JP6569718B2 - Imprint transfer board - Google Patents

Description

The present invention relates to transfer substrate for Lee down printing.

In recent years, a pattern forming technique using an imprint method has attracted attention as a fine pattern forming technique that replaces the photolithography technique. The imprint method is a pattern forming technique in which a fine structure is transferred at an equal magnification by using a mold member (mold) having a fine concavo-convex structure and transferring the concavo-convex structure to a molding resin. For example, in an imprint method using a photocurable resin as a molding resin, droplets of the photocurable resin are supplied to the surface of the transfer substrate, and the mold having the desired concavo-convex structure and the transfer substrate are brought to a predetermined distance. The concavo-convex structure is filled with a photocurable resin, and in this state, light is irradiated from the mold side to cure the photocurable resin. A pattern structure having an inverted uneven structure (uneven pattern) is formed.
In such an imprint method, the surface state of the mold and the transfer substrate is important. That is, the filling property of the photocurable resin into the concavo-convex structure of the mold is affected by the state of the interface between the mold and the photocurable resin and the interface between the transfer substrate and the photocurable resin. In addition, depending on the interface between the cured resin layer and the mold and the interface between the cured resin layer and the transfer substrate, damage to the concavo-convex structure of the mold or chipping of the resin layer may occur when the mold and the resin layer are separated. May occur. In particular, in the imprint method of the nanometer order, such a defect is likely to occur, and the surface state of the mold and the transfer substrate is extremely important. For this reason, in the imprint method, the surface state of the mold or the transfer substrate is controlled to a desired state by forming a release film on the mold or forming an adhesion film on the transfer substrate surface. (Patent Documents 1 and 2).

JP 2010-234575 A JP 2013-8911 A

However, as described above, when a release film is formed on the mold or an adhesion film is formed on the transfer substrate surface, the formed release film exhibits a desired release property or the formed adhesion film is desired. It is important whether the adhesiveness is expressed. For this reason, it is desired to manage the surface state of the release film provided on the mold and the adhesion film provided on the transfer substrate with a quantitative index. However, in order to suppress the influence on dimensional accuracy in imprints of nanometer order, the release film and adhesive film are formed as thin films in monolayer units, and optical measurement means can obtain quantitative values. It was difficult. Therefore, there has been a problem that a release film and an adhesive film that cannot exhibit desired performance cannot be reliably detected, and defects in imprint cannot be prevented.
In addition, when the performance of the release film provided in the mold deteriorates with time, the release film is removed and a new release film is formed again. However, it is not possible to remove the release film. When it is complete, there is a problem that the performance of the newly formed release film is lowered and the accuracy of the mold is lowered.
In addition, when the transfer substrate is provided with a metal thin film such as a chromium thin film on the surface, the state of the oxide film generated on the metal thin film and the charging characteristics affect the generation of defects in imprinting and the processing of the transfer substrate. There was a problem.
The present invention has been made in view of the circumstances as described above, and an object thereof is to provide a transfer substrate for Lee down printing.

In order to achieve such an object, the present invention provides an imprint transfer substrate that is used by providing an adhesive film in a desired region on the surface facing the mold, and is intended to form a pattern on the surface facing the mold. includes a conductive portion made provided the desired site in the region except the region, the surface of the conductive portion is made on purpose coplanar with respect to the mold surface opposed to, the entire surface of the conductive portion It is exposed, and the adhesive film is provided so as to cover at least the pattern formation scheduled region and the surface of the conductive portion . In the imprint transfer substrate, the conductive portion is configured to be used for inspecting the state of the adhesion film provided in the pattern formation scheduled region. In addition, the present invention is provided so as to cover a conductive portion provided in a desired portion of a region excluding the pattern formation scheduled region on a surface facing the mold, and to cover at least the pattern formation planned region and the surface of the conductive portion. The surface of the conductive part is flush with the surface facing the mold, and the entire surface of the conductive part is exposed.

Transfer substrate for Lee down print of the present invention, Lee down printing method, the implementation of the method of manufacturing a patterned structure shall facilitate to prevent breakage of the mold, stably producing a pattern structure of a high-precision The effect that it can be done is produced.

FIG. 1 is a drawing for explaining an embodiment of the film inspection method of the present invention. FIG. 2 is a drawing for explaining another embodiment of the film inspection method of the present invention. FIG. 3 is a diagram showing the correlation used in the film inspection method of the present invention and showing the relationship between the potential difference and film thickness in a desired substance. FIG. 4 is a diagram showing the correlation used in the film inspection method of the present invention, showing the relationship between the potential difference and the adhesion force in a desired substance. FIG. 5 is a view for explaining an embodiment of the imprint mold of the present invention, FIG. 5 (A) is a plan view, and FIG. 5 (B) is shown in FIG. 5 (A). It is a longitudinal cross-sectional view in the II line of the mold for imprinting. 6 is a view for explaining another embodiment of the imprint mold of the present invention, FIG. 6 (A) is a plan view, and FIG. 6 (B) is shown in FIG. 6 (A). It is a longitudinal cross-sectional view in the II-II line of the mold for imprint shown. 7 is a view for explaining another embodiment of the imprint mold of the present invention, FIG. 7 (A) is a plan view, and FIG. 7 (B) is shown in FIG. 7 (A). It is a longitudinal cross-sectional view in the III-III line of the mold for imprint shown. FIG. 8 is a view for explaining an embodiment of the imprint transfer substrate of the present invention, FIG. 8 (A) is a plan view, FIG. 8 (B) and FIG. It is a longitudinal cross-sectional view in the IV-IV line of the mold for imprint shown by FIG. 8 (A). FIG. 9 is a schematic side view illustrating an embodiment of the imprint apparatus according to the present invention. FIG. 10 is a schematic side view illustrating an embodiment of an imprint apparatus according to the present invention. FIG. 11 is a block diagram for explaining a processing unit in the imprint apparatus of the present invention. FIG. 12 is a process diagram for explaining an embodiment of an imprint method and a pattern structure manufacturing method according to the present invention. FIG. 13 is a process diagram for explaining an embodiment of an imprint method and a pattern structure manufacturing method according to the present invention. FIG. 14 is a diagram illustrating the relationship between the amount of change in potential difference and the adhesion force in Example 1. FIG. FIG. 15 is a diagram illustrating the relationship between the amount of change in potential difference and the adhesion force in Example 2. FIG. 16 is a diagram illustrating the relationship between the amount of change in potential difference and the adhesion force in Example 3. FIG. 17 is a graph showing the temporal relationship between the amount of change in potential difference and the adhesion force in Example 4. FIG. 18 is a graph showing the relationship between the number of days elapsed after production and the adhesion strength in Example 4.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Note that the drawings are schematic or conceptual, and the dimensions of each member, the ratio of sizes between the members, etc. are not necessarily the same as the actual ones, and represent the same members. However, in some cases, the dimensions and ratios may be different depending on the drawing.

[Film inspection method]
The film inspection method of the present invention is a film inspection method for inspecting the state of a film on a substrate, and utilizes the fact that the dielectric constant between electrodes changes due to the change in the state of a substance located between opposing electrodes. The detection electrode is disposed so as to face the conductive portion where the film exists and is located at a predetermined position above, and the state of the film is detected from the potential difference between the conductive portion and the detection electrode. Here, the state means thickness (abundance), characteristics, etc., for example, thickness of the organic film, adhesion between the organic film and the specific substance, releasability between the organic film and the specific substance, metal film The oxidation state of the natural oxide film formed on the surface of the metal, the charging characteristics of the metal film, and the distribution of these characteristics within the substrate surface vary. In the present invention, the material of the film is not limited to organic or inorganic, and the thickness of the film is not limited, but the state of the thin film in units of monolayers can be detected.

<First Embodiment>
FIG. 1 is a drawing for explaining an embodiment of the film inspection method of the present invention. In the example shown in FIG. 1, the state of the film 1 located on the substrate 11 is inspected. In this example, the substrate 11 has conductivity such as a metal substrate or a wafer, and the substrate 11 itself is a conductive portion. Then, the detection electrode 13 is disposed close to the substrate 11 through the film 1, and the potential difference V (V = V ₁ −V ₂ ) between the substrate 11 and the detection electrode 13 is measured. As shown in FIG. 2, when the substrate 11 'is made of an insulating material such as a quartz substrate or a glass substrate, the conductive portion 12 is provided on the surface of the substrate 11' on which the film 1 is provided, thereby detecting the conductive portion 12 and the substrate 11 '. The potential difference V (V = V ₁ −V ₂ ) of the electrode 13 is measured. It should be noted that the conductive substrate 11 and the conductive portion 12 that can be the conductive portion itself are not insulators, and their electrical conductivity is not particularly limited. For example, if it is 0.001 S / m or more Good.
Such a potential difference V between the substrate 11 and the conductive portion 12 and the detection electrode 13 is measured by, for example, periodically changing the capacitance by periodically changing the distance between the detection electrode 13 and the film 1 and monitoring the flowing current. can do.

  In the present invention, for a desired substance, the relationship between the potential difference between the electrodes where the substance is present and the state of the film is acquired in advance, and the potential difference between the substrate 11 and the conductive part 12 and the detection electrode 13 measured as described above. From V, the state of the film can be detected. For example, as shown in FIG. 3, for the substances A and B, the relationship between the potential difference between the electrodes where the substances exist and the film thickness is obtained in advance, so that the film 1 is separated from the substance A or B. In this case, the state of the film 1, in this case, the thickness of the film 1, can be detected from the measured potential difference V between the substrate 11 and the conductive part 12 and the detection electrode 13 and the correlation shown in FIG. 3. In addition, as shown in FIG. 4, with respect to the substance C and the substance D, the above-described film 1 is separated from the substance C or the substance D by acquiring the relationship between the potential difference between the electrodes where the substance exists and the adhesion force in advance. In this case, the state of the film 1, in this case, the adhesion force of the film 1, can be detected from the measured potential difference V between the substrate 11 and the conductive part 12 and the detection electrode 13 and the correlation shown in FIG. 4. Further, for a desired substance, a correlation between a potential difference between electrodes in which the substance exists and film characteristics such as releasability may be acquired in advance and used.

<Second Embodiment>
Further, in the present invention, the potential difference V between the substrate 11 or the conductive portion 12 and the detection electrode 13 as described above is measured, and thereafter, a predetermined charge is applied to the substrate 11 or the conductive portion 12. 12 and the detection electrode 13 are measured, and the state of the film can be detected from the difference between the potential difference V and the potential difference V ′. In addition to using the change in the dielectric constant between the electrodes due to the change in the state of the substance located between the electrodes facing each other, when the film is charged by applying a charge, the substance constituting the film This is based on the fact that an inherent potential change occurs. Then, for a desired substance, the relationship between the membrane state and the difference between the potential difference V and the potential difference V ′ is acquired in advance, and the membrane state is detected from the difference between the measured potential difference V and the potential difference V ′. Can do. The charge application to the substrate 11 and the conductive portion 12 can be performed using, for example, a corona discharge device, atmospheric pressure plasma, a plasma generator, or the like.
The measurement of the potential difference V ′ between the substrate 11 and the conductive portion 12 and the detection electrode 13 after the charge application as described above also flows by changing the capacitance by periodically changing the distance between the detection electrode 13 and the film 1. This can be done by monitoring the current.

<Third Embodiment>
Further, in the present invention, a predetermined charge is applied to the substrate 11 or the conductive portion 12 to measure the potential difference V ′ between the substrate 11 or the conductive portion 12 and the detection electrode 13, and then the substrate 11 or the conductive portion 12 and the detection electrode are measured. 13 potential differences V 'are measured over time, and the state of the membrane can be detected from the change in potential difference V'. In addition to using the change in the dielectric constant between the electrodes due to the change in the state of the substance located between the electrodes facing each other, it is inherent to the substances that make up the film by charging the film by applying a charge. This is based on the fact that the charge amount is attenuated. For a desired substance, the relationship between the state of the membrane and the change in potential difference V ′ (attenuation of charge amount) is acquired in advance, and the state of the membrane can be detected from the measured change in potential difference V ′. it can. The charge application to the substrate 11 and the conductive portion 12 can be performed using, for example, a corona discharge device, atmospheric pressure plasma, a plasma generator, or the like.
The time-lapse measurement of the potential difference V ′ between the substrate 11 or the conductive portion 12 and the detection electrode 13 after the charge application as described above also varies the capacitance by periodically changing the distance between the detection electrode 13 and the film 1. It can be implemented by monitoring the flowing current.

The film inspection method of the present invention as described above can be applied to confirm the state (thickness, characteristics, etc.) of the formed film at the time of film formation. In addition, the present invention can be applied to a state inspection of a film after film formation, for example, inspection of releasability and adhesion deterioration with time, generation of a surface oxide film in a metal film, change in charging characteristics in a metal film, and the like. Furthermore, the present invention can be applied to the cleaning management by grasping the degree of film removal (the degree of residual film generation) during the cleaning of the substrate. According to the film inspection method of the present invention, the state of the film at the time of film formation, the state of the film after formation, the remaining amount of film at the time of film removal, etc. can be inspected easily and accurately.
The above-described embodiments of the film inspection method are examples, and the present invention is not limited to these. For example, a predetermined charge may be applied to the conductive portion, and after the measurement of the potential difference between the conductive portion and the detection electrode is completed, the film to be inspected may be neutralized. Such film neutralization can be performed by using a soft X-ray irradiation type or corona discharge type ionizer.

[Imprint mold]
FIG. 5 is a view for explaining an embodiment of the imprint mold of the present invention, FIG. 5 (A) is a plan view, and FIG. 5 (B) is shown in FIG. 5 (A). It is a longitudinal cross-sectional view in the II line of the mold for imprinting. 5, an imprint mold 31 includes a mesa-structured base material 32 having a convex structure 34 on one surface 33a of a base 33, and a concavo-convex structure region A set on the surface 34a of the convex structure 34 (FIG. 5). 5 (A) and a concavo-convex structure 35 located in the concavo-convex structure region A. Moreover, the conductive part 36 is provided in the site | part outside the uneven | corrugated structure area | region A among the desired site | parts of the area | region except the uneven | corrugated structure area | region A, in the example of illustration, the surface 34a of the convex structure part 34. The surface of the conductive portion 36 is flush with the surface 34 a of the convex structure portion 34. Note that the concavo-convex structure 35 in FIG. 5B is shown for convenience and is not limited to this, and the concavo-convex structure 35 is not shown in FIG. 5A. .

  6 is a view for explaining another embodiment of the imprint mold of the present invention, FIG. 6 (A) is a plan view, and FIG. 6 (B) is shown in FIG. 6 (A). It is a longitudinal cross-sectional view in the II-II line of the mold for imprint shown. In FIG. 6, an imprint mold 41 includes a base material 42, a concavo-convex structure region A set on one surface 42 a of the base material 42 (a region surrounded by a chain line in FIG. 6A), and a concavo-convex structure. It has a concavo-convex structure 45 located in the region A. In addition, the conductive portion 46 is provided in a desired portion of the region outside the concavo-convex structure region A. The surface of the conductive portion 46 forms the same surface as the one surface 42a of the base material 42, but may be concave with respect to the surface 42a. Note that the concavo-convex structure 45 in FIG. 6B is shown for convenience and is not limited to this, and the concavo-convex structure 45 is not illustrated in FIG. 6A. .

  FIG. 7 is a view for explaining another embodiment of the imprint mold of the present invention, FIG. 7 (A) is a plan view, and FIG. 7 (B) is FIG. It is a longitudinal cross-sectional view in the III-III line of the mold for imprint shown by FIG. In FIG. 7, a mold 51 for imprinting has a mesa structure base 52 having a convex structure 54 on one surface 53a of a base 53, and an uneven structure region A set on the surface 54a of the convex structure 54 (FIG. 7 (A) and a concavo-convex structure 55 located in the concavo-convex structure region A. In addition, the conductive portion 56 is provided in a desired portion of the region excluding the concavo-convex structure region A, in the illustrated example, in a desired portion of one surface 53a of the base 53. The surface of the conductive portion 56 is convex with respect to the one surface 53 a of the base 53, but its thickness is smaller than the thickness of the convex structure portion 54. Note that the uneven structure 55 in FIG. 7B is shown for convenience and is not limited to this, and the uneven structure 55 is not shown in FIG. 7A. .

If the molding resin used for imprinting is photocurable, the material of the base material 32, 42, 52 of the imprinting mold 31, 41, 51 is transparent to the irradiation light for curing them. Possible materials can be used, for example, glass such as quartz glass, silicate glass, calcium fluoride, magnesium fluoride, acrylic glass, sapphire, gallium nitride, polycarbonate, polystyrene, acrylic, polypropylene, etc. These resins or any of these laminated materials can be used. In addition, when the molding resin to be used is not photocurable, or when it is possible to irradiate light for curing the molding resin from the transfer substrate side, the base materials 32, 42, and 52 have optical transparency. In addition to the above materials, for example, metals such as silicon, nickel, titanium, and aluminum and alloys thereof, oxides, nitrides, carbon materials such as DLC (diamond-like carbon), or these Any laminate material can be used.
The thicknesses of the base materials 32, 42, and 52 of the mold 1 can be set in consideration of the shape of the mold, the strength of the material, the handling suitability, etc., and can be set as appropriate within a range of about 300 μm to 10 mm, for example. .

The conductive portions 36, 46, 56 of the imprint molds 31, 41, 51 are formed so as to cover the uneven structure region A of the molds 31, 41, 51 and the conductive portions 36, 46, 56. It is a member for enabling a film to be inspected by the above-described film inspection method of the present invention. Such conductive portions 36, 46, and 56 only have to have an electric conductivity of 0.001 S / m or more. Preferably, a metal having a high electric conductivity such as gold, silver, copper, or aluminum, or ITO ( It may be a single layer structure composed of one type of conductive material such as an electrically conductive inorganic compound (such as indium tin oxide) or a laminated structure composed of two or more types. The thickness of the conductive portions 36, 46, and 56 can be appropriately set within a range of, for example, 0.010 to 100 μm. Further, the shape of the surface of the conductive portions 36, 46, and 56 is not particularly limited as long as the minimum width is 1 mm or more, and the surface area is preferably larger than the area of the detection electrode, for example, 1 mm ^2. As described above, it can be appropriately set within this range. Furthermore, the number of the conductive portions 36, 46, 56 provided in the molds 31, 41, 51 may be plural. In this case, the conductive portions 36, 46, 56 may also serve as mold alignment marks.

Such conductive portions 36, 46, and 56 may be connected to electrical wiring (not shown) in order to perform inspection by the above-described film inspection method of the present invention. Further, when performing the film inspection method, if measurement can be performed by connecting a terminal for inspection to the conductive portions 36, 46, 56, there may be no electrical wiring.
The above-described imprint mold of the present invention can accurately inspect the state of the release film formed so as to cover the conductive portion by the above-described film inspection method of the present invention. Therefore, the imprint method and the pattern structure manufacturing method of the present invention, which will be described later, can be easily carried out, the mold can be prevented from being damaged, and a highly accurate pattern structure can be stably produced.
In the present invention, when the base material 32, 42, 52 is made of a metal or the like, the mold 31, 41, 51 is substantially provided with a conductive portion. Further, it is not necessary to further provide the conductive portions 36, 46, 56 on the base materials 32, 42, 52.

[Transprint substrate for imprint]
FIG. 8 is a view for explaining an embodiment of the imprint transfer substrate of the present invention, FIG. 8 (A) is a plan view, and FIG. 8 (B) is shown in FIG. 8 (A). It is a longitudinal cross-sectional view in the IV-IV line of the mold for imprint shown. The imprint transfer substrate 61 of the present invention has a region 61 (a chain line in FIG. 8A) in which a pattern structure to which the concavo-convex structure of the mold is transferred is formed on a surface 61a facing the mold by imprinting. The conductive portion 62 is provided in a desired portion of the region excluding the region surrounded by).
The material of the transfer substrate 61 is, for example, glass such as quartz, soda lime glass, borosilicate glass, a resin substrate such as polycarbonate, polypropylene, polyethylene, or a composite material substrate made of any combination of these materials. It may be. Further, for example, a desired pattern structure such as a fine wiring used in a semiconductor or a display, a photonic crystal structure, an optical waveguide, or an optical structure such as holography may be formed.

The conductive portion 62 is a film inspection method according to the present invention described above, in which the adhesion film formed so as to cover the region P where the pattern structure is formed and the conductive portion 62 is formed on the surface 61a facing the mold of the transfer substrate. It is a member for enabling inspection. In FIG. 8B, the surface of the conductive portion 62 forms the same surface as the surface 61a of the transfer substrate 61. However, as shown in FIG. It may be convex. Such a conductive part 62 only needs to have an electric conductivity of 0.001 S / m or more, and is preferably a metal having high electric conductivity such as gold, silver, copper, or aluminum, or ITO (indium tin oxide). It may be a single layer structure composed of one type of conductive material such as an electrically conductive inorganic compound or a laminated structure composed of two or more types. The thickness of the electroconductive part 62 can be suitably set, for example in the range of 0.010-100 micrometers. The shape of the surface of the conductive portion 62 is not particularly limited as long as the minimum width is 1 mm or more, and the surface area is preferably larger than the area of the detection electrode, for example, 1 mm ² or more. It can be set as appropriate within the range. Furthermore, the number of conductive portions 62 provided on the transfer substrate 61 may be plural, and in this case, the conductive portions 62 may also serve as alignment marks of the transfer substrate 61.

In the example shown in FIG. 8, one region P in which the pattern structure is formed on the transfer substrate 61 is set. However, there may be a plurality of regions P. In this case, a conductive region is provided in the vicinity of each region P. The part 62 may be provided. Further, the transfer substrate 61 may have a mesa structure in which the region P is a convex flat surface in a state where the region P is one step or multi-step and higher than the surrounding region.
The above-described imprint transfer substrate of the present invention can accurately inspect the state of the adhesion film formed so as to cover the conductive portion by the above-described film inspection method of the present invention. Therefore, the imprint method and the pattern structure manufacturing method of the present invention, which will be described later, can be easily carried out, the mold can be prevented from being damaged, and a highly accurate pattern structure can be stably produced.
In the present invention, when the material of the transfer substrate 61 is a semiconductor such as silicon, gallium arsenide, or gallium nitride, a metal substrate, or a composite material substrate made of any combination of these materials, the transfer substrate 61 is: Since the conductive portion is substantially provided, the transfer substrate 61 does not need to further include the conductive portion 62.

[Imprint device]
9 and 10 are schematic side views showing an embodiment of the imprint apparatus according to the present invention. FIGS. 9 and 10 are examples in which the above-described imprint mold 31 and transfer substrate 61 according to the present invention are used.
9 and 10, the imprint apparatus 81 of the present invention includes a mold holding portion 82 for holding the mold 31, a substrate holding portion 84 for holding the transfer substrate 61, and molding on the transfer substrate 61. A resin supply unit 86 that supplies the resin and a film inspection unit 88 that inspects the release film of the mold 31 and / or the adhesion film of the transfer substrate 61 are provided.

(Mold holding part 82)
The mold holding unit 82 constituting the imprint apparatus 81 holds the mold 31. The holding mechanism of the mold 31 is, for example, a holding mechanism by suction, a holding mechanism by machine clamping, a holding mechanism by static electricity, or the like. There are no particular restrictions on the holding mechanism. Moreover, the mold holding part 82 may be movable up and down in the direction indicated by the arrow Z by the lifting mechanism 83. Above the mold holding portion 82, a light source and an optical system (not shown) for resin curing when a photo-curing resin is used as a resin to be molded may be disposed. In FIG. 9, the mold 31 is on an inspection stage 88 b of a film inspection unit 88 to be described later and is not held by the mold holding unit 82.

(Substrate holder 84)
The substrate holding portion 84 constituting the imprint apparatus 81 holds the imprint transfer substrate 61. The holding mechanism of the transfer substrate 61 is, for example, a holding mechanism by suction, a holding mechanism by mechanical clamping, or by static electricity. A holding mechanism or the like may be used, and the holding mechanism is not particularly limited. The substrate holding unit 84 can be moved on the XY stage 85 in a horizontal plane by a drive mechanism unit (not shown). 10 shows a state in which the transfer substrate 61 is on an inspection stage 88b of a film inspection unit 88 to be described later and is not held by the substrate holding unit 84.

(Resin supply part 86)
The resin supply unit 86 constituting the imprint apparatus 81 supplies droplets of the molding resin onto the transfer substrate 61 held by the substrate holding unit 84. The resin supply unit 86 is an inkjet apparatus (in the illustrated example, only the inkjet head 87 is used). As shown). The ink jet apparatus provided in the liquid drop supply unit 86 is a desired operation of the ink jet head 87 for supplying a droplet of the molding resin onto the transfer substrate 61 held by the substrate holding unit 84, for example, a horizontal plane of the XY stage 85. A drive unit that enables a reciprocating operation in a plane parallel to the ink jet, an ink supply unit to the inkjet head 87, a control unit that controls the inkjet head 87, the drive unit, and the ink supply unit.

(Membrane Inspection Unit 88)
The film inspection unit 88 constituting the imprint apparatus 1 inspects the release film of the mold 31 and / or the adhesion film of the transfer substrate 61, and is a potential measuring device (not shown) provided with the detection electrode 88a. ) And an inspection stage 88b for placing an object to be inspected. The potential measuring device including the detection electrode 88a is configured so that the state of the release film positioned on the conductive portion 36 of the mold 31 or the state of the adhesion film positioned on the conductive portion 62 of the transfer substrate 61 is determined by the conductive portions 36, The detection is performed by measuring the potential difference between 62 and the detection electrode 88a. Further, the inspection stage 88b includes a terminal, wiring, and the like (not shown) for electrically grounding the conductive portion 36 of the mold 31 or the conductive portion 62 of the transfer substrate 61.
9 shows a state in which the mold 31 is placed on the inspection stage 88b and a release film (not shown) included in the mold 31 is inspected. In FIG. 10, the transfer substrate is placed on the inspection stage 88b. 61 shows a state in which an adhesion film (not shown) included in the transfer substrate 61 is inspected.

  In order to detect the state of the release film or the state of the adhesion film from the measured potential difference between the conductive portions 36 and 62 and the detection electrode 88a, as described in the above-described film inspection method of the present invention, (1 ) The relationship between the potential difference between the electrodes where the substance is present and the state of the film is acquired in advance for the desired substance, and the state of the film is detected from the measured potential difference V between the conductive portions 36 and 62 and the detection electrode 88a. (2) The potential difference V between the conductive portions 36 and 62 and the detection electrode 88a is measured, then a predetermined charge is applied to the conductive portions 36 and 62, and the potential difference between the conductive portions 36 and 62 and the detection electrode 88a again. V ′ is measured, and a method of detecting the state of the film from the relationship between the state of the film acquired in advance and the difference between the potential difference V and the potential difference V ′, (3) a predetermined charge is applied to the conductive portions 36 and 62 After that, the conductive portions 36 and 62 and the detection electrode The potential difference V ′ of 8a is measured over time, and a method of detecting the state of the film from the relationship between the state of the film acquired in advance and the change in the potential difference V ′ (attenuation of charge amount) can be used. . As described above, when a predetermined charge is applied to the conductive portions 36 and 62, the film inspection unit 88 may include an application device that applies a charge to the conductive portions 36 and 62. Examples of such an application device include a corona discharge device, atmospheric pressure plasma, and a plasma generator.

Further, the film inspection unit 88 includes correlation data between the potential difference between the conductive units 36 and 62 and the detection electrode 88a and the state of a desired substance on the conductive units 36 and 62, and the conductivity measured by the potential measuring instrument. You may have a processing unit which detects the state of the film | membrane on the electroconductive parts 36 and 62 from the measurement result of the electrical potential difference of the parts 36 and 62 and the detection electrode 88a. FIG. 11 is a block diagram showing an example of such a processing unit. In FIG. 11, the processing unit 91 has an input unit 92, a storage unit 93, a determination unit 94, and an output unit 95 inside, and an input device 90 and an output device 100 are connected to the outside of the processing unit 91. ing.
In this processing unit 91, necessary information such as “correlation data” and “film state determination parameter” between the potential difference between the conductive portions 36 and 62 and the detection electrode 88 a and the state of the desired substance on the conductive portions 36 and 62. Is input from the input device 90 to the input unit 92, and the input data is stored in the storage unit 93. In the determination unit 94, necessary information is appropriately extracted from the storage unit 93, and the state of the film, for example, the release film of the mold 31 is determined based on the measurement result of the potential difference between the measured conductive units 36 and 62 and the detection electrode 88a. The thickness, releasability, thickness of the adhesive film of the transfer substrate 61, adhesive force, and the like can be determined, and the determination result can be output from the output unit 95 using the output device 100.

Such a film inspection unit 88 inspects the state of the release film of the mold 31 before starting imprinting and the state of the adhesion film of the transfer substrate 61, and also the mold after performing imprinting a plurality of times. The state of the release film 31, the state of the release film after cleaning the mold 31 (remaining amount), the remaining state in the adhesion film removal of the transfer substrate 61 after imprinting, etc. are inspected, and the state of the release film Judgment and state judgment of the adhesion film can be performed.
In the above-described imprint apparatus of the present invention, it is possible to prevent a mold from being damaged and to stably produce a highly accurate pattern structure by the imprint method.

The imprint apparatus according to the present invention is not limited to the illustrated example, and can move any members of the mold holding unit 82, the substrate holding unit 84, the ink jet head 87, and the film inspection unit 88, and relative to them. It may be an aspect in which the general position can be changed. Further, the film inspection unit 88 may be configured such that the mold release film can be inspected while the mold 31 is held by the mold holding unit 82, and the transfer substrate 61 is held by the substrate holding unit 84. The configuration may be such that the adhesion film can be inspected in a state.
Furthermore, the imprint apparatus according to the present invention may include a static eliminator that neutralizes the film to be inspected after the film inspection in the film inspection unit 88 is completed. Such a static eliminator can be a known ionizer of a soft X-ray irradiation method or a corona discharge method.

[Imprint Method and Pattern Structure Manufacturing Method]
12 and 13 are process diagrams for explaining an embodiment of an imprint method and a pattern structure manufacturing method according to the present invention. This embodiment is an example in which the above-described imprint mold 31 and the transfer substrate 61 of the present invention are used, and the above-described imprint apparatus 81 of the present invention is used.
In the present invention, an imprint mold 31 is prepared, and a release film 38 is formed including the surface having the concavo-convex structure 35 of the substrate 32 (FIGS. 12A and 12B). FIG. 12B is an enlarged view of a portion surrounded by a chain line in FIG.
The release film 38 is formed by, for example, a solution method such as a dipping method, a dip coating method, or a spin coating method using a fluorine-based silane compound, a fluorine-based surfactant, a silicone compound, or a vapor phase film-forming method. Can be formed.

  The mold release film 38 formed in this way determines whether or not a desired mold release property can be exhibited by examining the state of the mold release film 38 on the conductive portion 36 of the mold 31. That is, the detection electrode 88a is brought close to and opposed to the conductive portion 36 through the release film 38, and the state of the release film 38, for example, the thickness of the release film 38 or the release film 38 is determined by the above-described film inspection method of the present invention. The mold releasability of the mold film 38 is detected. If it is determined that the formed release film 38 can exhibit a desired release property (for example, the static contact angle of water droplets is 95 ° or more), the mold 31 is manufactured by the imprint method. Use in the method. If the state of the release film 38 is insufficient, the release film 38 is further formed until it is determined that the desired release property can be exhibited.

On the other hand, in the present invention, an imprint transfer substrate 61 is prepared, and an adhesion film 65 is formed on a surface 61a facing the mold 31 (FIGS. 12C and 12D). Note that FIG. 12D is an enlarged view of a portion surrounded by a chain line in FIG.
The adhesion film 65 is formed by using, for example, a silane compound containing a reactive functional group between the substrate and the resin, a phosphoric acid compound, an isocyanate compound, a thiol compound, a dipping method, a dip coating method, or a spin coating method. It can be formed by a solution method such as a method or a vapor phase film forming method.

The thus formed adhesion film 65 determines whether or not a desired adhesion force can be expressed by inspecting the state of the adhesion film 65 on the conductive portion 62. That is, the detection electrode 88a is brought close to and opposed to the conductive portion 62 through the adhesion film 65, and the state of the adhesion film 65, for example, the thickness of the adhesion film 65 or the adhesion film 65 is measured by the above-described film inspection method of the present invention. Detects adhesion and other factors. If it is determined that the formed adhesion film 65 can develop a desired adhesion force (for example, the static contact angle of the resin is 20 ° or less), the transfer substrate 61 is manufactured by the imprint method. Used for. Further, when the state of the adhesion film 65 is insufficient, the adhesion film 65 is further formed until it is determined that a desired adhesion force can be expressed.
Next, the mold 31 is held by the mold holding unit 82 of the imprint apparatus 81, and the transfer substrate 61 is held by the substrate holding unit 84.

Next, a droplet 101 of resin to be molded is discharged and supplied from a inkjet head 87 (not shown) to a desired region on the transfer substrate 61 (FIG. 13A). The number of molding resin droplets 101 to be supplied onto the transfer substrate 61, the distance between adjacent droplets, the drop amount of each droplet, the total amount of molding resin required, and the adhesion film 65 of the transfer substrate 61. The wettability of the resin to be molded with respect to the surface, the gap between the mold 31 and the transfer substrate 61 in the subsequent contact step, and the like can be set as appropriate. In FIG. 13, the release film 38 included in the mold 31 and the adhesion film 65 included in the transfer substrate 61 are omitted.
Next, the mold 31 and the transfer substrate 61 are brought close to each other, and the droplet 101 of the molding resin is developed between the mold 31 and the transfer substrate 61 to form the molding resin layer 102 (FIG. 13B). ).

Next, the molding resin layer 102 is cured to form a transfer resin layer 105 to which the uneven structure 35 of the mold 31 has been transferred (FIG. 13C). In this curing step, if the molding resin to be used is a photocurable resin, the molding resin layer 102 can be cured by performing light irradiation from the mold 31 side. When the transfer substrate 61 is made of a light transmissive material, light irradiation may be performed from the transfer substrate 61 side, or light irradiation may be performed from both sides of the transfer substrate 61 and the mold 31. On the other hand, if the molding resin to be used is a thermosetting resin, the molding resin layer 102 can be cured by heat treatment.
Next, the transfer resin layer 105 and the mold 31 are separated, and the pattern structure 111 that is the transfer resin layer 105 is positioned on the transfer substrate 61 (FIG. 13D).
Further, the transfer substrate 61 can be etched through the pattern structure 111 formed as described above, and a pattern structure 111 ′ in which the uneven structure 35 of the mold 31 is reversed can be formed on the transfer substrate 61. Furthermore, in the present invention, the transfer substrate on which the pattern structure is formed by etching as described above can be used as a replica mold to form a pattern having a concavo-convex structure as described above.
In the present invention, a semiconductor device can be manufactured by imprint lithography using a wafer as a transfer substrate.

The above-described embodiments of the imprint method and the pattern structure manufacturing method are exemplifications, and the present invention is not limited thereto. For example, a curable resin may be supplied onto the transfer substrate 61 by spin coating.
In addition to inspecting the state of the release film of the mold 31 before imprinting and the state of the adhesion film of the transfer substrate 61, the state of the release film of the mold 31 after performing imprinting a plurality of times The state of the release film after the mold 31 is washed (remaining amount), the remaining state in the removal of the adhesive film of the transfer substrate 61 after the imprinting, etc. are inspected to determine the state of the release film and the state of the adhesive film. May be performed.
In such an imprinting method and pattern structure manufacturing method of the present invention, the state of the mold release film and the state of the adhesion film of the transfer substrate can be easily and accurately inspected, and damage to the mold can be prevented. And a highly accurate pattern structure can be stably produced.

Next, the present invention will be described in more detail by showing more specific examples.
[Example 1]
A silicon wafer (diameter 150 mm) was prepared as a substrate. This substrate has a convex flat surface of 26 mm × 32 mm at the center of one surface, and the thickness of the substrate on this convex flat surface is 0.625 mm, and the thickness between the surroundings is 0.595 mm. It had a step of 0.03 mm. The electric conductivity of this substrate was 0.01 S / m, and it was confirmed that the substrate itself was a conductive part.
An adhesion film was formed on the convex flat surface side of this substrate by a vapor deposition method using an adhesion agent (KBM-5103 (3-acryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.). In the formation of the adhesion film, three types of samples 1 to 3 were produced in which the conditions of the adhesion film were changed by changing the vapor deposition conditions. When the thickness of each adhesion film formed in Samples 1 to 3 was measured using ellipsometry, it was in the range of 0.3 to 1.4 nm.

In the above three types of samples 1 to 3, a detection electrode (electrode surface: circle having a diameter of 6 mm) is brought close to the adhesion film so that the distance from the substrate surface is 1 mm, and the potential difference V between the substrate and the detection electrode is set. Measured. This potential difference was measured at 12 different locations on the substrate, and the average value was taken as the potential difference. Moreover, in said 3 types of samples 1-sample 3, the adhesive force was measured on the following measurement conditions.
(Measurement conditions for adhesion)
Measurement was performed based on the non-patent document “Measurement of Adhesive Force Between Mold and Photocurable Resin In Imprint Technology; Jpn. Appl. Phys. Vol. 41 (2002) pp. 4194-4197”. For the adhesion test, two glass substrates placed in a cross shape were used. The glass substrate was a substrate having a thickness of about 0.6 mm and a size of 75 mm × 50 mm. The breaking force between the resin and the substrate was defined as the adhesion force.

Next, in the three types of samples 1 to 3, a charge (1 As) is applied to the substrate using a corona discharge device, and the potential difference V ′ between the substrate immediately after and the detection electrode is measured in the same manner as described above. did. Thus, the potential difference V ′ measured after the charge addition is larger than the potential difference V before the charge addition, and based on the correlation between the potential difference V measured as described above and the adhesion, The relationship between the amount of change in potential difference (V′−V) and the adhesion force in Sample 3 was determined and shown in FIG.
As shown in FIG. 14, in the desired adhesive (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), the correlation between the amount of change in potential difference (V′−V) before and after the charge is added to the substrate and the adhesive force. A relationship was obtained. Therefore, the adhesion film formed on the silicon wafer using this adhesion agent measures the potential difference between the desired portion of the silicon wafer where the adhesion film exists and the detection electrode, and then immediately after the charge is applied to the silicon wafer. By measuring the potential difference and obtaining the difference, it is determined from the correlation between the potential difference change (V′−V) and the adhesion force shown in FIG. We were able to.

[Example 2]
A substrate similar to that in Example 1 was prepared, and an adhesion film was formed on the convex flat surface side of this substrate by changing the vapor deposition conditions as in Example 1. 3 was produced.
For the three types of samples 1 to 3, the potential difference V between the substrate and the detection electrode was measured in the same manner as in Example 1, and the adhesion was measured in the same manner as in Example 1.
Next, in the above three types of samples 1 to 3, as in Example 1, a charge was applied to the substrate, and the potential difference V ′ between the substrate and the detection electrode immediately after was set in the same manner as in Example 1. Measured. Further, the potential difference V ″ between the substrate and the detection electrode was measured for 60 seconds. The potential difference V ″ measured after 60 seconds had elapsed since the charge was added in this way was higher than the potential difference V ′ immediately after the charge was added. Based on the correlation between the potential difference V and the adhesion force measured as described above, the relationship between the amount of change in the potential difference (V′−V ″) and the adhesion force in Sample 1 to Sample 3 is obtained. 15 shows.

  As shown in FIG. 15, in the desired adhesive (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), the amount of change in potential difference (V′−V ″) after the charge is added to the substrate and the adhesive force. Therefore, the adhesion film formed on the silicon wafer using this adhesion agent is immediately after the charge is applied to the silicon wafer, and the desired portion of the silicon wafer where the adhesion film exists and the detection electrode The potential difference is measured, and the potential difference is measured 60 seconds after the charge is applied, and the difference is obtained, whereby the potential difference change (V′−V ″) and the adhesion force shown in FIG. From this correlation, it was possible to determine whether or not the desired adhesion could be achieved.

[Example 3]
A glass substrate (152 mm × 152 mm, thickness 6.35 mm) was prepared as a substrate. A chromium thin film was formed on one surface of the substrate by a vacuum film forming method to form a conductive portion. The electrical conductivity of this conductive part was 0.1 S / m.
An adhesion film was formed on the conductive part side of the substrate by a vapor deposition method using an adhesion agent (KBM-5103 (3-acryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.).
In the formation of this adhesion film, three types of samples A to C were produced in which the conditions of the adhesion film were changed by changing the vapor deposition conditions.

In the above three types of samples A to C, a detection electrode (electrode surface: circle having a diameter of 6 mm) is placed close to the release film so that the distance from the surface of the conductive portion is 1 mm, and the conductive portion and the detection electrode are The potential difference V was measured in the same manner as in Example 1.
Further, in the above three types of Sample A to Sample C, the adhesion was measured under the same measurement conditions as in Example 1.
Next, in the above three types of samples A to C, a charge (1 As) is applied to the conductive portion using a corona discharge device, and the potential difference V ′ between the substrate immediately after and the detection electrode is set in the same manner as described above. Measured. Thus, the potential difference V ′ measured after the charge addition is larger than the potential difference V before the charge addition, and based on the correlation between the potential difference V measured as described above and the adhesion force, the samples A to A The relationship between the amount of change in potential difference (V′−V) and the adhesion force in sample C was determined and is shown in FIG.
As shown in FIG. 16, in the desired adhesive (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), the amount of change in potential difference (V′−V) before and after adding a charge to the conductive portion provided on the glass substrate. Correlation between adhesion and adhesion was obtained. Therefore, the adhesion film formed on the glass substrate using this adhesion agent measures the potential difference between the desired part of the conductive part where the adhesion film is present and the detection electrode, and then immediately after applying a charge to the conductive part. By measuring the potential difference and obtaining the difference, it is determined from the correlation between the potential difference change amount (V′−V) shown in FIG. We were able to.

[Example 4]
A substrate similar to that in Example 1 was prepared, and an adhesive film was formed on the convex flat surface side of this substrate under predetermined vapor deposition conditions in the same manner as in Example 1 to prepare Sample A.
With respect to this sample A, the potential differences V ₁ , V ₂ , V ₃ between the substrate and the detection electrode were measured in the same manner as in Example 1 immediately after fabrication, after 3 days, and after 6 days. Similarly, the adhesion was measured.
Next, in the above-described sample A immediately after fabrication, 3 days later, and 6 days later, in the same manner as in Example 1, a charge was applied to the substrate, and the potential difference V ′ ₁ , V ′ between the substrate and the sensing electrode immediately after the sample was applied. ₂ and V ′ ₃ were measured in the same manner as in Example 1. As described above, the potential differences V ′ ₁ , V ′ ₂ , and V ′ ₃ measured after the addition of the charge are decreased with time, and more than the corresponding potential differences V ₁ , V ₂ , and V ₃ before the addition of the charge. It was an increase. Based on the correlation between the potential differences V ₁ , V ₂ , and V ₃ measured as described above and the adhesion, the amount of change in potential difference (V′−V) [change amount immediately after fabrication (V ′ ₁₋ V ₁ ), the amount of change after 3 days (V ′ ₂ −V ₂ ), the amount of change after 6 days (V ′ ₃ −V ₃ )] Indicated. Further, FIG. 18 shows the relationship between the number of days elapsed after the production and the adhesion.

  As shown in FIG. 17 and FIG. 18, in the desired adhesive (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), the correlation between the amount of change in potential difference (V′−V) taking into account the passage of time and the adhesive strength. A relationship was obtained. Therefore, when the adhesive film is formed on the silicon wafer using this adhesive and the lapse of time after the film formation is unavoidable, the desired portion of the silicon wafer where the adhesive film is present at the time of use. The potential difference from the detection electrode is measured, and then the electric potential is measured immediately after applying the charge to the silicon wafer. By obtaining the difference, the amount of change in potential difference (V′−V) shown in FIG. From the correlation with the force, it was possible to determine whether or not the adhesive film at the time of use was in a state where the desired adhesive force could be expressed.

  The present invention can be applied to the manufacture of various products having a thin film forming process, the manufacture of various pattern structures using an imprint method, and the fine processing of workpieces such as substrates.

DESCRIPTION OF SYMBOLS 1 ... Film | membrane 11 ... Board | substrate 12 ... Conductive part 13 ... Detection electrode 31, 41, 51 ... Mold 35, 45, 55 ... Uneven structure 36, 46, 56 ... Conductive part 38 ... Release film 61 ... Transfer substrate 62 ... Conductive part DESCRIPTION OF SYMBOLS 65 ... Adhesion film | membrane 81 ... Imprint apparatus 82 ... Mold holding part 84 ... Substrate holding part 86 ... Resin supply part 88 ... Film test | inspection part 88a ... Detection electrode 91 ... Processing unit

Claims (3)

In the imprint transfer substrate used by providing an adhesion film in a desired region of the surface facing the mold,
Provided with a conductive portion provided in a desired part of the region excluding the pattern formation scheduled region on the surface facing the mold,
Surface of the conductive portion is made on purpose coplanar with respect to the mold surface facing,
The entire surface of the conductive portion is exposed;
The adhesion film is provided so as to cover at least the pattern formation scheduled region and the surface of the conductive portion.
Imprint transfer substrate. The conductive portion is used for inspecting the state of the adhesion film provided in the pattern formation scheduled region.
The imprint transfer substrate according to claim 1. A conductive portion provided in a desired portion of a region excluding a pattern formation scheduled region on a surface facing the mold, and an adhesion film provided so as to cover at least the pattern formation planned region and the surface of the conductive portion. Prepared,
The surface of the conductive part is in the same surface state with respect to the surface facing the mold,
The entire surface of the conductive part is exposed.
Imprint transfer substrate.

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