 0.005 micron to 0.1 micron. The use of sorbent media 23 having pores having an average diameter within the above range allows the particles to be efficiently adsorbed or absorbed. When the average diameter of the pores of the sorption medium 23 is more than 0.5 μm or less than 0.001 μm, the ability of the sorption medium 23 to adsorb the particles and the metal ions tends to be low. Incidentally, the average diameter of the pores of the sorption medium 23 can be determined by, for example, a mercury injection method. As used herein, the term "average diameter of pores" means the average diameter of the pores in a state in which the sorption medium 23 is washed and dried.

Examples of the sorbent medium 23 include a multi-porous polyolefin film such as a polyethylene (PE) film and a polypropylene (PP) film, a multi-pore fluororesin film such as a polytetrafluoroethylene film, and a multi-pore polysiloxane. Amine film, multi-pore polyimide film such as nylon 6 film and nylon 6,6 film, cellulose, pearlite, diatomaceous earth, glass fiber, silicone, activated carbon, zeolite, and molecular sieve. The sorption medium 23 can be granular (spherical) or fibrous.

The sorbent medium 23 is preferably made of a material such as cellulose, diatomaceous earth, polyethylene, nylon, activated carbon, or silicone. This is because this material does not contain, for example, as much responsibility as possible for the production of such metal impurities. Metal elements such as aluminum and sodium. Nylon, diatomaceous earth, cellulose, and the like have polarity and ability to adsorb the metal ions, and are therefore particularly preferred.

In the present invention, the sorbent medium 23 is preferably surface modified with the ion exchange group. It is especially preferred that the sorbent medium 23 is a plurality of small pores and is surface modified with the ion exchange group. This allows the contact area between the liquid 9 and the sorption medium 23 to be large, and thus the ability of the sorption medium 23 to adsorb the metal ions is high. The inner surface of the storage bag 8 can be surface modified with the plasma exchange group.

The type of the plasma exchange group is not particularly limited. The plasma exchange group is preferably a cation exchange group. The use of such cation exchange groups enables efficient adsorption of metal ions as cations. The plasma exchange group is preferably a sulfonic acid group and a carboxyl group of a cation exchange group.

As described above, surface modification of the sorption medium 23 or the inner surface of the storage bag 8 by the ion exchange group enables the metal impurities to be removed based on the principle of ion exchange in the form of ions It is present in the liquid 9.

The sorbent medium 23 which is surface-modified by the ion exchange group may be, for example, Zeta Plus (registered trademark) EC series filter B47-40QSH or Zeta Plus (registered trademark) EC series filter B47-020GN (by 3M Japan Limited) Made by the company, which is a sorption medium composed of cellulose, diatomaceous earth, and ion exchange resin.

The sorption medium 23 modified by the ion exchange group can be a fiber Dimensional ion exchange resin. Preferred examples of the fiber ion exchange resin include IONEX (registered trademark) TIN-100 and IONEX (registered trademark) TIN-600 (both produced by Toray Pan Chemical Co., Ltd.). IONEX (registered trademark) TIN-100 is a polystyrene/polyolefin synthetic fiber obtained by exchanging a group surface-modified polystyrene resin with a sulfonic acid. IONEX (registered trademark) TIN-600 is a polystyrene/polyolefin synthetic fiber obtained by exchanging a group surface-modified polystyrene resin with iminodiacetic acid. Both IONEX (registered trademark) TIN-100 and IONEX (registered trademark) TIN-600 have a fiber diameter of 40 μm and a fiber length of 0.5 mm. The ion exchange resins of these fibers have excellent adsorption ability and large surface area, and also have good chemical stability, and are preferred as the sorption medium 23.

When the sorbent medium 23 is a fiber, the average diameter of the pores corresponds to the average diameter of the space between the interwoven fibers forming the sorption medium 23. The average diameter can be measured by means of the filter in which the filter is prepared using the sorption medium 23 and the gold nanoparticles having a conventional diameter pass through the filter.

When the sorbent medium 23 is a fiber, the fibers preferably have a diameter of from about 1 micron to 500 microns and more preferably from 10 microns to 100 microns. The fibers preferably have a length of from about 0.1 mm to 100 mm and more preferably from 0.50 mm to 50 mm. When the diameter and length of the fibers are within the upper range, the ability of the sorbent medium 23 to adsorb the particles and the metal ions can be increased.

In this embodiment, the sorbent medium 23 preferably contains the drying Agent. When the absorbing medium 23 contains the desiccant, water contained in the liquid 9 is adsorbed on the absorbing medium 23 or absorbed in the absorbing medium 23, and thus water can be prevented from being discharged from the venting port. 10 discharge.

The desiccant is not particularly limited and may have a function of adsorbing or absorbing moisture. The desiccant can be, for example, a chemical or physical desiccant.

The chemical desiccant utilizes one of the chemical reactivity or dissolution with water to dissolve the properties inherent in the chemical. Examples of the chemical desiccant include calcium oxide, barium oxide, magnesium oxide, barium oxide, lithium sulfate, sodium sulfate, gallium sulfate, titanium sulfate, nickel sulfate, lithium chloride, calcium chloride, magnesium chloride, aluminum chloride, calcium sulfate. , magnesium sulfate, zinc sulfate, potassium acetate, dimethylamine hydrochloride, orthophosphoric acid, guanidine hydrochloride, strontium phosphate, bismuth sulfamate, methyl hydrazine phosphate, cesium carbonate, potassium hydroxide, sodium hydroxide, magnesium hydroxide , phosphorus pentoxide, magnesium perchlorate, cerium oxide, potassium oxide, cerium oxide, sodium oxide, polyvinyl alcohol, starch-acrylic acid graft copolymer, starch-acrylonitrile graft copolymer, cellulose-acrylonitrile A saponified product of a branched copolymer, a cross-linked polyvinyl alcohol, a sodium cross-linked polyacrylate, and a methyl acrylate-vinyl acetate copolymer.

The physical desiccant utilizes one of the adsorption of water molecules on a multi-pore medium. Examples of such physical drying agents include activated carbon, silicone, polyvinyl alcohol, strontium talc, and synthetic zeolites.

The desiccant preferably does not contain a metal element that can affect the semiconductor properties of the semiconductor device as much as possible. That is, the desiccant preferably does not contain sodium, calcium, iron, potassium, zinc, aluminum, magnesium, nickel, chromium, copper, lead, manganese, lithium, tin, palladium, iridium, cobalt, and lanthanum. The desiccant is preferably selected from the group consisting of sulfur Gallium hydride, titanium sulphate, dimethylamine hydrochloride, orthophosphoric acid, guanidine hydrochloride, strontium phosphate, bismuth sulfamate, methyl hydrazine phosphate, cesium carbonate, phosphorus pentoxide, polyvinyl alcohol, starch-acrylic acid graft copolymerization , starch-acrylonitrile graft copolymer, cellulose-acrylonitrile graft copolymer, crosslinked polyvinyl alcohol, saponified product of methyl acrylate-vinyl acetate copolymer, cerium oxide, cerium oxide, activated carbon, and At least one of the group consisting of silicones.

The desiccant may additionally have the ability to adsorb the particles or the metal ions. Another sorption medium different from the sorption medium 23 can be used. That is, a plurality of sorbent media including the sorbent medium 23 can be used.

When the sorption medium 23 is not fixed to the inner surface of the storage bag 8, the absorbing medium 23 is preferably suspended in the liquid 9 in the storage bag 8. When the sorption medium 23 is suspended in the liquid 9 in the storage bag 8, the discharge port 10 is not blocked during the discharge of the liquid 9, and thus the reduction in discharge performance can be suppressed. As such, the density of the sorbent medium 23 is preferably less than or equal to the density of the liquid 9. In particular, the density of the sorbent medium 23 is preferably from 30% to 100%, more preferably from 50% to 100%, and particularly preferably from 80% to 100%, of the density of the liquid 9. When the density of the sorption medium 23 is within the upper range, the sorption medium 23 can be suspended in the liquid 9.

The absorbing medium 23 preferably has a size larger than the diameter of the discharge port 10 such that the sorption medium 23 is not discharged from the discharge port 10 when the liquid 9 is discharged from the head 3. The size of the absorbing medium 23 is preferably 150% or more, and more preferably 200% or more, of the diameter of the discharge port 10. The size of the sorption medium 23 can be determined by, for example, sedimentation The effective diameter or equivalent diameter determined by the method, the laser scattering method, or the sieving method.

Alternatively, the sorbent medium 23 can be secured to the inner surface of the storage bag 8. That is, the sorption medium 23 can be attached to the inner surface of the storage bag 8. In this case, the sorption medium 23 is attached to the inner surface of the storage bag 8 in the form of a film, or the sorption medium 23 is attached or embedded in the storage bag 8 in the form of spheres or particles. The absorbing medium 23 can be fixed to the inner surface of the storage bag 8 in a manner of the inner surface. Alternatively, the sorbent medium 23 can be secured to the inner surface of the storage bag 8 with a fibrous member.

As mentioned above, the sorption medium 23 is preferably placed so as not to block the discharge ports 10. If the sorption medium 23 is placed such that the discharge ports 10 are blocked, that is, the passage of the liquid 9 is blocked, the discharge performance can be reduced as much as possible. If the liquid 9 is discharged by increasing the pressure of the storage bag 8 in this state, other impurities such as nanobubbles or particles may be generated as much as possible in the discharged liquid 9. In this embodiment, the sorption medium 23 is suspended in the liquid 9 or fixed to the inner surface of the storage bag 8; therefore, blocking the discharge port 10 by the absorbing medium 23 can be avoided. This allows the aforementioned reduction in discharge performance and suppression of generation of impurities due to discharge.

[nanoimprinted liquid storage tank]

A nanoimprint liquid storage tank 70 (hereinafter referred to as the "bucket 70") according to an embodiment of the present invention is described below with reference to FIG. 7A. Figure 7A is a schematic view of the barrel 70.

The tub 70 includes a storage section 80 that stores the liquid 9. The tub 70 contains the sorption medium 23. The sorption medium 23 is placed in the storage section 80 and adsorbs or absorbs particles, metal ions, and/or water contained in the liquid 9. The material and properties of the sorption medium 23 are as described above.

As shown in FIG. 7A, in the tub 70, the sorption medium 23 is suspended in the liquid 9. 7B is a schematic view of a nanoimprinted liquid storage tank 701, which is a modification of the storage tub 70. The nanoimprint liquid storage tank 701 includes a storage section 801, and the sorption medium 23 is fixed to an inner surface of the storage section 801.

The presence of the sorption medium 23 in the tank 70 as described above allows the concentration of particulates, metallic impurities, or water in the liquid 9 to be suppressed over time, and is used for the liquid in the nanoimprinting process. It is stored in the tub 70.

[nanoimprint liquid]

The type of the liquid 9 is not particularly limited and may be a liquid material used in the nanoimprinting process. Liquid Example 9 includes, but is not limited to, (1) hardenable components, such as hardenable components for resists and hardenable components for forming mold replicas, for forming fine patterns, and (2) hardening Layer - forming a hardenable component, such as an adhesive layer - forming a hardenable component, a primer layer - forming a hardenable component, an interposer - forming a hardenable component, a top coating layer - forming a hardenable component, and a smoothing layer - forming a hardenable component .

The liquid 9 is preferably a photohardenable component P (hereinafter referred to as the "component P"). The component P which is the liquid 9 is described below.

[photohardenable component]

The component P contains a component (A) which is a polymerizable compound; and a component (B) which is a photopolymerization initiator. As used herein, the term "photohardenable component" means a component that is hardened by light irradiation. The component P is preferably used as a photohardenable component of a photon imprint. The component P containing the component (A) and the component (B) is not particularly limited and may be cured by light irradiation. The component P may contain, for example, a compound containing the component (A) and the component (B) in the molecule of the compound.

As used herein, the term "hardened product" means a person obtained by partially or completely hardening a polymer obtained by polymerizing a polymerizable compound contained in a photohardenable component. Incidentally, among the hardened products, such as a comparatively large area, a hardened product having a very small thickness is described as a "hardened film" in some cases. The shape of the hardened product and the film is not particularly limited. The hardened product and the cured film may have a surface pattern shape.

[Component (A): polymerizable compound]

This component (A) is the polymerizable compound. As used herein, the term "polymerizable compound" means that a compound reacts with a polymerization factor (free radical, etc.) produced by the component (B) (photopolymerization initiator) to carry out a chain reaction (polymerization). The reaction) forms a polymer film.

An example of a polymerizable compound is a radical polymerizable compound. The polymerizable compound which is the component (A) may be composed of a single type of polymerizable compound or a plurality of types of polymerizable compounds.

The radical polymerizable compound is preferably a compound having one or more groups of acryloyl or methacryl groups, that is, a (meth)acrylic compound.

Accordingly, the polymerizable compound which is the component (A) of the component P preferably contains the (meth)acrylic compound. The main component of the component (A) is more preferably a (meth)acrylic compound. This component (A) is optimally the (meth)acrylic compound. Incidentally, the fact that the main component of the component (A) is the (meth)acrylic compound means that the (meth)acrylic compound amounts to 90% or more by weight of the component (A).

When the radical polymerizable compound is composed of a plurality of types of compounds having one or more groups of acryloyl or methacryloyl groups, the radical polymerizable compound preferably contains a monofunctional (meth)acrylic acid. Monomer and multifunctional (meth)acrylic monomers. This is because a hardened product having high mechanical strength is obtained by using the monofunctional (meth)acrylic monomer and the multifunctional (meth)acrylic monomer in combination.

[Component (B): Photopolymerization initiator]

This component (B) is the photopolymerization initiator.

As used herein, the term "photopolymerization initiator" means a compound that absorbs light having a certain wavelength to produce the polymerization factor (freedom) base). In particular, the photopolymerization initiator is a polymerization initiator (radical generator) which generates radicals by light rays (infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X rays, charged particle beams such as electron beams, or radiation). .

This component (B) may be composed of a single type of photopolymerization initiator or a plurality of types of photopolymerization initiators.

The amount of the component (B) which is mixed in the component P and is the photopolymerization initiator is preferably 0.01% to 10% by weight of the component (A), which is the polymerizable compound, and more preferably The ground system is from 0.1% to 7% by weight.

When the amount of the component (B) is 0.01% by weight or more based on the amount of the component (A), the hardening rate of the component P is high, and thus the efficiency of the reaction can be increased. When the amount of the component (B) is 10% by weight or less of the component (A), the obtained hardened product has a certain mechanical strength.

[Component (C): another additive component]

In addition to the component (A) and the component (B), the component P may further contain an additive component (C) depending on various purposes, unless the effects of the present invention are impaired. Examples of the additive component (C) include a sensitizer, a hydrogen donor, an internal mold release agent, a surfactant, an oxidation inhibitor, a solvent, a polymer component, and a polymerization initiator different from the component (B).

The sensitizer is suitably added to a compound for the purpose of promoting polymerization or increasing reaction conversion. An example of such a sensitizer is a sensitizing dye.

The sensitizing dye is a compound which absorbs light having a specific wavelength, whereby it is excited, and it interacts with a photopolymerization initiator which is the component (B). As used herein, the term "interaction" includes the transfer of energy from the excited sensitizing dye to the photopolymerization initiator of component (B) and the transport of electrons.

The sensitizer can be used alone or in combination with another sensitizer.

The hydrogen-providing system reacts with a radical which is generated by a photopolymerization initiator of the component (B) to initiate a radical or a radical which grows at the growth end to generate more reactive radicals. When the photopolymerization initiator of the component (B) is a photo radical generator, the hydrogen donor is preferably used.

The hydrogen donor can be used alone or in combination with another hydrogen donor. The hydrogen donor may have a function as a sensitizer.

When the component P contains the sensitizer or the hydrogen donor as the additive component (C), the amount of the sensitizer or hydrogen donor contained in the component P is preferably a component of the polymerizable compound. The amount of (A) is from 0.01% to 20% by weight, more preferably from 0.1% to 5.0% by weight, and still more preferably from 0.2% to 2.0% by weight. When the amount of the sensitizer contained therein is 0.1% by weight or more based on the amount of the component (A), the effect of enhancing the polymerization can be effectively exhibited. When the amount of the sensitizer or hydrogen donor contained therein is 5.0% by weight or less based on the amount of the component (A), the polymer compound forming the prepared hardened product has a sufficiently high molecular weight, and Dissolution in component P fails or The deterioration of the storage stability of the component P can be suppressed.

The internal mold release agent may be added to the component P for the purpose of reducing the bonding strength between the interface between the mold and the resist, that is, the release force in the demolding step below. As used herein, the term "internal" means that an internal release agent is added to the component P prior to the placing step below.

Examples of the internal mold release agent include surfactants such as an anthrone surfactant, a fluorinated surfactant, and a hydrocarbon surfactant. In this embodiment, the internal release agent is non-polymerizable. The internal mold release agent can be used alone or in combination with another internal mold release agent.

When the component P contains the internal mold release agent as the additive component (C), the amount of the internal mold release agent contained therein is preferably 0.001% of the amount of the component (A) of the polymerizable compound. Up to 10% by weight, more preferably 0.01% to 7% by weight, and still more preferably 0.05% to 5% by weight.

The component P may contain a solvent, and is preferably substantially free of a solvent. Herein, the fact that substantially no solvent is contained means that any solvent which is inadvertently contained, such as an impurity, is contained. That is, the content of the solvent in the component P is preferably, for example, 3% by weight or less and more preferably 1% by weight or less. As used herein, the term "solvent" means a solvent that is used in combination with a component or photoresist. The type of the solvent is not particularly limited, and the solvent may be a compound which dissolves and uniformly disperses the compound used in the examples and does not react with the compounds.

The ratio between the component (A) and the component (B) can be such that the The P and/or the hardened product obtained by hardening the component P are determined by means of infrared spectroscopy, ultraviolet spectroscopy, pyrolysis gas chromatography-mass spectrometry or the like. The ratio between the component (A) and the component (B) in the component P can be determined by the ratio between the component (A) and the component (B) in the hardened product. When the component P contains the additive component (C), the ratio between the component (A), the component (B), and the additive component (C) in the component P can be similarly determined.

[The temperature of the photohardenable component during mixing]

When the component P is prepared, the component (A) and the component (B) are mixed together and dissolved under a predetermined temperature condition. In particular, the component (A) and the component (B) are mixed together in the range of 0 ° C to 100 ° C. This applies to the case where the component P contains the additive component (C).

[Adhesiveness of photohardenable components]

The mixture of the components excluding the component P of the solvent preferably has a viscosity of from 1 mPas to 100 mPas, more preferably from 1 mPas to 50 mPas, and still more preferably from 1 mPas to 6 mPas at 25 °C.

When the viscosity is 100 mPas or less, when the component P is brought into contact with the mold, it does not take a long time for the component P to be filled into the concave portion of the fine pattern on the mold. That is, the photon imprint process can be performed with high productivity. Furthermore, pattern defects due to poor filling are less likely to occur.

When the viscosity is 1 mPas or more, uneven application is less likely to occur during the operation of applying the component P to the substrate. Further, when the component P is brought into contact with the mold, the component P is less likely to be discharged from the end portion of the mold.

[surface tension of photohardening component]

The mixture excluding the components of the component P of the solvent is preferably from 5 mN/m to 70 mN/m, more preferably from 7 mN/m to 35 mN/m, and still more preferably from 10 mN/m to 32 mN at 23 °C. /m surface tension. When the surface tension is 5 mN/m or more, when the component P is brought into contact with the mold, it takes no time to fill the concave portion of the fine pattern on the mold when the component P is filled.

When the surface tension is 70 mN/m or less, the hardened product obtained by hardening the component P has surface flatness.

[Method of washing sorption medium and method of filling photo-radical polymerizable compound into liquid storage unit]

In this embodiment, the sorbent medium 23 is preferably sufficiently pre-washed before the component P is filled into the storage bag 8 in the unit 4, such that the sorption medium 23 does not act as such. Particles or sources of such metallic impurities. The structure of the unit 4 is described below. An example of a method of washing the sorbent medium 23 is described with reference to FIG.

The component P stored in the container 201 is pumped by the pump 204 through a communication member 203 such as a tube. The component P is passed by the pump 204 through the trench The through piece 203, the particle counter 205, the particulate filter 206, and the metal impurity removing filter 207 are fed to the storage bag 8 in the unit 4. The sorption medium 23 is placed in the storage bag 8 in advance. After the storage bag 8 is filled with the component P, the overflow component P is fed back to the container 201 via the communication member 203.

While the operation of the pump 204 continues, the component P passes through the particulate filter 206 and the metal impurity removal filter 207 several times. This allows the particles or the metal impurities to be removed. If the particles or the metal impurities are produced by the sorption medium 23, the particles or the metal impurities flow into the component P and are removed in the process.

The concentration of the particles in the component P is measured by the particle counter 205, if necessary. After the concentration of the particles in the component P reaches a predetermined value or less, the pump 204 is stopped, and the unit 4 is separated from the communication member 203 and then fully sealed.

In such a manner that the appropriate amount of the component P is taken by the container 201 at the predetermined instant, the content of the metal impurities in the component P can be checked, and the metal element is determined. After the content of the metal impurities in the component P reaches a predetermined value or less, the pump 204 can be stopped.

Examples of such pumps 204 include tube pumping, diaphragm pumping, and gear pumping. Examples of the particle counter 205 include a liquid particle sensor KS series (manufactured by RION Co., Ltd.), a liquid particle counter UltraChem series (manufactured by Particle Measurement Systems, Inc.), and a liquid particle counter SLS series (by Particle Measurement Systems, Inc., and Liquid Particle Counter HSLIS Series (by Particle Measurement System) Manufactured by the company).

Examples of the particulate filter 206 include "Ultipleat P-Nylon 66" (manufactured by Nihon Pall Co., Ltd.), "Ultipor N66" (manufactured by Nihon Pall Co., Ltd.), "P Emflon" (by Nihon Pall) Co., Ltd.), "LifeASSURE PSN Series" (manufactured by Sumitomo 3M Co., Ltd.), "LifeASSURE EF Series" (manufactured by Sumitomo 3M Co., Ltd.), "Photoshield" (manufactured by Sumitomo 3M Co., Ltd.) ), "Electropor II EF" (manufactured by Sumitomo 3M Co., Ltd.), "Microgard" (manufactured by Nihon Entegris KK), "Optimizer D" (manufactured by Nihon Entegris KK), "Impact Mini" (Manufactured by Nihon Entegris KK) and "Impact 2" (manufactured by Nihon Entegris KK). These filters can be used on their own or in combination.

Examples of the metal impurity removal filter 203 include "Zeta Plus GN grade" (manufactured by Sumitomo 3M Co., Ltd.), "Electropor" (manufactured by Sumitomo 3M Co., Ltd.), "Posidyne" (by Nihon Pall) "Ionkleen AN" (manufactured by Nihon Pall Co., Ltd.), "Ionkleen SL" (manufactured by Nihon Pall Co., Ltd.), and "Protego" (manufactured by Nihon Entegris KK) . These filters can be used on their own or in combination.

The particulate filter 206 and the metal impurity removal filter 207 preferably have a thickness of, for example, 0.001 micrometers to 5.0 micrometers, and more preferably 0.003. A pore size of micron to 0.01 micron. When the pore size of the particulate and metal impurity removal filters 206 and 207 is greater than 5.0 microns, the particulate and metal impurity removal filters 206 and 207 have low ability to adsorb the particles and the metal ions. When the particle size of the particulate and metal impurity removal filters 206 and 207 is less than 0.001 microns, the particulate and metal impurity removal filters 206 and 207 capture components of the component P, and thus may vary as much as possible The ingredients of ingredient P can be inserted as much as possible.

The sorbent medium 23 is preferably washed at a temperature of, for example, 0 ° C to 80 ° C, more preferably 10 ° C to 60 ° C, and particularly preferably 20 ° C to 50 ° C. The pump 204 preferably has a flow rate of, for example, from 0.01 ml/min to 100 ml/min and more preferably from 1 ml/min to 10 ml/min.

[liquid discharge device]

The present invention is applicable to any liquid discharge device, including a storage of a nanoimprinted liquid, a fully sealed storage section such as a photohardenable component. As used herein, the term "liquid" includes fluids having a relatively low viscosity, such as sol-like materials. Examples of liquid discharge devices according to embodiments of the present invention are described below with reference to Figures 1, 4 and 5. The invention is not limited to this example.

1 is a schematic view of a liquid discharge device 1 (hereinafter referred to as "device 1") according to an embodiment of the present invention. The device 1 is a device for discharging the liquid 9. As shown in FIG. 1, the device 1 includes the unit 4 and a pressure regulator 12. The device 1 places the head 3 opposite the bottom plate 2, which head is included in the device 1. The device 1 can discharge the liquid 9 To the substrate 6 (treated substrate) placed on the substrate 2. The bottom plate 2 is covered with a transfer member 5. The substrate 6 is attracted to the transfer member 5 using a suction unit not shown.

The unit 4 comprises the head 3, a fully enclosed outer casing 7 (storage section), and the storage bag 8. The storage bag 8 is placed in the outer casing 7 and is flexible. The space in the outer casing 7 (storage section) is divided into a first storage space that communicates with the discharge port 10 of the head 3, and is isolated from the first storage space by the storage bag 8 that is a divider. Second storage space. In this embodiment, in the space in the outer casing 7, the space in the storage bag 8 forms the first storage space, and the space outside the storage bag 8 forms the second storage space.

The present invention is not limited to a set of configurations in which the first storage space and the second storage space are separated from each other using the storage bag 8. The first storage space and the second storage space may be separated from each other using a flexible separator. The separator does not have to be bagged. The inside of the outer casing 7 can be separated into at least two spaces by a flexible separator such as a film. The space in the storage bag 8 may be the second storage space, and the space outside the storage bag 8 may be the first storage space.

In the case of storing a liquid filler, as described below, water is contained in the second storage space, and a separator made of a material having poor water permeability is preferably used. Examples of such materials include tetrafluoroethylene-perfluoroalkyl vinyl alcohol copolymer (PFA), modified polytetrafluoroethylene (modified PTFE), nylon (Ny), low density polyethylene (LDPE), and polypropylene. (PP).

The liquid 9 is stored in the first storage space, that is, in the space in the storage bag 8. The liquid 9 stored in the space in the storage bag 8 is supplied to the head 3, and is discharged from the discharge port 10 of the head 3. The liquid 9 is preferably pre-degassed.

In the unit 4, the sorption medium 23 is stored in the first storage space, that is, the space in the storage bag 8. The sorption medium 23 can be suspended in the liquid 9 or can be fixed to the inner surface of the storage bag 8. It is preferred that the sorption medium 23 does not block the discharge port 10.

The storage bag 8 is directly connected to the head 3 without a tube or valve therebetween. In the present embodiment, since a sliding member such as a valve is not used between the storage bag 8 and the head portion 3, generation of particles in the liquid 9 and contamination of the liquid 9 with fine dust are suppressed.

The apparatus 1 further includes a liquid filler 11 that is a fluid that is filled in the second storage space, and a pressure regulator 12 that adjusts the pressure of the liquid filler 11 filled in the second storage space. The liquid filler 11 is a fluid which is not compressible, that is, an incompressible fluid, and may be, for example, a liquid or a gelatinous substance. The liquid filler 11 is preferably an aqueous liquid or a gel.

The second storage space, that is, the space in which the liquid filling material 11 is filled, is connected to the pressure regulator 12 via a communication member 13 such as a pipe. The communication member 13 is provided with a valve 14, a valve 15, and a joint 16 placed between the valve 14 and the valve 15.

The joint 16 is constructed of two separable joint portions (not shown). Since the communication member 13 is provided with the joint 16, the communication member 13 can be at a position between the pressure regulator 12 and the valve 14 and the pressure adjustment The separator 12 is separated. As a result, the unit 4 can be separated by the body of the device 1.

As mentioned above, the unit 4 is constructed to be detachable from the body of the device 1. In the case where the unit 4 is damaged or the liquid 9 stored in the storage bag 8 is used up, this allows the device 1 to be used again only by replacing the unit 4.

The valve 14 and the valve 15 are closed before the unit 4 is separated by the body of the device 1. Here, in a state where the pressure in the outer casing 7 is maintained at a negative pressure by the pressure regulator 12, the valve 14 is closed, whereby the pressure in the outer casing 7 is maintained at a negative pressure. Therefore, the liquid 9 can be prevented from leaking from the discharge port 10. By closing the valve 15, the feeding of the liquid packing 11 by the pressure regulator 12 is stopped, and thus the leakage 11 of the liquid packing 11 can be prevented.

The liquid filler 11 is filled in the second storage space. If compared to the volume of a gas, the volume of liquid and colloid is less likely to be affected by changes in temperature and pressure. Thus, even if the ambient temperature or pressure of the apparatus 1 fluctuates, the volume of the liquid filler 11 is almost constant, and the change in the pressure of the liquid 9 in the first storage space is suppressed.

A portion of the outer casing 7 can form a buffer portion 17. In particular, a portion of the wall surface of the outer casing 7 is made of a flexible film, whereby the buffer portion 17 is formed. The buffer portion 17 functions when the operation of the device 1 is stopped or the power is supplied to the device 1 during the operation.

The volume of the liquid filler 11 and the liquid 9 slightly varies due to changes in pressure or temperature. Due to the liquid filler 11 and the liquid 9 The buffer portion 17 absorbs pressure fluctuations in the change in volume; therefore, the pressure fluctuation of the liquid 9 in the first storage space is controlled to be small.

If compared to the volume of the gas, since the volume of the liquid filler 11 is less likely to be affected by changes in temperature or pressure, as compared to the case where the gas is filled in the second storage space, this embodiment is more advantageous. The buffer portion 17 can be reduced in size. The buffer portion 17 is not limited to the configuration in which the outer casing 7 is provided with the buffer portion 17. The communication member 13 can be provided with the buffer portion 17.

According to this embodiment, the liquid 9 is stored in the storage bag 8, and the liquid filler 11 is filled in the space between the outside of the storage bag 8 and the outer casing 7. Therefore, the storage bag 8 is hardly in contact with the gas. Thus, the gas hardly enters the storage bag 8, and the increase in the pressure of the liquid 9 in the storage bag 8 can be suppressed.

The flexible member constituting the storage bag 8 may be, for example, a member having low gas permeability, such as a multilayer aluminum film. Even if bubbles are generated in the liquid filler 11, the use of such a member having low gas permeability suppresses the permeation of the bubbles into the storage bag 8, and thus the increase in the pressure of the liquid 9 in the storage bag 8 can be suppressed. .

The liquid 9 is stored in the first storage space, and the liquid filler 11 is filled in the second storage space. The difference in density between the liquid 9 and the liquid filler 11 is less than the difference in density between the liquid 9 and the gas. When an impact is applied to the outer casing 7, reducing the difference between the density of the material stored in the first storage space and the density of the material filled in the second storage space enables the sway of the storage bag 8 to be reduced.

In the case where, for example, a gas is filled in the second storage space, the density of the gas is negligibly small as compared to the liquid 9. In this case, the gas moves in accordance with the movement of the storage bag 8 storing the liquid 9. Thus, when an impact is applied to the outer casing 7, the gas hardly inhibits the movement of the storage bag 8, and thus the storage bag 8 swings considerably.

A liquid filler 11 having a small difference in density from the liquid 9 stored in the first storage space is filled in the second storage space. Therefore, the liquid filler 11 moves in the outer casing 7 regardless of the movement of the storage bag 8 containing the liquid 9. That is, when the impact is applied to the outer casing 7, the movement of the liquid filler 11 and the movement of the storage bag 8 containing the liquid 9 are suppressed from each other; therefore, the sway of the storage bag 8 is reduced.

The liquid filler 11 preferably has a density from 80% to 120% of the density of the liquid 9. When the liquid filler 11 has a density within this range, the sway of the storage bag 8 can be effectively reduced.

When the gas is filled in the second storage space, the difference in density between the liquid 9 stored in the first storage space and the gas filled in the second storage space is regarded as 100%. When the liquid filler 11 has a density from 80% to 120% of the density of the liquid 9, the difference in density between the liquid filler 11 and the liquid 9 is 20% or less. Therefore, the swing of the storage bag 8 can be reduced to one-fifth or less as compared with the case where the gas is filled in the second storage space. Since the difference in density between the liquid filler 11 and the liquid 9 is small, the storage bag 8 is less likely to sway. Pressure fluctuation of the liquid 9 stored in the storage bag 8 It is suppressed by reducing the sway of the storage bag 8.

According to this embodiment, the pressure fluctuation of the liquid 9 stored in the storage bag 8 can be suppressed as described above. Thus, the pressure fluctuation of the liquid 9 in the head 3 communicating with the first storage space is suppressed, and the pressure in the head 3 is maintained negative. As a result, leakage (liquid leakage) of the liquid 9 from the head 3 can be suppressed.

In this embodiment, for example, the outer casing 7 may have a volume of 400 ml, the liquid 9 may have an initial volume of about 250 ml, the sorption medium 23 may have a volume of 50 ml, and the initial volume of the liquid filler 11 Can be about 100 ml. The invention is not limited to this configuration. The volume of the outer casing 7, the initial volume of the liquid 9, the volume of the sorption medium 23, and the initial volume of the liquid filler 11 can be appropriately determined. For example, the outer casing 7 may have a volume of 400 ml, the sorption medium 23 may have a volume of 50 ml, and the liquid 9 may have an initial volume of about 350 ml, and no liquid filler 11 may be filled in the initial state. In the second storage space.

The flexible member constituting the storage bag 8 has a thickness of about 10 micrometers to 200 micrometers and as much as possible a volume of up to about 5 milliliters to 6 milliliters. Thus, the volume of the flexible member constituting the storage bag 8 is about 1% of the sum of the volume of the liquid filler 11 and the volume of the liquid 9, and is sufficiently small. Therefore, the difference in density between the flexible member constituting the storage bag 8 and the liquid filler 11, and the difference in density between the flexible member constituting the storage bag 8 and the liquid 9 are negligible.

An example of a flexible member constituting the storage bag 8 is a laminated film made of aluminum, which has a relatively high airtightness. The laminated film typically has a thickness of about 10 microns. The density of aluminum is 2.7 g/cm ³ and is considerably larger than the density of the liquid filler 11 and the density of the liquid 9. The storage bag 8 has a volume ratio of the volume of the liquid filler 11 to the sum of the volumes of the liquid 9 of less than 1%. Therefore, the density of the storage bag 8 is negligible.

The inside of the outer casing 7 is filled with the liquid 9 and the liquid filler 11; therefore, the rocking of the storage bag 8 can be reduced. As a result, the leakage of the liquid 9 from the discharge port 10 can be suppressed.

In some cases, in the state in which the unit 4 is attached to the unit 4, an external force is applied to the communication member 13 to cause the outer casing 7 to swing considerably. Again, in some cases, the unit 4 moves in the device 1. Even in these cases, the sway of the storage bag 8 in the unit 4 is reduced, and thus the leakage of the liquid 9 from the head 3 can be suppressed.

FIG. 3A is an illustration of the pressure regulator 12. As shown in FIG. 3A, the pressure regulator 12 can include a pressure sensor 18, a pump 19, a valve 20, a reservoir 21, and a controller 22.

The pressure sensor 18 is a pressure measuring unit for measuring the pressure of the liquid filler 11 in the communication member 13. The pressure measured by the pressure sensor 18 is the relative pressure of the liquid packing 11 relative to the pressure in the apparatus 1. To avoid the effects of disturbances, the pressure sensor 18 is preferably placed in proximity to the valve 15.

The liquid filler 11 is stored in the storage tub 21. The pump 19 transfers the liquid filling 11 between the storage tub 21 and the outer casing 7. Examples of pumps 19 include tube pumps, diaphragm pumps, and gear pumps. The valve 20 is located between the pump 19 and the reservoir 21 and is normally closed.

The pressure sensor 18 measures the pressure of the liquid fill 11 and transmits a signal corresponding to its pressure to the controller 22. The controller 22 controls the operation of the valve 20 and the pump 19 based on the pressure of the liquid packing 11 in the communication member 13. In this state, the pump 20 is driven to move the liquid filler 11 between the storage tubs 21 to adjust the pressure in the outer casing 7 to a predetermined value.

The operation of the apparatus 1 is described below with reference to Figures 3B and 4. Fig. 3B is an illustration showing the state in which the storage bag 8 is contracted by the state shown in Fig. 3A, and is associated with the consumption of the liquid 9. Figure 4 is a flow chart showing how the pressure of the liquid fill 11 is controlled using the pressure sensor 18 and the controller 22.

When the device 1 is actuated, the controller 22 begins to control the pressure in the housing 7.

Discharging the liquid 9 from the discharge port 10 of the head 3 reduces the amount of liquid 9 stored in the storage bag 8 to reduce the volume of the storage bag 8. In the state in which the valve 20 is closed, the outer casing 7 and the communication member 13 are sealed; therefore, the pressure of the liquid filler 11 in the outer casing 7 and the communication member 13 is reduced.

The controller 22 allows the pressure sensor 18 to measure the pressure of the liquid filling 11 in the communication member 13 (S40). The pressure sensor 18 transmits a signal corresponding to the measured pressure of the liquid fill 11 to the controller 22. The controller 22 controls the operation of the pump 19 and the valve 20 based on signals transmitted by the pressure sensor 18.

In particular, the controller 22 determines the liquid filler in the communication member 13. Whether the pressure of 11 is within a predetermined range (S41). In the case where the controller 22 determines that the pressure of the liquid filler 11 in the communication member 13 is lower than the predetermined range, the controller 22 opens the valve 20 and drives the pump 19 (S42). The pump 19 feeds the liquid packing 11 from the storage tank 21 to the outer casing 7, whereby the pressure in the outer casing 7 is increased (filling step).

Thereafter, the pressure sensor 18 measures the pressure of the liquid filler 11 in the communication member 13 again (S40), and the controller 22 determines whether the pressure of the liquid filler 11 in the communication member 13 is within the predetermined range ( S41). In this case, the controller 22 determines that the pressure of the liquid fill 11 in the communication member 13 is within the predetermined range, and the controller 22 closes the valve 20 and stops the pump 19. As a result, the liquid filler 11 is stopped by the feeding of the storage tub 21 to the outer casing, and the increase in the pressure in the outer casing 7 is stopped.

As described above, the controller 22 controls the operation of the valve 20 and the pump 19 based on the results measured using the pressure sensor 18, whereby the pressure in the outer casing 7 is adjusted within the predetermined range (pressure Adjustment steps).

In the case where the pressure in the outer casing 7 is excessively increased, the liquid filling 11 is transferred from the outer casing 7 to the storage tub 21 using the pump 19. This allows the pressure in the outer casing 7 to be reduced.

After the pressure in the casing 7 is adjusted, the controller 22 determines whether the pressure control is stopped (S43). In the case where the controller 22 determines that the pressure control is not stopped, the controller 22 allows the pressure sensing The device 18 measures the pressure of the liquid filler 11 in the communication member 13 (S40).

In this embodiment, the pressure regulator 12 adjusts the pressure of the liquid 9 in the head 3 as described above, whereby the crescent shape of the liquid 9 in the discharge port 10 is well maintained. As such, the discharge stability of the head 3 is enhanced.

Since the liquid filling 11 is filled in the second storage space in association with the consumption of the liquid 9, the pressure of the liquid 9 in the head 3 is maintained irrespective of the consumption of the liquid 9. This is advantageous for the device 1 when the outer casing 7 has a large volume. Increasing the volume of the outer casing 7 enables the frequency of replacing the unit 4 to be reduced.

A movable mechanism such as a pump has a problem that a particle system is caused by its operation. In this embodiment, the pressure regulator 12 is not in direct contact with the liquid 9. Therefore, even if the particles are generated by the operation of the pressure regulator 12, the particles enter only the liquid filler 11 and do not enter the liquid 9. Thus, there is an advantage that the liquid 9 can be reduced by the particulate regulator due to the pressure regulator 12.

According to this embodiment, the outer casing 7 is filled with the liquid 9 and the liquid filler 11, and thus the pressure of the liquid 9 can be determined only by measuring the pressure of the liquid filler 11. The change in the pressure of the liquid filler 11 is hardly affected by the deformation of the storage bag 8. Thus, the pressure of the liquid 9 is precisely determined by measuring the pressure of the liquid filler 11.

Since the pressure of the liquid 9 is precisely determined, the liquid 9 in the head 3 can be maintained at a desired negative pressure, and the crescent of the liquid 9 in the discharge ports 10 is well maintained. As a result, the discharge of the head 3 Stability is enhanced.

Since the liquid filler 11 and the liquid 9-series liquid, the change in the volume of the liquid filler 11 and the liquid 9 is less than the change in the volume of the gas, and the pressure of the liquid filler 11 and the liquid 9 does not rapidly change.

When the storage bag 8 is contracted in association with the consumption of the liquid 9 as shown in Fig. 3B, the outer casing 7 is refilled with the liquid filling 11 depending on the contraction of the storage bag 8. The difference in density between the liquid filler 21 and the liquid 9 is quite small. Therefore, even if the volume ratio between the liquid filler 11 and the liquid 9 in the outer casing 7 fluctuates, the change in density in the outer casing 7 associated with the consumption of the liquid 9 is relatively small. Therefore, the pressure fluctuation does not have to be compensated due to the change in the volume ratio therebetween, and the structure of the apparatus 1 can be simplified.

[Method of Manufacturing Hardened Product Pattern]

A method of manufacturing a hardened product pattern according to an embodiment of the present invention is described below. 5A to 5G are schematic cross-sectional views showing a method of manufacturing the hardened product pattern.

The method for producing the hardened product pattern comprises the first step (1) of placing the photohardenable component on the substrate using the liquid discharge device, and the second step (2) of bringing the photohardenable component into contact with the mold, a third step (3) of irradiating the photohardenable component with light to harden the photohardenable component into a hardened product, and a fourth step of separating the hardened product obtained in the third step from the mold (the fourth step) 4).

The method of manufacturing the hardened product pattern is a method using the photon imprint process.

The hardened product pattern is preferably a patterned hardened product having a size of from 1 nanometer to 10 millimeters, and more preferably from 10 nanometers to 100 micrometers. In general, a pattern forming technique for preparing a hardened product having a pattern (irregular structure) having a nanometer size (1 nm to 100 nm) using light is referred to as the photon nanoimprinting process. The method of manufacturing the hardened product pattern uses the photon nanoimprint process.

Each step is described below.

[Placement step (1)]

In this step (placement step), as shown in Fig. 5A, the liquid 9 is placed (applied) on the substrate 6 using the apparatus 1, whereby a wet film is formed.

The substrate 6 as the target on which the liquid 9 is placed is a processed substrate, and is usually a germanium wafer. In the case of manufacturing an imprint mold by a method of manufacturing the hardened product pattern, the substrate 6 may be a quartz substrate. In the case of manufacturing the imprint mold, the substrate 6 may be a quartz substrate having a metal compound layer thereon.

In the present embodiment, the substrate 6 is not limited to the hydrophobic water or the quartz substrate. The substrate 6 can be arbitrarily selected from conventional semiconductor device substrates such as an aluminum substrate, a titanium tungsten alloy substrate, an aluminum-niobium alloy substrate, an aluminum-copper alloy substrate, a tantalum oxide substrate, and a tantalum nitride substrate. The substrate 6 (treated substrate) used may be a substrate subjected to surface treatment including 矽 The alkane coupling treatment, the decane treatment, and the formation of an organic film have an increased affinity for the liquid 9.

The thickness of the shape transfer layer (wet film) depends on its application, and is, for example, from 0.01 micrometers to 100.0 micrometers.

[Mold contact step (2)]

Next, as shown in Fig. 5B, a mold 104 having a fine pattern for transferring a pattern shape is brought into contact with the wet film, which is made of the liquid 9, and is in the previous step ( The placement step) (Fig. 5B1) is formed. This allows the portion of the wet film made of the liquid 9 to be filled into the concave portion of the fine pattern of the mold 104, whereby the coating film 106 is formed so as to be filled in the fine pattern of the mold 104. Medium (Figure 5B2).

Considering this next step (light irradiation step), the mold 104 is preferably made of a light transmissive material. In particular, the material constituting the mold 104 is preferably glass, quartz, a transparent resin such as polymethyl methacrylate (PMMA) or polycarbonate, a transparent vapor deposited metal film such as polydimethyl methoxyoxane. Flexible film, photo-cured film, metal film, etc. of film. In the case of using the transparent resin to constitute the mold 104, the transparent resin needs to be selected so as not to be dissolved in the component contained in the liquid 9. The material constituting the mold 104 is particularly preferably quartz because quartz has a small coefficient of thermal expansion and the strain strain of the pattern is small.

The fine pattern of the mold 104 preferably has a height of 4 nm to 200 nm and an aspect ratio of 1 to 10.

To enhance the peelability of the mold 104 from the liquid 9, the mold 104 can be surface treated prior to this step by bringing the liquid 9 into a mold contact step in contact with the mold 104.

In this step (mold contact step), when the liquid 9 is brought into contact with the mold 104 as shown in Fig. 5B1, the pressure applied to the liquid 9 is not particularly limited. In this step, the contact time of the liquid 9 with the mold 104 is not particularly limited.

This step can be carried out under any of an air atmosphere, a vacuum atmosphere, and an inert atmosphere, and is preferably carried out under a vacuum or an inert atmosphere because the influence of oxygen or moisture on the hardening reaction can be prevent.

The mold contacting step can be performed under an atmosphere containing a condensable gas (hereinafter referred to as "the atmosphere of the condensable gas"). As used herein, the term "condensable gas" means a gas that is condensed and liquefied by the capillary pressure, and a gas in the atmosphere is filled into the mold 104 along with (part of) the coated film 106. The capillary pressure is generated when the concave portion of the fine pattern and the gap between the mold 104 and the substrate 6 are formed. Before the liquid 9 (shape transfer layer) is brought into contact with the mold 104 (Fig. 5B1), the condensable gas system is present in the atmosphere.

The gas system filled in the concave portion of the fine pattern is liquefied by performing the mold contacting step under the atmosphere of the condensable gas, and thus the bubbles are eliminated; therefore, the filling property is excellent. The condensable gas can be dissolved in the liquid 9.

[Alignment step (3)]

Next, the position of the mold 104 and/or the position of the substrate 6 is adjusted as needed such that the positioning mark 105 of the mold 104 coincides with the positioning mark 103 of the substrate 6. The alignment step is indispensable and can be omitted depending on the application.

[Light irradiation step (4)]

Next, as shown in FIG. 5D, in a state in which the mold 104 and the substrate 6 are aligned with each other in the alignment step, a portion of the liquid 9 in contact with the mold 104 is light passing through the mold 104. Irradiation. In particular, the coated film 106 that is filled in the fine pattern of the mold 104 is irradiated with light passing through the mold 104. (Fig. 5D1). This allows the coated film 106 filled in the fine pattern of the mold 104 to be hardened by light, thereby forming a hardened product 108 (Fig. 5D2). The light applied to the liquid 9 is selected depending on the sensitivity wavelength of the liquid 9, which constitutes the coated film 106 which is filled in the fine pattern of the mold 104. In particular, ultraviolet rays, X-rays, electron beams, and the like having a wavelength of from 150 nm to 400 nm are appropriately selected and preferably used.

The light (irradiation light 107) applied to the liquid 9 is particularly preferably ultraviolet. This is because most commercially available hardening aids (photopolymerization initiators) are UV sensitive.

[Mold release step (5)]

Second, the hardened product 108 and the mold 104 are separated from each other. In this operation, the substrate 6 has a predetermined pattern shape (hardened product pattern) The hardened film 109 of the case is overlaid.

In this step (release step), as shown in FIG. 5E, the hardened product 108 and the mold 104 are separated from each other, and the hardened film 109 is obtained. The cured film 109 has a pattern shape, is formed in the step (4) (light irradiation step), and is reversed from the fine pattern of the mold 104.

The cured film 109 can be obtained by a series of steps (manufacturing processes) including the above steps (1) to (5) so as to have a desired irregular pattern shape at a desired position (in the mold 104) The pattern shape after the fine pattern). The obtained hardened film 109 can be used as, for example, an optical member such as a Fresnel lens or a diffraction grating (including a case where the hardened film 109 is used as a component of an optical member). In this case, the following members can be obtained: an optical member including the substrate 6 and the cured film 109, which has a pattern shape and is placed on the substrate 6.

In the method of producing the hardened product pattern, the repeating unit (emission) composed of the steps (1) to (5) can be repeatedly performed several times on the same treated substrate. Repeating the repeating unit (emission) composed of the steps (1) to (5) several times enables an irregular pattern shape (a fine pattern in the mold 104) having a plurality of desired positions on the processed substrate A cured film of the subsequent pattern shape is obtained.

[Removing the residual film of the partially cured film and removing the step (6)]

Although the hardened film 109 obtained in the demolding step, that is, in the step (5) has a specific pattern shape, one portion of the cured film 109 The portion is sometimes left in a region different from the region having the shape of the pattern (this portion of the cured film 109 is hereinafter referred to as the "residual film"). In this case, as shown in Fig. 5F, the residual film in the region to be removed is removed from the cured film 109, which has the obtained pattern shape. This allows the hardened product pattern 110 (the pattern shape after the fine pattern of the mold 104) having the desired irregular pattern to be obtained.

The method of removing the residual film is as follows: For example, the residual film as the concave portion of the cured film 109 is removed by a process such as etching, so that the surface of the substrate 6 passes through the cured film 109. The concave portion of the pattern that is owned is exposed.

In the case of removing the residual film as the concave portion of the cured film 109 by etching, the special process used is not particularly limited, and, for example, a conventional process such as a dry etching method can be used. For dry etching, conventional dry etching systems can be used.

The hardened product pattern 110 can be obtained by a manufacturing process including the above steps (1) to (6) to have a desired irregular pattern shape at a desired position (after the fine pattern of the mold 104) Pattern shape). An article having the hardened product pattern 110 can be obtained. Furthermore, the following substrate processing step (step (7)) is performed in the case of processing the substrate 6 using the hardened product pattern 110.

The optical component can be obtained using the hardened product pattern 110 as an optical member such as a diffraction grating or a polarizer (including the case where the hardened product pattern 110 is used as a component of an optical member). In this case, the following components can be obtained: including the substrate 6 and being placed on the substrate The optical member of the hardened product pattern 110 on 6.

[Substrate processing step (7)]

The hardened product pattern 110 obtained in this embodiment can be used as an interlayer insulating film for use in a typical electronic component such as a large-scale integrated circuit (LSIs), system LSIs, dynamic random memory by a semiconductor device. Take memory (DRAMs), synchronous DRAMs (SDRAMs), Rambus DRAMs (RDRAMs), and Direct RDRAMs (D-RDRAMs). Further, the hardened product pattern 110 can be used as a resist film for semiconductor device fabrication.

In the case of using the hardened product pattern 110 as a resist film, there is a portion of the substrate 6 in the residual film removal step, that is, the surface exposed in the step (6) (by FIG. 5F The area represented by reference numeral 111 is etched or ion implanted. In this operation, the hardened product pattern 110 is used as an etching mask. Further, a circuit structure 112 (FIG. 5G) based on the pattern shape of the hardened product pattern 110 can be formed on the substrate 6 by forming an electronic component. This enables, for example, a circuit board for use in semiconductor devices such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, and D-RDRAMs. Furthermore, an electronic device such as a display, camera, or medical device can be formed by connecting the circuit board to a circuit control mechanism for the circuit board.

Likewise, the electronic component can be obtained in such a manner that an etching method, ion implantation, or the like is performed using the hardened product pattern 110 as a mask (resist mask).

Alternatively, the imprinting mold can be made in such a manner that the quartz substrate corresponding to the substrate 6 is etched using the hardened product pattern 110. In this case, the quartz substrate corresponding to the substrate 6 can be etched using the hardened product pattern 110 as a mask. Alternatively, the quartz substrate can be etched such that the second hardened product is formed in the recessed portion of the hardened product pattern 110 using the second hardenable material and used as a mask.

The etching method and ion implantation are described as a method of processing the substrate 6 using the hardened product pattern 110 as a mask. The method of processing the substrate 6 is not limited to etching or ion implantation. For example, plating or the like may be performed in a state where the hardened product pattern 110 is placed on the substrate 6.

In the case of preparing the circuit board or the like, the hardened product pattern 110 may be finally removed by the processed substrate 6, or may be retained in the form of a member constituting a device.

[Other Embodiments]

An apparatus 1 applicable to a nanoimprinting apparatus is described in the above embodiment. The invention is not limited to the device 1. That is, the unit 4 that can be mounted to the device 1 is included in the present invention. The following apparatus is also included in the present invention: a nanoimprinting apparatus, the apparatus 1 can be mounted to the nanoimprinting apparatus, and a resin having a predetermined shape is formed on the substrate by the above-described photon imprinting process pattern.

Figure 6 is a schematic view of a nanoimprinting apparatus 600 in accordance with an embodiment of the present invention. The nanoimprinting apparatus 600 is such that it is placed on the substrate 6 The upper liquid 9 is a device for performing the photon imprint process by molding the mold 104 and then hardening, the mold 104 is separated from the hardened liquid 9, and the pattern is thereby transferred to the substrate 6 . The details of the photon imprint process are as described above.

The nanoimprinting apparatus 600 includes a mold head 610, a structural body 611, a light source 612, an illumination optical system 613, a bottom plate 2, a transfer section 5, and a control section 618. The nanoimprinting apparatus 600 further includes means 1 for discharging the liquid 9. The device 1 is detachably mounted to the body of the nanoimprinting apparatus 600. The entire device 1 can be detachably mounted to the body of the nanoimprinting apparatus 600. Alternatively, a portion of the device 1, such as the unit 4, can be detachably mounted only to the body of the nanoimprinting device 600.

The mold head 610 is attached to the structural body 611 and serves as a clamp for holding and moving the mold 104. The mold head 610 includes a mold chuck that vacuum clamps or electrostatically clamps the mold 104, and also includes a moving mechanism for moving the mold 104. The mold head 610 has a hardened liquid 9 that presses the mold 104 against the substrate 6 (the mold 104 is brought into contact with the hardened liquid 9), and is separated (hardened) by the hardened liquid 9 on the substrate 6. Go) the function of the mold 104.

The light source 612 and the illumination optical system 613 form an illumination system for emitting light for hardening the liquid 9 on the substrate 6. The light emitted by the light source 612 can be appropriately selected depending on the type of the liquid 9.

The bottom plate 2 is overlapped by the transfer section 5. The transfer section 5 holds and moves the substrate 6. The conveying section 5 includes a vacuum sandwiching the substrate 6 The substrate chuck 616 also includes a moving mechanism for moving the substrate 6.

The device 1 supplies the liquid 9 to the substrate 6. The liquid 9 can be applied to the upper region (emission region) of the substrate 6 in such a manner that the transport section 5 is moved (scanning motion or step motion) while the liquid 9 is being supplied by the device 1. .

The control section 618 includes a central processing unit (CPU), a memory, the like, and the like, and controls the operation of the nanoimprinting apparatus 600 (photon nanoimprinting process). In other words, the control section 618 broadly controls each section of the nanoimprinting apparatus 600 to perform the photon nanoimprinting process. In particular, in a state in which the mold 104 is pressed against the liquid 9 on the substrate 6, the control section 618 moves the mold head 610 and illuminates the light from the light source 612 and the illumination optical system 613. The liquid 9 thereby hardens the liquid 9. The control section 618 moves the mold head 610 to separate the mold 104 from the hardened liquid 9 on the substrate 6, whereby the pattern 104 of the mold 104 is transferred to the substrate 6.

〔example〕

The invention is described in further detail below with reference to examples. The technical scope of the present invention is not limited to the following examples.

[Example 1]

First, the component (A), the component (B), and the additive component (C) are mixed together underneath. The mixture is filtered through a 0.2 micron mesh filter made of ultra high molecular weight polyethylene, whereby the light can be hardened into A is obtained.

(1-1) Component (A): a total of 94 weight ratio

(A-1) Isobornyl acrylate (IB-XA ^TM , produced by Kyoeisha Chemical Co., Ltd.): 9.0 by weight mix ratio

(A-2) benzyl acrylate (V#160T ^TM , produced by): 38.0 by weight mix

(A-3) pentanediol diacrylate (NP-A ^TM , produced by Kyoeisha Chemical Co., Ltd.): 47.0 by weight mix ratio

(1-2) Component (B): a total of 3.5 weight ratio

(B-1) Lucirin TPO (produced by BASF): 3 weight ratio

(B-2) 4,4' bis(diethylamino)benzophenone (produced by Tokyo Chemical Industry Co., Ltd.): 0.5 weight ratio

(1-3) Additive component (C): 1.6 weight ratio

(C-1) Polyoxyethylene stearate SR-730 (produced by Aoki Oil & Fat Industry Co., Ltd.): 1.6 weight ratio

Subsequently, 100 ml of the photohardenable component a was measured and then loaded into a bottle made of PFA having a volume of about 100 ml. Thereafter, the absorbing medium (p-1) is charged into the bottle containing the photohardenable component a. In this example, the sorbent medium (p-1) used is a Zeta Plus (registered trademark) EC series filter, B47-40QSH (a diameter of about 47 mm and a thickness of about 3 mm, by 3M Japan Co., Ltd. production). The sorption medium (p-1) is made of cellulose, diatomaceous earth, and ion exchange resin.

The sorption medium (p-1) was loaded into the bottle and then held stationary for up to one month. Thereafter, an inductively coupled plasma (ICP) emission spectrometer, CIROS CCD (manufactured by Spike Analytical Instruments), which hardens each metal element in the component a (17 elements: sodium, calcium, iron) The contents of potassium, zinc, aluminum, magnesium, nickel, chromium, copper, lead, manganese, lithium, tin, palladium, ruthenium, cobalt, and rhodium are determined. Incidentally, the metal elements are similarly determined before the absorbing medium (p-1) is loaded into the bottle.

Before the sorption medium (p-1) was loaded into the bottle, 6.6 ppm of K was present in the photohardenable component a in the bottle. However, after the sorption medium (p-1) is loaded into the bottle and held stationary for one month, the concentration of K in the photohardenable component a is lower than that of the ICP emission spectrum analyzer. Limit (1.1ppm). Before the sorption medium (p-1) was charged into the bottle, 4.5 ppm of nickel was present in the photohardenable component a in the bottle. However, the concentration of nickel in the photohardenable component a was 3.6 ppm after the sorbent medium (p-1) was charged into the bottle and held stationary for one month. After the sorption medium (p-1) is loaded into the bottle and held stationary for one month, the concentration of each of the other metal elements in the photohardenable component a is lower than the ICP emission spectrum analysis. The detection limit of the instrument.

The metal elements are present in the photohardenable component a at any point in time when the photohardenable component a is prepared and loaded into the bottle. In this example, the amount of the metal elements can be reduced by adsorbing the metal element onto the sorption medium (p-1). According to this, when the light can be hard When the component a is brought into contact with, for example, a metal member such as an ink jet head including a discharge port, even if the photohardenable component a is contaminated with metal impurities, the amount of the metal impurities increases as time can be inhibition.

[Example 2]

After the photohardenable component a was prepared in the same manner as described in Example 1, 100 ml of the photohardenable component a was measured, and then loaded into a bottle made of PFA, having about 100 ml. volume of. Thereafter, the absorbing medium (p-2) is charged into the bottle containing the photohardenable component a. In this example, the sorbent medium (p-2) used is a Zeta Plus (registered trademark) EC series filter, B47-020GN (a diameter of about 47 mm and a thickness of about 3 mm, by 3M Japan Co., Ltd. production). The sorption medium (p-2) is made of cellulose, diatomaceous earth, and ion exchange resin.

The sorption medium (p-2) was loaded into the bottle and then held stationary for up to one month. Thereafter, using an ICP emission spectrometer, CIROS CCD (manufactured by Spike Analytical Instruments, Inc.), each of the metal elements in the photohardenable component a (17 elements: sodium, calcium, iron, potassium, zinc, aluminum) The contents of magnesium, nickel, chromium, copper, lead, manganese, lithium, tin, palladium, ruthenium, cobalt, and rhodium are determined. Incidentally, the metal elements are similarly determined before the absorbing medium (p-2) is loaded into the bottle.

Before the sorption medium (p-2) was loaded into the bottle, 6.6 ppm of K was present in the photohardenable component a in the bottle. However, the sorption medium (p-2) was loaded into the bottle and held stationary for up to one month. Thereafter, the concentration of K in the photohardenable component a is lower than the detection limit (1.1 ppm) of the ICP emission spectrum analyzer. Before the sorption medium (p-2) was charged into the bottle, 4.5 ppm of nickel was present in the photohardenable component a in the bottle. However, the concentration of nickel in the photohardenable component a was 3.3 ppm after the sorption medium (p-2) was loaded into the bottle and held stationary for one month. After the sorption medium (p-2) is loaded into the bottle and held stationary for one month, the concentration of each of the other metal elements in the photohardenable component a is lower than the ICP emission spectrum analysis. The detection limit of the instrument.

The metal elements are present in the photohardenable component a at any point in time when the photohardenable component a is prepared and loaded into the bottle. In this example, the amount of the metal elements can be reduced by adsorbing the metal elements onto the sorption medium (p-2). According to this, when the photohardenable component a comes into contact with, for example, a metal member such as an ink jet head including a discharge port, the light hardenable component a is contaminated with metal impurities, and the amount of such metal impurities is over time. The increase can be suppressed as much as possible.

While the invention has been described with reference to the exemplary embodiments thereof, it is understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following patent application is to be accorded the breadth of

1‧‧‧Liquid discharge device

2‧‧‧floor

3‧‧‧ head

4‧‧‧Liquid storage unit

5‧‧‧Transfer member

6‧‧‧Substrate

7‧‧‧Storage section

8‧‧‧storage bag

9‧‧‧Light nanoimprinting liquid

10‧‧‧Exhaust port

11‧‧‧Liquid packing

12‧‧‧ Pressure Regulator

13‧‧‧Communication

14‧‧‧ Valve

15‧‧‧ valve

16‧‧‧Connectors

17‧‧‧ buffer

23‧‧‧Sucking media

Claims (24)

A liquid discharge device comprising: a storage section for storing a liquid for nanoimprinting; and a discharge port communicating with the storage section, and discharging the liquid for nanoimprinting, wherein the liquid The discharge device is detachably mounted to the nanoimprinting apparatus, and wherein the storage section contains a sorption medium that adsorbs or absorbs at least one selected from the group consisting of particles, metal ions, and water. The liquid discharge device of claim 1, wherein the sorption medium is not discharged from the discharge port when the liquid for nanoimprinting is discharged from the discharge port. A liquid discharge device according to claim 1 or 2, wherein the sorbent medium has a small pore medium having an average pore diameter of from 0.001 μm to 0.5 μm. A liquid discharge device according to claim 1 or 2, wherein the sorption medium has a cation exchange group on a surface thereof. A liquid discharge device according to claim 1 or 2, wherein the sorption medium contains a physical or chemical desiccant. The liquid discharge device of claim 1 or 2, wherein the sorption medium has a size larger than a diameter of the discharge port, and is suspended in the storage section for the liquid for nanoimprinting in. A liquid discharge device according to claim 1 or 2, wherein The sorption medium is fixed to the inside of the storage section. The liquid discharge device of claim 7, wherein the density of the sorption medium is from 30% to 100% of the density of the liquid imprinted by the nanometer. The liquid discharge device of claim 1 or 2, wherein the sorption medium is at least one selected from the group consisting of cellulose, diatomaceous earth, polyethylene, nylon, silicone, and activated carbon. Made of materials. A liquid discharge apparatus according to claim 1 or 2, wherein the liquid system for nanoimprinting has a photohardenable component. A liquid discharge device comprising: a discharge port configured to discharge a liquid for nanoimprinting; and a storage section, wherein a space in the storage section is divided into a first storage space and a second storage space The first storage space stores the liquid for nanoimprinting and communicates with the discharge port, the second storage space is not connected to the discharge port by a separator, and the second storage space is fluidized Filling, wherein the first storage space contains a sorption medium that adsorbs or absorbs at least one selected from the group consisting of particles, metal ions, and water. The liquid discharge device of claim 11, further comprising: a pressure regulator communicating with the second storage space and adjusting a pressure of the fluid filled in the second storage space; a communication member configured to communicate the second storage space and the pressure regulator with each other; and a valve disposed in the communication unit, wherein the communication unit is adjustable from the pressure between the pressure regulator and the valve Separation. A liquid discharge apparatus according to claim 11 or 12, wherein the flow system contains an incompressible fluid of water. A liquid discharge apparatus according to claim 11 or 12, wherein the volume of the first storage space is reduced as the liquid for nanoimprinting is discharged. A liquid discharge apparatus according to claim 11 or 12, wherein the sorption medium is not discharged from the discharge port when the liquid for nanoimprinting is discharged from the discharge port. A liquid discharge device comprising: a storage section for storing a liquid for nanoimprinting; and a discharge port communicating with the storage section, and discharging the liquid for nanoimprinting, wherein the storing The section contains a sorption medium that adsorbs or absorbs at least one selected from the group consisting of particles, metal ions, and water, and wherein the sorption medium is configured to not block for nanopressure The channel of the liquid printed. A nanoimprinting apparatus for causing a mold to be pressed against a light hardenable component placed on the substrate and the photohardenable component to be hardened The method of forming a hardened product pattern on a substrate, the nanoimprinting apparatus comprising the liquid discharge device of claim 10, wherein the liquid hardenable component is placed on the substrate using the liquid discharge device. A liquid storage tank comprising a storage section for storing a liquid for nanoimprinting, wherein the storage section contains a sorption medium that adsorbs or absorbs a group selected from the group consisting of particles, metal ions, and water. At least one, and wherein the sorption medium is suspended in the liquid for nanoimprinting and/or adheres tightly to the inner surface of the storage section. A liquid storage tank according to claim 18, wherein the liquid for nanoimprinting is stored in the storage section. A method of producing a pattern of a hardened product, comprising: a first step of placing the photohardenable component on a substrate using a liquid discharge device according to claim 10; and bringing the photohardenable component into contact with the mold a second step of irradiating the photohardenable component with light to harden the photohardenable component into a hardened product; and a fourth step of separating the hardened product from the mold. A method of manufacturing an optical component comprising the step of obtaining a hardened product pattern by the method of claim 20 of the patent application. A method of manufacturing a circuit board, comprising: a step of forming a hardened product pattern on a substrate by the method of claim 20; and The step of etching or ion implanting the substrate using the hardened product pattern as a mask. The method of claim 22, wherein the circuit board is for use in a circuit board of a semiconductor device. A method of manufacturing an imprint mold, comprising: a step of forming a hardened product pattern on a substrate by a method as in claim 20; and a step of etching the substrate using the hardened product pattern.