JP2018019041A - Liquid filling method, imprinting method, and article manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid filling method capable of suppressing the remaining of air bubbles in a head. SOLUTION: This is a liquid filling method for filling a liquid discharge device including a head for discharging a first liquid and a storage portion for storing the first liquid with the first liquid, in which the inside of the head and the inside of the storage portion are filled. It has a step of filling with a condensable gas and a filling step of filling the head and the accommodating portion with the first liquid in a state where the head and the accommodating portion are sealed and filled with the condensable gas. .. [Selection diagram] Fig. 4

Description

  The present invention relates to a liquid filling method, an imprinting method, and an article manufacturing method.

  The demand for miniaturization of semiconductor devices and MEMS has advanced, and in addition to conventional photolithography technology, microfabrication technology that forms an imprint material on a substrate with a mold and forms a pattern of the imprint material on the substrate attracts attention. Collecting. This technique is also called an imprint technique, and can form a fine structure on the order of several nanometers on a substrate. For example, as one of imprint techniques, there is a photocuring method. In an imprint apparatus employing this photocuring method, first, a photocurable imprint material is applied to a shot area which is an imprint area on a substrate. Next, while aligning the pattern area of the mold and the shot area, the pattern area of the mold is brought into contact (imprinted) with the imprint material, and the imprint material is filled into the pattern area. Then, the imprint material is cured by irradiating ultraviolet rays, and a pattern of the imprint material is formed in a shot region on the substrate by separating the mold from the cured imprint material.

  In such an imprint technique, in the step of applying the imprint material to the shot area, a liquid ejection head (hereinafter referred to as “head”) is a device that ejects the imprint material that is a liquid onto a substrate. ) Is used.

  There is also known a liquid ejection apparatus that is integrally provided with a head and a liquid storage unit that stores a liquid. The head uses MEMS or the like in order to control the discharge amount of the liquid to a very small amount, and its structure is fine and complicated.

  Patent Document 1 proposes a method of filling a liquid by depressurizing a liquid storage unit. Patent Document 2 proposes a method of supplying a liquid to the head while maintaining a minute negative pressure with high accuracy.

JP 2003-334963 A JP 2008-260311 A

  In the method of adjusting the pressure and filling (supplying) the liquid disclosed in Patent Document 1 and Patent Document 2, the gas in the head is in contact with the degassed liquid, so that the gas is dissolved in the liquid, The head is filled with liquid.

  However, since the structure in the head is fine and complicated, gas that does not dissolve in the liquid remains in the head as bubbles. When bubbles remain in the head, there is a problem in that the amount of liquid ejected is smaller and ejection defects occur than when bubbles do not remain in the head.

  Therefore, there has been a demand for a method for suppressing bubbles from remaining in the head when the head is filled with liquid.

  Therefore, an object of the present invention is to provide a liquid filling method, an imprinting method, and an article manufacturing method capable of suppressing bubbles remaining in the head.

  A liquid filling method as one aspect of the present invention that solves the above-described problem is a liquid filling method that fills a liquid ejection apparatus that includes a head that ejects a first liquid and an accommodating portion that accommodates the first liquid. In the method, the step of filling the head and the housing with a condensable gas, and the head and the housing filled with the condensable gas in a state where the head and the housing are sealed. Filling the first liquid.

  According to the present invention, it is possible to provide a liquid filling method, an imprinting method, and an article manufacturing method that can prevent bubbles from remaining in the head.

1 is a diagram illustrating an imprint apparatus according to Embodiment 1. FIG. 1 is a diagram illustrating a liquid ejection apparatus according to Embodiment 1. FIG. FIG. 3 is a diagram illustrating a head of the liquid ejection apparatus according to the first embodiment. 5 is a flowchart illustrating a method for filling an imprint material in the liquid ejection apparatus according to the first embodiment. 1 is a diagram showing a condensable gas according to Example 1. FIG. 6 is a diagram illustrating a process of filling an imprint material according to Example 1. FIG. FIG. 3 is a diagram illustrating a discharge unit in the liquid discharge apparatus after being filled with an imprint material according to the first embodiment. FIG. 6 is a diagram illustrating a liquid ejection apparatus according to a second embodiment. It is a figure for demonstrating the manufacturing method of articles | goods.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In each figure, the same members are denoted by the same reference numerals, and redundant description is omitted.

  A typical apparatus configuration of the imprint apparatus according to the first embodiment will be described with reference to FIG. The imprint apparatus 1 is an apparatus for forming a pattern of a cured product in which a concave / convex pattern of a mold is transferred by bringing an imprint material supplied on a substrate into contact with a mold and applying energy for curing to the imprint material. It is.

  Here, as the imprint material, a curable composition (which may be referred to as an uncured resin) that is cured when energy for curing is applied is used. As the energy for curing, electromagnetic waves, heat, or the like is used. The electromagnetic wave is, for example, light such as infrared light, visible light, or ultraviolet light whose wavelength is selected from a range of 150 nm to 1 mm.

  A curable composition is a composition which hardens | cures by irradiation of light or by heating. Among these, the photocurable composition cured by light contains at least a polymerizable compound and a photopolymerization initiator, and may contain a non-polymerizable compound or a solvent as necessary. The non-polymerizable compound is at least one selected from the group consisting of a sensitizer, a hydrogen donor, an internal release agent, a surfactant, an antioxidant, and a polymer component.

  The imprint material is applied in a film form on the substrate by a spin coater or a slit coater. Alternatively, the liquid ejecting head may be applied to the substrate in the form of droplets, or in the form of islands or films formed by connecting a plurality of droplets. The imprint material has a viscosity (viscosity at 25 ° C.) of, for example, 1 mPa · s or more and 100 mPa · s or less.

  As the substrate, glass, ceramics, metal, semiconductor, resin, or the like is used, and a member made of a material different from the substrate may be formed on the surface as necessary. Specific examples of the substrate include a silicon wafer, a compound semiconductor wafer, and quartz glass.

  In this embodiment, the imprint apparatus 1 will be described as adopting a photocuring method in which the imprint material is cured by light irradiation. In the following, the direction parallel to the optical axis of the irradiation optical system to be described later, which irradiates the imprint material on the substrate with ultraviolet rays, is defined as the Z axis, and two directions orthogonal to each other in a plane perpendicular to the Z axis are defined. The X axis and the Y axis are assumed.

  As shown in FIG. 1, the imprint apparatus 1 includes an irradiation unit 2, a mold holding mechanism 3, a substrate stage 4, a liquid ejection device 5, a control unit 6, a magnification correction mechanism 18, and an alignment measurement system 22. And have. Further, the imprint apparatus 1 supports the bridge surface plate 25, which extends from the base surface plate 24 on which the substrate stage 4 is placed, the bridge surface plate 25 that fixes the mold holding mechanism 3, and the base surface plate 24. And a support 26 for the purpose. The imprint apparatus 1 includes a mold conveyance mechanism (not shown) that conveys the mold 7 from the outside of the apparatus to the imprint apparatus 1 (mold holding mechanism 3), and the substrate 11 from the outside of the apparatus to the imprint apparatus 1 (substrate stage 4). And a substrate transfer mechanism (not shown) for transferring.

  The irradiation unit 2 includes a light source (not shown) and an irradiation optical system (not shown), and the irradiation optical system includes a combination of optical elements described later. In the imprint process, the irradiation unit 2 irradiates the imprint material 14 on the substrate 11 with ultraviolet rays 8 (that is, light for curing the imprint material 14) 8 through the mold 7. The irradiation unit 2 includes a light source 9 and optical elements (lens, mirror, light shielding plate, etc.) for adjusting the ultraviolet light 8 from the light source 9 to a light state suitable for imprint processing (light intensity distribution, illumination region, etc.). ) 10. In the present embodiment, since the photocuring method is employed, the imprint apparatus 1 includes the irradiation unit 2. However, when the thermosetting method is employed, the imprint apparatus 1 has a heat source for curing the imprint material (thermosetting imprint material) instead of the irradiation unit 2.

  The mold 7 has a rectangular outer peripheral shape, and includes a pattern portion (a concavo-convex pattern to be transferred to the substrate 11 such as a circuit pattern) formed in a three-dimensional shape on a surface (pattern surface) facing the substrate 11. 7a. The mold 7 is made of a material that can transmit the ultraviolet light 8, for example, quartz.

  The mold 7 has a cavity (concave portion) 7b for facilitating deformation of the mold 7 on the surface opposite to the pattern surface (incident surface on which the ultraviolet rays 8 are incident). The cavity 7b has a circular planar shape. The thickness (depth) of the cavity 7 b is set according to the size and material of the mold 7.

  The cavity 7 b communicates with an opening 17 provided in the mold holding mechanism 3, and a light transmitting member 13 is disposed in the opening 17 to make a space 12 surrounded by a part of the opening 17 and the cavity 7 b a sealed space. Has been. The pressure in the space 12 is controlled by a pressure adjustment mechanism (not shown). For example, when the mold 7 is pressed against the imprint material 14 on the substrate 11, the pressure in the space 12 is made higher than the external pressure by the pressure adjustment mechanism, and the pattern portion 7 a of the mold 7 is moved against the substrate 11. Bend into a convex shape. As a result, the mold 7 comes into contact with the imprint material 14 on the substrate 11 from the central portion of the pattern portion 7a. Therefore, the gas (air) is suppressed from being confined between the pattern portion 7a and the imprint material 14, and the imprint material 14 can be efficiently filled in the pattern portion 7a.

  The mold holding mechanism 3 includes a mold chuck 15 that attracts and holds the mold 7 by vacuum suction force or electrostatic force, and a mold moving mechanism 16 that holds the mold chuck 15 and moves the mold 7 (mold chuck 15). The mold chuck 15 and the mold moving mechanism 16 have an opening 17 at the center (inner side) so that the ultraviolet light 8 from the irradiation unit 2 is irradiated onto the imprint material 14 on the substrate 11.

  The magnification correction mechanism 18 is disposed on the mold chuck 15 and applies a force (displacement) to the side surface of the mold 7 held by the mold chuck 15 to correct the shape of the pattern portion 7a of the mold 7 (that is, the pattern portion 7a is corrected). Deform). The magnification correction mechanism 18 includes, for example, a piezo element that expands and contracts by a volume change when a voltage is applied, and is configured to pressurize a plurality of portions on each side surface of the mold 7. The magnification correction mechanism 18 deforms the pattern portion 7 a of the mold 7, thereby matching the shape of the pattern portion 7 a of the mold 7 with the shape of the shot region formed on the substrate 11.

  However, there may be a case where it is difficult for the magnification correction mechanism 18 to match the shape of the pattern portion 7 a of the mold 7 with the shape of the shot area formed on the substrate 11. In such a case, the shot region formed on the substrate 11 is also deformed so as to reduce the shape difference between the shape of the pattern portion 7a of the mold 7 and the shape of the shot region formed on the substrate 11. May be. In order to deform the shot region formed on the substrate 11, for example, the substrate 11 may be heated and thermally deformed.

  The mold moving mechanism 16 selectively presses (imprints) the mold 7 on the imprint material 14 on the substrate 11 or pulls the mold 7 away from the imprint material 14 on the substrate 11 (release). As is done, the mold 7 is moved in the Z-axis direction. The actuator applicable to the mold moving mechanism 16 includes, for example, a linear motor and an air cylinder. The mold moving mechanism 16 may be composed of a plurality of drive systems such as a coarse drive system and a fine drive system in order to position the mold 7 with high accuracy. The mold moving mechanism 16 may be configured to be able to move the mold 7 not only in the Z-axis direction but also in the X-axis direction and the Y-axis direction. Further, the mold moving mechanism 16 may be configured to have a tilt function for adjusting the position of the mold 7 in the θ (rotation around the Z axis) direction and the tilt of the mold 7.

  Impression and release of the mold 7 in the imprint apparatus 1 are realized by moving the mold 7 in the Z-axis direction as in the present embodiment. However, it may be realized by moving the substrate 11 (substrate stage 4) in the Z-axis direction. Further, the stamping and releasing of the mold 7 may be realized by relatively moving both the mold 7 and the substrate 11 in the Z-axis direction.

  The substrate stage 4 can move while holding the substrate 11. When pressing the mold 7 against the imprint material 14 on the substrate 11, the substrate stage 4 is moved to align the substrate 11 with the mold 7. The substrate stage 4 includes a substrate chuck 19 that attracts and holds the substrate 11 by vacuum suction force or electrostatic force, and a substrate moving mechanism 20 that mechanically holds the substrate chuck 19 and can move in the XY plane. In addition, a reference mark 21 used for positioning the substrate stage 4 is disposed on the substrate stage 4.

  Actuators applicable to the substrate moving mechanism 20 include, for example, a linear motor and an air cylinder. The substrate moving mechanism 20 may be composed of a plurality of drive systems such as a coarse motion drive system and a fine motion drive system in order to position the substrate 11 with high accuracy. The substrate moving mechanism 20 may be configured to be able to move the substrate 11 not only in the X-axis direction and the Y-axis direction but also in the Z-axis direction. Further, the substrate moving mechanism 20 may be configured to have a tilt function for adjusting the position of the substrate 11 in the θ (rotation around the Z axis) direction and the tilt of the substrate 11.

  The liquid ejecting apparatus 5 supplies the imprint material 14 onto the substrate 11 based on preset supply amount information. The supply amount (that is, supply amount information) of the imprint material 14 supplied from the liquid ejection device 5 is, for example, the thickness of the pattern of the imprint material 14 formed on the substrate 11 (the thickness of the remaining film). And the pattern density of the imprint material 14 are set.

  The control unit 6 is configured by a computer including a CPU, a memory, and the like, and controls the entire imprint apparatus 1 according to a program stored in the memory. The control unit 6 controls the imprint process for forming a pattern on the substrate by controlling the operation and adjustment of each unit of the imprint apparatus 1. The control unit 6 may be configured integrally with other parts of the imprint apparatus 1 (in a common casing), or may be configured in a different pair (within another casing) from the other parts of the imprint apparatus 1. It may be configured. Moreover, the control part 6 is good also as a structure which consists of a some computer.

  The alignment measurement system 22 measures the positional deviation between the alignment mark formed on the substrate 11 and the alignment mark formed on the mold 7 in the X axis and Y axis directions. The controller 6 adjusts the position of the substrate stage 4 based on the positional deviation measured by the alignment measurement system 22 so that the position of the mold 7 and the position of the substrate 11 are aligned with each other. The alignment measurement system 22 can also measure the shape of the pattern portion 7 a of the mold 7 and the shape of the shot area formed on the substrate 11. Therefore, the alignment measurement system 22 also functions as a measurement unit that measures the alignment state between the region of the substrate 11 to be subjected to the imprint process and the pattern portion 7a of the mold 7. In this embodiment, the alignment measurement system 22 measures the shape difference between the pattern portion 7a of the mold 7 and the shot area formed on the substrate 11.

  The liquid ejection apparatus according to the first embodiment will be described with reference to FIG. The liquid ejection device 5 is a device that ejects a liquid (first liquid) such as an imprint material.

  The liquid ejection device 5 includes a storage portion 51 that stores the imprint material 14 that is a liquid. In addition, the liquid ejection device 5 includes an accommodation unit 51 and a head 52 including a plurality of ejection units 53 for ejecting the imprint material 14 onto the substrate 11. The discharge unit 53 communicates with the storage unit 51 and discharges the imprint material 14 stored in the storage unit 51. Also, normally, in the manufacturing process of the liquid ejection device 5, after the housing portion 51 and the head 52 are combined and integrated, the imprint material 14 is filled into the housing portion 51 and the head 52.

  The head 52 of the liquid ejection device 5 according to the first embodiment will be described with reference to FIG. The head 52 includes a plurality of ejection units 53. FIG. 3 shows one ejection unit 53 among the plurality of ejection units 53 included in the head 52. The discharge unit 53 is appropriately designed according to the characteristics, volume, and required accuracy of the imprint material 14 to be discharged, and is subjected to fine processing. For example, the diameter of the discharge part 53 is 1.0 μm or more and 999 μm or less. In addition, the discharge unit 53 is configured with a diaphragm 55 for discharging the imprint material 14. The diaphragm 55 includes an elastic thin film, and the imprint material 14 can be discharged by increasing the pressure of the imprint material 14 in the discharge portion 53.

  A method of filling the liquid ejection apparatus according to the first embodiment with a liquid will be described with reference to FIG. In S <b> 401, a liquid (second liquid) obtained by liquefying the condensable gas 27 is injected into the storage unit 51. Here, the condensable gas 27 is liquefied by being cooled below the boiling point. By liquefying the condensable gas 27, the volume is reduced as compared with the gas state, so that a large amount of condensable gas can be easily injected into the accommodating portion 51.

  The condensable gas 27 will be described with reference to FIG. The condensable gas 27 has a boiling point at atmospheric pressure of −10 ° C. to 25 ° C., and a vapor pressure at 25 ° C. of 0.1 MPa to 0.4 MPa. For example, as the condensable gas 27, 1,1,1,3,3-pentafluoropropane (CF3CH2CHF2, hereinafter referred to as “PFP”) can be used. PFP has a boiling point of 15.3 ° C. at atmospheric pressure and a vapor pressure of 0.15 MPa at 25 ° C. It cools to 15.3 degrees C or less under atmospheric pressure, or liquefies at 25 degreeC by applying a force of 50 kPa in addition to a vapor pressure of 0.15 MPa, ie, atmospheric pressure.

As another example of the condensable gas 27, as shown in FIG. 5, a condensable gas represented by the following gas characteristic formulas (1) to (12) may also be included.
CH3 (CH2) 2CH3 (1)
CHF2 (CF2) 2CF3 (2)
CF3CHFCF2CF3 (3)
CH (CF3) 3 (4)
CF3CHCH3CF3 (5)
CH3 (CH2) 2CF3 (6)
c- (CF2) 4 (7)
CF3 (CF2) 2CF3 (8)
CHF2CHFCF3 (9)
CFCl3 (10)
CHClCHCF3 (11)
C (CH3) 4 (12)

  Moreover, even if it is other than said condensable gas, if the boiling point or vapor pressure satisfy | fills said conditions, it can be contained in the condensable gas 27. FIG.

  The accommodating part 51 etc. in S401 are demonstrated using Fig.6 (a). The injection port 56 is provided in a location different from the location where the head 52 is located in the accommodating portion 51. A liquid 27 a obtained by liquefying the condensable gas 27 is injected from the injection port 56. At this time, the head 52 is directed upward. Since the liquid 27 a is heavier than the air 28, it accumulates in the lower part of the accommodating part 51, and the air 28 having the same volume as the liquid 27 a is discharged outside from the discharge part 53. Further, the volume of the liquid 27a to be injected is set to about 1/10 of the volume of the storage part 51, so that the air 28 remains in the storage part 51.

  Returning to FIG. 4, S402 will be described. In S402, the accommodating part 51 is heated so that the inside of the accommodating part 51 becomes normal temperature (for example, 23 degreeC), and the liquid 27a which liquefied the condensable gas 27 is vaporized. The accommodating part 51 in S402 is demonstrated using FIG.6 (b). The liquid 27a is vaporized when the inside of the accommodating part 51 becomes normal temperature. The volume of the condensable gas 27 obtained by vaporizing the liquid 27a is about 200 times. Usually, since the condensable gas 27 is heavier than the air 28, only the excess condensable gas 27 goes out from the discharge part 53 together with the air 28. Therefore, the condensable gas 27 is filled in the accommodating portion 51. Further, when the liquid 27a is vaporized, the temperature inside the accommodating portion 51 may decrease due to the heat of vaporization, or the pressure in the accommodating portion 51 may increase because the discharge portion 53 is narrow. Therefore, there is a possibility that all the liquid 27a is not vaporized, and it is necessary to determine whether or not it is vaporized. For example, when the weight of the container 51 is measured and becomes substantially the same as the weight before injecting the liquid 27a, it is determined that the liquid 27a has been completely vaporized, and S402 can be ended.

  In addition, the concentration of the condensable gas 27 in the accommodating portion 51 is desirably 99% or more. Therefore, S401 and S402 may be repeated a plurality of times in order to more reliably fill the condensable gas 27 in the housing 51. The number of repetitions necessary for filling the condensable gas 27 in the accommodating portion 51 varies depending on the size and shape of the discharge portion 53. Therefore, an experiment or the like may be performed in advance to obtain the number of repetitions in advance. Thereby, the density | concentration of the condensable gas 27 in the accommodating part 51 can be made high concentration, for example, 99% or more.

  Returning to FIG. 4, S403 will be described. In S <b> 403, the sealing body 57 is attached to the head 52, the discharge unit 53 is closed, and the storage unit 51 is sealed. The material of the sealing body 57 is, for example, a resin material such as isoprene rubber, fluorine rubber, urethane rubber, silicon rubber, polycarbonate, polypropylene, polyethylene, or a metal material such as SUS, and a mixture thereof. The accommodating part 51 etc. in S403 are demonstrated using FIG.6 (c). The sealing body 57 has a shape that covers the entire discharge portion 53. By attaching the sealing body 57 to the head 52 and fixing the sealing body 57 to the head 52 with a seal or the like, the entire discharge portion 53 is closed and the accommodating portion 51 is sealed.

  Returning to FIG. 4, S404 will be described. In S <b> 404, the imprint material 14 is injected from the injection port 56. With reference to FIG. 6D, the storage unit 51 and the like in S404 will be described. By injecting the imprint material 14 from the injection port 56, the pressure in the accommodating portion 51 rises and exceeds the saturated vapor pressure of the condensable gas 27. The condensable gas 27 is liquefied to become a liquid 27a. The liquid 27 a obtained by liquefying the condensable gas 27 has a volume of about 1/300 or more and 1/100 or less and is dissolved in the imprint material 14. Further, when all the condensable gas 27 is not liquefied, the accommodating portion 51 may be cooled so that the temperature in the accommodating portion 51 is equal to or lower than the boiling point of the condensable gas 27. In addition, an external temperature measuring device may be used to measure the temperature in the housing part 51, or a temperature sensor may be provided in the housing part 51. Thereby, all the condensable gas 27 is liquefied and dissolved in the imprint material 14. At this time, it is necessary to determine whether or not all the condensable gas 27 is liquefied. For example, the weight of the container 51 is measured, and the weight obtained by subtracting the weight of the injected imprint material 14 from the increased weight can be regarded as the weight of the liquid in which the condensable gas 27 is liquefied. If the weight of the liquid in which all the condensable gas 27 equal to the volume of the storage unit 51 is liquefied increases, it can be determined that all the condensable gas 27 has been liquefied, and S404 can be ended.

  The discharge part 53 after filling the imprint material will be described with reference to FIG. FIG. 7A shows the discharge unit 53 after filling the printing material in the filling method of this embodiment. As shown in FIG. 7A, the ejection unit 53 is filled with the imprint material without any bubbles remaining. This is because the condensable gas 27 filling the inside of the accommodating portion 51 is dissolved in the imprint material 14. Further, even when air remains in the accommodating portion 51 and bubbles remain in the discharge portion 53, the volume of the remaining bubbles can be reduced to such an extent that the discharge amount is not affected. On the other hand, FIG.7 (b) has shown the discharge part 53 after filling the printing material in the conventional filling method as a comparative example. When the imprint material 14 is discharged in a state where air bubbles remain in the discharge portion 53 together with the imprint material 14 and the air bubbles remain, an imprint material 14 having an amount smaller than a preset supply amount is generated. There is a problem of being supplied.

  The imprint material 14 in FIG. 7A includes a liquid 27a obtained by liquefying the condensable gas 27 in S404. When the contraction rate when changing from a gas to a liquid is determined from the molecular weight of the condensable gas 27, the liquid 27a of about 0.3 to 1.0% with respect to the imprint material is included. The imprint material 14 containing the liquid 27a has a contact angle with the material of the head 52 and becomes liquid repellent. In particular, when the condensable gas 27 is a fluorine-containing material such as PFP, the effect becomes remarkable. In the case of the fluorine-containing condensable gas 27, since it has the property of appearing on the surface of the droplets, even a very small amount has a remarkable effect. Further, in the case of the condensable gas 27 other than the fluorine-containing material, it is possible to obtain characteristics necessary for becoming liquid repellent by selecting the composition. Therefore, the imprint material 14 containing the liquid 27a suppresses bubbles from remaining in the vicinity of the discharge port 54 of the discharge portion 53 and the curved portion of the discharge portion 53, compared to the imprint material 14 that does not contain the liquid 27a. Is done. In addition, the imprint material 14 containing the liquid 27a is less likely to remain in the discharge unit 53 and in the vicinity of the discharge port 54, so that the cleaning of the head 52 becomes unnecessary or the number of cleanings of the head 52 is reduced. The liquid 27a volatilizes after being supplied onto the substrate 11 together with the imprint material 14, and therefore does not remain on the substrate 11.

  Therefore, in the liquid ejection device filled with the liquid using the liquid filling method of the first embodiment, it is possible to suppress the bubbles from remaining in the head 52. Further, in the imprint apparatus to which the liquid ejection apparatus filled with the liquid using the liquid filling method of the first embodiment is applied, a preset supply amount of the imprint material can be supplied onto the substrate, A line width pattern can be formed with high accuracy.

  Next, a liquid ejection apparatus and a liquid filling method according to the second embodiment will be described. In addition, the matter which is not mentioned here can follow Example 1. FIG.

  A liquid ejection apparatus according to the second embodiment will be described with reference to FIG. As illustrated in FIG. 8A, the accommodating portion 51 according to the second embodiment is not provided with the injection port 56. Thereby, it can suppress that a foreign material mixes in the accommodating part 51 from the injection port 56. FIG.

  When the liquid 27 a obtained by liquefying the condensable gas 27 in S 401 in FIG. 4 is injected into the storage unit 51, the liquid 27 a is injected from a part of the discharge unit 53. Further, when the imprint material 14 is injected into the storage unit 51 in S404 in FIG. In addition, when the liquid 27a or the imprint material 14 is injected into the storage unit 51, the liquid 27a or the imprint material 14 may be injected from the plurality of ejection units 53 using a plurality of tubes (not shown).

  Further, as shown in FIG. 8B, a sealing body 58 may be attached when the liquid 27a or the imprint material 14 obtained by liquefying the condensable gas 27 is injected into the accommodating portion 51. The sealing body 58 has a shape that partially covers the discharge portion 53. The material of the sealing body 58 is the same as the material of the sealing body 57 of the first embodiment. By attaching the sealing body 58 to the head 52 and fixing the sealing body 58 to the head 52 with a seal or the like, a part of the discharge portion 53 is blocked and the accommodating portion 51 is sealed. Thereby, some discharge parts 53 can be sealed and it can suppress that a foreign material mixes in the accommodating part 51 from some discharge parts 53. FIG.

  Therefore, in the liquid ejection apparatus that is filled with the liquid using the liquid filling method according to the second embodiment, bubbles can be prevented from remaining in the head 52. Further, in the imprint apparatus to which the liquid discharge apparatus filled with the liquid using the liquid filling method of the second embodiment is applied, a desired amount of liquid can be supplied onto the substrate, and a fine line width pattern can be increased. It can be formed with high accuracy. Furthermore, in the liquid ejection device that is filled with the liquid using the liquid filling method according to the second embodiment, it is possible to prevent foreign matter from being mixed into the housing portion.

(Product manufacturing method)
The pattern of the cured product formed using the imprint apparatus is used permanently on at least a part of various articles or temporarily used when manufacturing various articles. The article is an electric circuit element, an optical element, a MEMS, a recording element, a sensor, or a mold. Examples of the electric circuit elements include volatile or nonvolatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensor, and FPGA. Examples of the mold include an imprint mold.

  The pattern of the cured product is used as it is as a constituent member of at least a part of the article, or temporarily used as an imprint material mask. After etching or ion implantation is performed in the substrate processing step, the imprint material mask is removed.

  Next, a specific method for manufacturing an article will be described. As shown in FIG. 9A, a substrate 1z such as a silicon wafer on which a workpiece 2z such as an insulator is formed is prepared. A printing material 3z is applied. Here, a state is shown in which the imprint material 3z in the form of a plurality of droplets is applied on the substrate.

  As shown in FIG. 9B, the imprint mold 4z is made to face the imprint material 3z on the substrate with the side having the concave / convex pattern formed thereon. As shown in FIG. 9C, the substrate 1z provided with the imprint material 3z is brought into contact with the mold 4z, and pressure is applied. The imprint material 3z is filled in a gap between the mold 4z and the workpiece 2z. In this state, when light is irradiated as energy for curing through the mold 4z, the imprint material 3z is cured.

  As shown in FIG. 9D, when the imprint material 3z is cured and then the mold 4z and the substrate 1z are separated, a pattern of a cured product of the imprint material 3z is formed on the substrate 1z. This cured product pattern has a shape in which the concave portion of the mold corresponds to the convex portion of the cured product, and the concave portion of the mold corresponds to the convex portion of the cured product, that is, the concave / convex pattern of the die 4z is transferred to the imprint material 3z. It will be done.

  As shown in FIG. 9 (e), when etching is performed using the pattern of the cured product as an anti-etching mask, the portion of the surface of the workpiece 2z where there is no cured product or remains thin is removed, and the grooves 5z and Become. As shown in FIG. 9 (f), when the pattern of the cured product is removed, an article in which the groove 5z is formed on the surface of the workpiece 2z can be obtained. Although the cured product pattern is removed here, it may be used as, for example, a film for interlayer insulation contained in a semiconductor element or the like, that is, a constituent member of an article without being removed after processing.

  As mentioned above, although preferred embodiment of this invention was described, it cannot be overemphasized that this invention is not limited to these embodiment, A various deformation | transformation and change are possible within the range of the summary.

Claims (16)

A liquid filling method for filling a first liquid with a liquid ejecting apparatus including a head for ejecting a first liquid and a housing for housing the first liquid,
Filling the inside of the head and the housing with a condensable gas;
A liquid filling method comprising: filling the first liquid into the head and the housing portion in a state where the head and the housing portion are sealed with the condensable gas. . The step of filling the inside of the head and the inside of the accommodating portion with the condensable gas,
An injection step of injecting a second liquid in which the condensable gas is liquefied into the accommodating portion;
The liquid filling method according to claim 1, further comprising: a vaporizing step of vaporizing the second liquid in the housing portion. In the filling step, the first liquid is filled from an inlet provided in a place different from the place where the head is located in the housing part,
In the injection step, the second liquid is injected from the injection port.
The liquid filling method according to claim 2, wherein: In the filling step, the first liquid is filled from the discharge portion of the first liquid of the head,
Injecting the second liquid from the discharge portion of the first liquid of the head in the injecting step;
The liquid filling method according to claim 2, wherein:   5. The liquid filling method according to claim 1, wherein, in the filling step, a sealing body is attached to the head to seal the housing portion. 6. In the filling step, the storage portion is cooled so as to be equal to or lower than the boiling point of the condensable gas, and the first liquid is filled in the head and the storage portion.
The liquid filling method according to any one of claims 1 to 5, wherein the liquid filling method is performed.   In the filling step, the amount of the first liquid in the head and in the accommodating portion is measured based on the weight of the head and the accommodating portion, and it is determined whether or not to end the injection of the first liquid. The liquid filling method according to any one of claims 1 to 6, wherein:   In the vaporizing step, the amount of the condensable gas that vaporizes the second liquid in the head and in the accommodating portion is measured based on the weight of the head and the accommodating portion, and the vaporization of the second liquid is completed. The liquid filling method according to claim 2, wherein whether or not to perform the determination is determined.   9. The liquid filling according to claim 2, wherein in the injecting step, the second liquid is injected into the housing portion with the head positioned higher than the housing portion. Method.   10. The liquid filling method according to claim 2, wherein, in the vaporization step, the second liquid is vaporized by placing the head at a position higher than the housing portion.   11. The liquid filling method according to claim 1, wherein the liquid ejecting apparatus includes the head and the housing unit as a single unit.   The condensable gas has a boiling point at atmospheric pressure of -10 ° C to 25 ° C and a vapor pressure at 25 ° C of 0.1 MPa to 0.4 MPa. The liquid filling method according to claim 1.   The condensable gases are CF3CH2CHF2, CH3 (CH2) 2CH3, CHF2 (CF2) 2CF3, CF3CHFCF2CF3, CH (CF3) 3, CF3CHCH3CF3, CH3 (CH2) 2CF3, c- (CF2) 4, CF3 (CF2) 2CF3, CHF2CHFCF3. The liquid filling method according to any one of claims 1 to 12, wherein any one of C1, CHCl3, CHClCHCF3, and C (CH3) 4 is contained. An imprint method for forming a pattern of an imprint material on a substrate using a mold,
Prepare a liquid ejection device with an empty head and housing,
Filling the inside of the head and the accommodating portion with a condensable gas,
In a state where the head filled with the condensable gas and the housing portion are sealed, the imprint material is filled in the head and the housing portion,
Discharging the imprint material from the head filled with the imprint material toward the substrate;
Curing the imprint material on the substrate in a state where the mold is in contact with the imprint material supplied onto the substrate by the discharge,
Pulling the mold away from the cured imprint material;
An imprint method characterized by the above. Injecting a liquid in which the condensable gas is liquefied into the accommodating portion, and vaporizing the liquid in the accommodating portion, thereby filling the inside of the head and the accommodating portion with a condensable gas,
The imprint method according to claim 14, wherein: A step of forming a pattern on a substrate by the imprint method according to claim 14 or 15,
Processing the substrate on which the pattern has been formed in the step.
A method for manufacturing an article.