JP5760412B2 - Imprint method and imprint apparatus - Google Patents

Description

  The present invention relates to an imprint method and an imprint apparatus for transferring and forming a desired pattern (a figure such as a line or a pattern) on a workpiece.

Attention has been focused on imprinting as a microfabrication technology. This imprinting method is a pattern formation technique that uses a mold member (mold) in which a fine concavo-convex structure is formed on the surface of a substrate, and transfers the concavo-convex structure to a workpiece to transfer the fine structure at an equal magnification.
As the above imprint method, for example, an optical imprint method is known. In this optical imprinting method, for example, a photocurable resin layer is disposed as a workpiece on the substrate surface, and a mold having a desired uneven structure is pressed against the resin layer. Then, in this state, the resin layer is irradiated with light from the mold side to be cured, and then the mold is separated from the resin layer, thereby forming a concavo-convex structure (concavo-convex pattern) in which the concavo-convex structure of the mold is inverted as a workpiece. It can form in a layer (patent document 1).
As described above, in the imprint method, a process of supplying a resin material, which is a workpiece, to the substrate surface, a process of filling the resin into the uneven structure of the mold, a process of curing the resin layer, a process of releasing the mold and the resin layer, Among them, shortening the filling process time is an important issue from the viewpoint of throughput. That is, a resin with good wettability with respect to the mold can be easily filled into the uneven structure of the mold and the filling process time can be shortened, but the problem is that the cured resin layer easily adheres to the mold in the mold release process. There is. Conversely, by using a resin having poor wettability with respect to the mold, it is possible to prevent the cured resin layer from adhering to the mold in the mold release step, but air ( Bubble) easily enters, and it is necessary to lengthen the time required for filling, resulting in a decrease in throughput.

  For this reason, an imprint method has been proposed in which the time required to fill the resin into the concavo-convex structure of the mold is short, and air is prevented from entering. For example, a method in which resin is supplied to the mold side as fine droplets by an ink jet method and cured to form a resin film, which is then adhered to a resin substrate via an adhesive layer, and the resin film is released from the mold (Patent Document 2) ), A method of filling air by sequentially feeding air from the center of the lower surface of the work placed on the set table in the peripheral direction, pressing the work against the mold, and spreading the resin on the work (Patent Document 3), There is a method (Patent Document 4) or the like in which a resin is applied to the substrate side, integrated and cured at the time of imprinting, and then the mold is released.

Special Table 2002-539604 JP 2007-230166 A JP 2007-305895 A JP 2009-208409 A

  However, in the imprint method described in Patent Document 2, if the number of dropping points of the resin droplets is small, air is likely to enter as in the conventional case, and in order to prevent this, it is necessary to increase the time required for filling. If the number of dropping points of resin droplets is increased, filling of the mold becomes easy, but it takes time to supply resin droplets, and in any case, it is not possible to prevent a decrease in throughput. . Moreover, since it adheres to the resin substrate through the adhesive layer, the resin film can be prevented from adhering to the mold upon releasing from the mold, but the resin film on the resin substrate becomes thick and the remaining film (formed pattern) There is also a problem that the thickness of the resin remaining in the recesses) tends to increase, and the risk of pattern dimension fluctuations increasing during the removal of the remaining film increases, impeding the use in lithography.

Further, in the imprint method described in Patent Document 3, the control of the drive of the set table, the timing of feeding air, etc. is extremely complicated, and high mechanical accuracy is required, and the mold can be easily filled. There is a problem that the greater the (affinity to the mold), the more easily the cured resin adheres to the mold upon release from the mold.
Further, in the imprint method described in Patent Document 4, the resin pattern formed on the substrate becomes thick, and the thickness of the remaining film (resin remaining in the recessed portion of the formed pattern) tends to increase, and the remaining film is removed. There is a problem that the risk of causing pattern dimension fluctuations increases in the meantime, which hinders the use in lithography.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an imprint method and an imprint apparatus that can stably perform high-definition imprint transfer.

In order to achieve such an object, the imprinting method of the present invention includes a supplying step of supplying a resin material to at least one of a surface having a concavo-convex structure region of a mold and a base material for filling; A filling step of filling the resin material between a surface having a structural region and the filling substrate; and the filling substrate and the mold are separated by leaving the resin material in an uncured state or an incompletely cured state. A separation step of leaving the resin material on the mold side, a pressing step of bringing the substrate for imprinting into contact with the resin material, and a release step of separating the mold from the resin material, Contact angle θm of the resin material with respect to the mold, contact angle θj of the resin material with respect to the base material for filling, and contact angle θk of the resin material with respect to the substrate for imprinting During, θk <θm <θj relationship is configured as established.

As another aspect of the present invention, the difference between the contact angle θj and the contact angle θm is 30 ° or more, and the difference between the contact angle θm and the contact angle θk is 30 ° or more.
As another aspect of the present invention, a resin material is dropped onto the mold in the supplying step, and the mold and the filling base material are brought close to each other in the filling step.
As another aspect of the present invention, as the base material for filling, a material provided with at least one supply hole on the surface facing the mold is used, and the resin material is supplied from the supply hole to the mold and the mold. It was set as the structure supplied between the base materials for filling.
As another aspect of the present invention, a material having a groove on the surface facing the mold is used as the filling substrate, and the resin material is used for the mold and the filling base by utilizing capillary action of the groove. It was set as the structure filled between materials.
As another aspect of the present invention, the base material for filling is provided with a plurality of suction holes at the peripheral edge of the surface facing the mold, and the resin material and the mold are sucked from the suction holes. It was set as the structure filled between the said base materials for filling.
As another aspect of the present invention, a configuration is adopted in which an excess of the resin material is sucked and collected from the suction hole.
As another aspect of the present invention, in the separation step, the resin material is set in an uncured state or an incompletely cured state, and the filling base material and the mold are separated from each other.

An imprint apparatus according to the present invention includes a mold holding apparatus for holding a mold, a substrate holding apparatus for holding a substrate for imprinting, and a base material holding apparatus for filling for holding a base material for filling. the provided, the filling substrate holding apparatus, Ri disjunction can der against mold held a filling base material held in the mold holding apparatus, the mold held by the mold holding device A supply mechanism for supplying a resin material to at least one of the surface having the concavo-convex structure region and the filling substrate held by the filling substrate holding device, the surface having the concavo-convex structure region of the mold, and the A filling mechanism for filling the resin material between the filling substrate and separating the filling substrate from the mold when the resin material is in an uncured state or an incompletely cured state; Ru It was UNA configuration.
Another aspect of the present invention, a positioning mechanism for positioning the mold resin material held in the mold holding apparatus is filled, to a desired imprint portion of the substrate for imprinting held by the substrate holding apparatus, A transfer mechanism that allows the mold holding device and the substrate holding device to be separated from each other is provided.

As another aspect of the present invention, the substrate holding device is configured to be movable in two orthogonal directions within a holding surface for holding the imprint substrate.
As another aspect of the present invention, the supply mechanism is configured to have means for supplying a resin material to the surface of the mold having the concavo-convex structure region.
As another aspect of the present invention, the supply mechanism includes a means for supplying a resin material to the supply hole of the filling base material held by the filling base material holding device.

  In the imprint method of the present invention, the mold and the filling material are used by using the filling base material having the contact angle θj of the resin material that satisfies the relationship of θm <θj with respect to the contact angle θm of the resin material to the mold. Since the resin material is filled between the base material and the resin material, the resin material is easily filled in the concave portion of the concave-convex structure region of the mold, air (bubbles) is prevented from entering, and the base material for filling is separated from the mold. In addition, the resin material can be reliably left on the mold side, and the contact angle θm of the resin material to the mold has a relationship of θk <θm with the contact angle θk of the resin material to the imprint substrate. Therefore, when the mold is pulled apart, the resin material is reliably transferred to the imprint substrate, whereby high-definition imprint transfer can be stably performed.

  In the imprint apparatus of the present invention, the filling base material and the mold can be separated from each other by the filling base material holding device, so that the resin material is sandwiched between the mold and the filling base material, and air (bubbles) are generated. The resin material can be filled in the concave portion of the concave / convex structure region of the mold while suppressing the intrusion, and the relationship of θm <θj is established with respect to the mold having a resin material contact angle θm and the contact angle θm. The filling base material having the contact angle θj of the resin material to be held is held in the mold holding portion and the filling base material holding portion, respectively, and the relationship of θk <θm is established with respect to the contact angle θm of the resin material with respect to the mold. By holding the substrate for imprinting having the contact angle θk of the resin material on the substrate holding part, the imprinting method of the present invention can be performed reliably.

It is process drawing which shows one Embodiment of the imprint method of this invention. It is a figure for demonstrating the other example of the base material for filling used for the imprint method of this invention. It is a figure for demonstrating the other example of the base material for filling used for the imprint method of this invention. It is process drawing which shows other embodiment of the imprint method of this invention. It is a figure for demonstrating the other example of the base material for filling used for the imprint method of this invention. It is a figure for demonstrating the other example of the base material for filling used for the imprint method of this invention. It is a top view which shows one Embodiment of the imprint apparatus of this invention. It is a side view from the Y-axis direction of the imprint apparatus shown by FIG. It is a side view from the X-axis direction of the imprint apparatus shown by FIG. It is an enlarged view of the site | part I enclosed with the chain line in the imprint apparatus shown by FIG. FIG. 10 is an enlarged view of a part II surrounded by a chain line in the imprint apparatus shown in FIG. 9. It is an enlarged view of the site | part III enclosed with the chain line in the imprint apparatus shown by FIG. It is a figure corresponding to FIG. 11 for demonstrating other embodiment of the imprint apparatus of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
<Imprint method>
FIG. 1 is a process diagram for explaining an embodiment of an imprint method of the present invention.
In the present embodiment, in the supplying step, the resin material 5 is supplied to the surface 1a having the concavo-convex structure region A1 of the mold 1 (FIG. 1A). The surface 1a of the mold 1 includes a concavo-convex structure region A1 having a concave portion 2 and a non-concave / convex structure region A2 in which the concavo-convex structure is not formed. Examples of means for supplying the resin material 5 to the surface 1a of the mold 1 include a dispenser and an ink jet. In the illustrated example, a plurality of droplets of the resin material 5 are shown, but the number of droplets of the resin material 5 and the dropping position can be appropriately set.
The contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 is between the contact angle θj of the resin material 5 with respect to the base material for filling 11 used in the subsequent process and the contact angle θk of the resin material 5 with respect to the substrate 7 for imprinting. Further, the relationship θk <θm <θj is established, and preferably the difference between the contact angle θj and the contact angle θm is 30 ° or more, and the difference between the contact angle θm and the contact angle θk is also 30 ° or more. is there. Such a contact angle θm can be set in a range of, for example, 30 ° to 70 °, preferably 40 ° to 65 ° in consideration of the filling property of the concave-convex structure region A1 into the concave portion 2. In the present invention, the contact angle of the resin material is set to a contact angle measuring device (Kyowa Interface Science Co., Ltd.) 20 seconds after dropping the resin material from the microsyringe to the object at a temperature of 25 ° C., a humidity of 30% and atmospheric pressure. ) Manufactured by CA-Z type).

The material of such a mold 1 can be selected as appropriate, but when the resin material 5 is photocurable, it is formed using a transparent base material that can transmit irradiation light for curing the resin material 5. For example, quartz glass, silicate glass, calcium fluoride, magnesium fluoride, acrylic glass, or any of these laminated materials can be used. Further, the mold 1 may include a release agent layer for adjusting the contact angle θm of the resin material 5 with respect to the surface 1a to a desired range. The thickness of the mold 1 can be set in consideration of the shape of the concavo-convex structure, the strength of the base material, the suitability for handling, and the like, and can be appropriately set within a range of about 300 μm to 10 mm, for example. The mold 1 may have a so-called mesa structure in which the concavo-convex structure region A1 has a convex structure with respect to the non-concave structure region A2.
In the supplying step, the resin material 5 may be supplied to the surface 11a of the filling base 11 facing the mold 1, or the resin material 5 may be supplied to both the mold 1 and the filling base 11. Also good.

Next, in the filling step, the surface 11a of the filling substrate 11 is opposed to the surface 1a having the uneven structure region 1A of the mold 1, the mold 1 and the filling substrate 11 are brought close to each other, and the surface 1a of the mold 1 The resin material 5 is filled between the surface 11a of the base material 11 for filling (FIG. 1 (B)). The filling substrate 11 has a relationship of θm <θj between the contact angle θj of the resin material 5 with respect to the surface 11a and the contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 as described above. To do. This contact angle θj can be set in a range of, for example, 40 ° or more, preferably 60 ° or more in consideration of the filling property into the concave portion 2 of the mold 1.
Such a filling base material 11 may be made of a material having rigidity such as quartz or a silicon substrate, and the shape of the surface 11a facing the mold 1 can be a flat surface. Further, the filling and spreading of the resin material 5 may be promoted by making the shape of the surface 11a a convex curved surface. In addition, the filling base material 11 is made of a flexible material such as a fluororesin, for example, and is deformed so as to be convex toward the mold 1 to promote filling and spreading of the resin material 5. May be. Such a filling substrate 11 may include a release agent layer for adjusting the contact angle θj of the resin material 5 with respect to the surface 11a to a desired range.

Next, in the separation step, the filling substrate 11 and the mold 1 are pulled apart (FIG. 1C). Since the relationship θm <θj is established between the contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 and the contact angle θj of the resin material 5 with respect to the surface 11a of the filling base material 11, When the material 11 and the mold 1 are separated, the resin material 5 remains in the mold 1 in an uncured state. Further, by setting the difference between the contact angle θj and the contact angle θm to be 30 ° or more, the separation of the filling substrate 11 from which the resin material 5 remains in the mold 1 and the mold 1 is further ensured.
In the present invention, the resin material 5 may be in an incompletely cured state before separating the filling base material 11 and the mold 1 in the separation step. The incomplete curing state in this case is a curing state in a range where the cured resin material can be fixed to the imprint substrate when the imprint substrate is brought into contact with the resin material 5 and cured in the subsequent process. And

  Next, in the pressing step, the imprint substrate 7 and the resin material 5 are brought into contact (FIG. 1D). The substrate 7 for imprinting is, for example, glass such as quartz, soda lime glass, borosilicate glass, semiconductor such as silicon, gallium arsenide, gallium nitride, resin substrate such as polycarbonate, polypropylene, polyethylene, metal substrate, or these It may be a composite material substrate made of any combination of these materials. 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. As described above, the contact angle θk of the resin material 5 with respect to the surface 7a of the substrate 7 and the contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 have a relationship of θk <θm. It is.

  Next, in the mold release step, the resin material 5 is cured, and the mold 1 is separated from the resin material 5, whereby the resin layer 5 ′ in which the concavo-convex structure obtained by inverting the concavo-convex structure of the mold 1 is formed is used for imprinting. Is transferred onto the substrate 7 (FIG. 1E). Since the relationship of θk <θm is established between the contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 and the contact angle θk of the resin material 5 with respect to the surface 7a of the substrate 7 for imprinting, the mold 1 In the separation, the cured resin material 5 (resin layer 5 ′) is reliably transferred and held on the substrate 7. Further, by setting the difference between the contact angle θm and the contact angle θk to be 30 ° or more, the resin layer 5 ′ can be transferred and held on the substrate 7 more reliably. The resin material 5 is cured by irradiating light from the mold 1 side when the resin material is photo-curable, and is heated by heating when the resin material is thermo-curable. In the case of thermoplasticity, it can be performed by lowering the temperature of the resin material in the plastic state.

Moreover, in the above-mentioned embodiment, what is provided with the several suction hole as the base material 11 for a filling can be used. FIG. 2 is a view corresponding to FIG. 1 (B) showing a state in which such a filling base material 11 is used, and on the peripheral portion of the surface 11a of the filling base material 11 facing the surface 1a of the mold 1. A plurality of suction holes 13 are provided. Resin material that fills between the surface 1a of the mold 1 and the surface 11a of the filling substrate 11 and protrudes around the mold 1 by performing suction from the suction hole 13 using a suction device (not shown). The surplus of 5 can be aspirated. Thereby, adhesion of the resin material 5 to an unnecessary part can be prevented, and reuse of the collect | recovered resin material 5 can be aimed at. The shape, size, number, and arrangement position of the suction holes 13 can be set as appropriate. For example, the through holes having a circular cross section can be used, and the opening diameter can be in the range of 100 to 1000 μm.
Moreover, the base material 11 for a filling may be provided with the groove part in the surface 11a. The groove portion is intended to promote the filling and spreading of the resin material 5 by capillary action, and the depth and width of the groove part exhibit the capillary phenomenon, and the filling base material 11 in the separation step. It can be set in consideration of the viscosity of the resin material 5, the contact angle θj with respect to the surface 11 a of the filling substrate 11, and the like so that the shape of the groove portion does not remain on the surface of the resin material 5 after peeling. For example, the depth of the groove can be set in the range of 1 to 100 μm, and the width of the groove can be set in the range of 1 to 100 μm. FIG. 3 is a view showing such a groove portion 14 and the surface 11a of the filling base material 11 provided with the suction hole 13, and in the illustrated example, the groove portion 14 is radiated from the center of the filling base material 11. A plurality of suction holes 13 are provided in the peripheral portion of the surface 11a so as to be provided between the groove portions. In addition, the shape, number, and arrangement position of the suction hole 13 and the groove portion 14 are not limited to the illustrated example.

FIG. 4 is a process diagram for explaining another embodiment of the imprint method of the present invention.
In the present embodiment, first, the surface 21a of the filling base material 21 is opposed to the surface 1a having the concavo-convex structure region A1 of the mold 1 via a desired gap (FIG. 4A). Thereafter, the resin material 5 is supplied from the supply hole 22 of the filling substrate 21. Then, the resin material 5 is filled between the surface 1a of the mold 1 and the surface 21a of the filling substrate 21 (FIG. 4B).
The mold 1 is the same as the mold 1 in the above embodiment, and the contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 is the contact angle θj of the resin material 5 with respect to the filling substrate 21 to be used. The relationship of θk <θm <θj is established between the contact angle θk of the resin material 5 and the substrate 7, and preferably the difference between the contact angle θj and the contact angle θm is 30 ° or more, and the contact angle The difference between θm and contact angle θk is 30 ° or more. Such a contact angle θm can be set in a range of, for example, 30 ° to 70 °, preferably 40 ° to 65 ° in consideration of the filling property of the concave-convex structure region A1 into the concave portion 2.

The filling base material 21 has one opening end of the supply hole portion 22 positioned on the surface 21 a facing the mold 1, and a resin material supply device (not shown) at the other opening end of the supply hole portion 22. Are connected via a transfer pipe or the like. The position and number of the supply holes 22 can be appropriately set in consideration of the filling property of the resin material 5 between the surface 1a of the mold 1 and the surface 21a of the filling base material 21, for example, filling One supply hole 22 can be provided at a substantially central portion of the surface 21a of the base material 21 for use. The filling base material 21 has a relationship of θm <θj between the contact angle θj of the resin material 5 with respect to the surface 21a and the contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 as described above. Is established. This contact angle θj can be set in a range of, for example, 40 ° or more, preferably 60 ° or more in consideration of the filling property into the concave portion 2 of the mold 1.
Such a filling base material 21 may be made of, for example, a material having rigidity such as quartz or a silicon substrate, and the shape of the surface 21a facing the mold 1 can be a flat surface. Further, the filling and spreading of the resin material 5 may be promoted by making the shape of the surface 21a a convex curved surface. Moreover, the base material 21 for filling may be provided with a release agent layer for adjusting the contact angle θj of the resin material 5 with respect to the surface 21a to a desired range.

  In the filling process of the resin material 5 between the surface 1a of the mold 1 and the surface 21a of the filling substrate 21, the gap between the surface 21a of the filling substrate 21 and the surface 1a of the mold 1 is set in advance. The gap can be maintained by supplying the resin material 5 from the supply hole 22 of the base material 21 for filling. In addition, the gap between the surface 21a of the filling base material 21 and the surface 1a of the mold 1 before filling with the resin material 5 is made larger than a preset gap, and the supply hole portion of the filling base material 21 is provided. While the resin material 5 is being supplied from 22, or after the resin material 5 is filled between the surface 1a of the mold 1 and the surface 21a of the filling substrate 21, the mold 1 and the mold 1 are filled so as to have a preset gap. You may make the base material 21 for approach approach.

Next, in the separation step, the filling base material 21 and the mold 1 are separated (FIG. 4C). The relationship θm <θj is established between the contact angle θm of the resin material 5 with respect to the surface 1a of the mold 1 and the contact angle θj of the resin material 5 with respect to the surface 21a of the base material 21 for filling. When the material 21 and the mold 1 are separated, the resin material 5 remains in the mold 1 in an uncured state. In addition, by setting the difference between the contact angle θj and the contact angle θm to be 30 ° or more, it is more certain that the filling substrate 21 and the mold 1 are separated so that the resin material 5 remains in the mold 1. .
In the present invention, the resin material 5 may be in an incompletely cured state before separating the filling base material 11 and the mold 1 in the separation step. The incomplete curing state in this case is a curing state in a range where the cured resin material can be fixed to the imprint substrate when the imprint substrate is brought into contact with the resin material 5 and cured in the subsequent process. And

Next, as in the above-described embodiment, the imprint substrate 7 and the resin material 5 are brought into contact with each other in the pressing process (FIG. 4D), and then the resin material 5 is bonded in the mold release process. By curing and separating the mold 1 from the resin material 5, the resin layer 5 ′ having the concavo-convex structure in which the concavo-convex structure of the mold 1 is inverted is transferred to the imprint substrate 7 (FIG. 4E )).
Moreover, in the above-mentioned embodiment, what is provided with the several suction hole as the base material 21 for filling can be used. FIG. 5 is a view corresponding to FIG. 4B showing a state in which such a filling base material 21 is used, and is formed on the peripheral portion of the surface 21 a of the filling base material 21 facing the surface 1 a of the mold 1. A plurality of suction holes 23 are provided. By performing suction from the suction hole 23 using a suction device (not shown), the surface 1a of the mold 1 and the surface 21a of the base material 21 for filling are supplied from the supply hole 22 of the base material 21 for filling. The surplus portion of the resin material 5 that is filled in between and protrudes around the mold 1 can be removed by suction. Thereby, adhesion of the resin material 5 to an unnecessary part can be prevented, and reuse of the collect | recovered resin material 5 can be aimed at. The shape, size, number, and arrangement position of the suction holes 23 can be set as appropriate. For example, the through holes can have a circular cross section, and the opening diameter can be in the range of 100 to 1000 μm.

  Moreover, the base material 21 for filling may be provided with the groove part in the surface 21a. The groove portion is intended to promote the filling and spreading of the resin material 5 by capillary action, and the depth and width of the groove part exhibit the capillary phenomenon and the filling substrate 21 in the separation step. It can be set in consideration of the viscosity of the resin material 5, the contact angle θj with respect to the surface 21 a of the filling base material 21, etc. so that the shape of the groove portion does not remain on the surface of the resin material 5 after peeling. For example, the depth of the groove can be set in the range of 1 to 100 μm, and the width of the groove can be set in the range of 1 to 100 μm. FIG. 6 is a view showing such a groove portion 24 and the surface 21a of the filling base material 21 provided with the suction hole 23. In the illustrated example, the supply hole located at the center of the filling base material 21 is shown. A plurality of groove portions 24 are provided radially from the portion 22, and a plurality of suction holes 23 are provided in the peripheral portion of the surface 21 a so as to be located between the groove portions. In addition, the shape, number, and arrangement position of the suction hole 23 and the groove part 24 are not limited to the illustrated example.

In the present invention, the filling base materials 11 and 21 having the contact angle θj of the resin material 5 satisfying the relationship θm <θj with respect to the contact angle θm of the resin material 5 with respect to the mold 1 are used. Since the resin material 5 is filled between the mold 1 and the base materials 11 and 21 for filling, the resin material 5 is easily filled in the concave portion 2 of the concavo-convex structure region 1A of the mold 1 and air (bubbles) may enter. Is prevented. Further, when the filling base materials 11 and 21 are separated from the mold 1, the resin material 5 can be reliably left on the mold 1 side. Further, since the relationship of θk <θm is established between the contact angle θm of the mold 1 and the contact angle θk of the imprint substrate 7, the cured resin material (resin layer) is removed when the mold 1 is pulled away. 5 ') is reliably transferred to the substrate 7 for imprinting. Thereby, high-definition imprint transfer can be performed stably.
The above-described embodiments of the imprint method are examples, and the present invention is not limited to these embodiments.

<Imprint device>
An imprint apparatus according to the present invention includes a mold holding apparatus for holding a mold, a substrate holding apparatus for holding a substrate for imprinting, and a base material holding apparatus for filling for holding a base material for filling. It is equipped with. And the base material holding device for filling can be separated from the mold held by the mold holding device.
7 is a plan view showing an embodiment of such an imprint apparatus of the present invention, FIG. 8 is a side view from the Y-axis direction of FIG. 7, and FIG. 9 is from the X-axis direction of FIG. FIG. 10 is an enlarged view of a part I surrounded by a chain line in FIG. 8, FIG. 11 is an enlarged view of a part II surrounded by a chain line in FIG. 9, and FIG. 12 is surrounded by a chain line in FIG. FIG. 7 to 12, the imprint apparatus is an example using the mold 1, the imprint substrate 7, and the filling base material 11 for carrying out the imprint method of the present invention described in FIG. Show.

7 to 12, the imprint apparatus 51 includes a substrate holding device 52 and a plurality of base material holding devices 55 arranged around the substrate holding device 52 (in the illustrated example, arranged on three sides of the substrate holding device 52). Three filling base material holding devices 55A, 55B, 55C) and a driving arm 75 (in the illustrated example, three filling base material holding devices 55A, 55B, 55C) A mold holding device 58 is detachably disposed on the drive arm 75).
The substrate holding device 52 constituting the imprint apparatus 51 has a holding member 53 for holding the imprint substrate 7. The holding member 53 can hold the substrate 7 by, for example, a holding mechanism by suction, a holding mechanism by mechanical clamping, or the like. Further, the substrate holding device 52 can be moved in two orthogonal directions (X-axis direction and Y-axis direction shown in FIG. 7) in the plane of the holding member 53 that holds the substrate 7 by a driving device (not shown). Yes.
The filling base material holding device 55 constituting the imprint apparatus 51 has a holding member 56 for holding the filling base material 11. The holding member 56 can hold the filling substrate 11 by, for example, a holding mechanism by suction, a holding mechanism by mechanical clamping, or the like. The filling substrate holding device 55 can be moved in a direction perpendicular to the holding surface of the holding member 53 of the substrate holding device 52 (Z-axis direction shown in FIGS. 8 and 9) by a driving device (not shown). Yes.

The mold holding device 58 constituting the imprinting device 51 holds the mold 1 so that the surface 1a having the concavo-convex structure region faces upward. Although the mold holding device 58 has a mechanical chuck 59 in the illustrated example and holds the mold 1 in a sandwiched manner, it is not limited to this.
The drive arm 75 on which the mold holding device 58 is detachably provided is arranged below each of the filling base material holding devices 55A, 55B, 55C, and holds the substrate holding device 52 and each of the filling base materials. The mold holding device 58 can be reciprocated on a path connecting the devices 55A, 55B, and 55C. Further, a through opening 76 (see FIG. 12) is provided at a portion of the drive arm 75 where the mold holding device 58 is detachably disposed. The through opening 76 is an opening for inserting the elevating member 94 of the elevating device 92 when the drive arm 75 is driven and the mold holding device 58 is positioned above the elevating device 92 described later. The bottom surface of the mold holding device 58 is larger than the through opening 76. When the mold holding device 58 is placed on the drive arm 75, the through opening 76 is closed by the mold holding device 58. In order to prevent unnecessary displacement of the mold holding device 58 on the drive arm 75, for example, a peripheral portion of the bottom surface of the mold holding device 58 and a portion in the vicinity of the through-opening portion 76 of the drive arm 75 that contacts the mold holding device 58. May be provided with a recessed portion and a protruding portion that are detachably engaged, or a chuck mechanism.

  Further, the imprint apparatus 51 of the present invention has a supply mechanism 61. The supply mechanism 61 supplies a resin material to the 1a surface having the concavo-convex structure region 1A of the mold 1 held by the mold holding device 58. In the illustrated example, the supply mechanism 61 includes an inkjet device 62. 7 and 8, when the drive arm 75 positions the mold holding device 58 below the supply mechanism 61, the resin material 5 is supplied from the inkjet device 62 onto the mold 1 (FIG. 7). 10). Further, the supply mechanism 61 of the imprint apparatus 51 may supply a resin material to the filling base material 11 held by the filling base material holding device 55. In this case, the supply mechanism 61 may include an inkjet device 62 that can move up and down below the filling substrate holding device 55 as shown by a two-dot chain line in FIG. Then, as shown in FIG. 8, when the drive arm 75 is positioned outside the lower side of the filling base material holding device 55A, the ink jet device 62 moves upward, and the filling base material holding device 55A is moved to the upper side. The resin material is supplied to the holding base material 11 that is held, and then returns to the lower standby position so as not to disturb the drive of the drive arm 75. Such a supply mechanism 61 may include a dispenser device or the like instead of the inkjet device 62. In the present invention, the supply mechanism 61 may supply the resin material to both the mold 1 and the filling substrate 11.

  Further, the imprint apparatus 51 has a filling mechanism 71. The filling mechanism 71 fills the resin material 5 between the 1a surface having the uneven structure region 1A of the mold 1 and the filling base material 11, and then separates the filling base material 11 from the mold 1. In the illustrated example, the filling substrate holding device 55 functions as the filling mechanism 71. That is, as shown in FIGS. 9 and 11, when the drive arm 75 positions the mold holding device 58 below the filling substrate holding device 55B, the filling substrate holding device 55B is driven not shown. The machine is lowered in the Z-axis direction (see FIGS. 9 and 11) and approaches the mold 1 so as to provide a predetermined gap. Thereby, the resin material supplied to the mold 1 is filled between the surface 1a of the mold 1 and the surface 11a of the base material 11 for filling (see FIG. 11). Thereafter, the filling substrate holding device 55B is raised in the Z-axis direction (see FIGS. 9 and 11) by a driving device (not shown), the filling substrate 11 is pulled away from the mold 1, and the resin material 5 is moved to the mold 1. Remain. The drive arm 75 can be moved up and down in the Z-axis direction (see FIGS. 9 and 11) while maintaining its axial direction, and the held mold holding device 85 is raised in the direction of the substrate holding device 55 for filling. The mold 1 may be brought close to the surface 11a of the base material 11 for filling.

  In addition, the imprint apparatus 51 has a positioning mechanism 81. The positioning mechanism 81 positions the mold 1 held by the mold holding device 58 and filled with the resin material 5 at a desired imprint portion of the imprint substrate 7 held by the substrate holding device 52. is there. In the illustrated example, the substrate holding device 52 functions as the positioning mechanism 81. That is, as shown in FIGS. 8 and 12, when the drive arm 75 positions the mold holding device 58 below the substrate holding device 52 and above the transfer mechanism 91 described later, the substrate holding device. 52 is moved in a biaxial direction (X-axis direction and Y-axis direction shown in FIG. 7) orthogonal to each other in the plane of the holding member 53 that holds the substrate 7 by a driving device (not shown) and imprinted on the mold 1. The desired imprint portion of the substrate 7 can be positioned. The positioning of the mold 1 and the substrate 7 is performed by a method using alignment of the XY coordinate position of the mold 1 (transfer mechanism 91 described later) with the XY coordinate position of each imprint region of the substrate holding device 52, or the alignment mark of the mold 1 And the alignment mark for each imprint region of the substrate 7 can be used.

Further, the imprint apparatus 51 has a transfer mechanism 91. The transfer mechanism 91 enables the mold holding device 58 and the substrate holding device 52 to be separated from each other. In the illustrated example, an elevating device 92 functions as the transfer mechanism 91, and the elevating device 92 can move the elevating member 94 up and down in the Z-axis direction (see FIGS. 8 and 12) by the driving device 93. That is, after the mold 1 is positioned at a desired imprint portion of the imprint substrate 7 by the positioning mechanism 81 described above, the elevating member 94 of the elevating device 92 is raised, and the leading end surface 94a thereof penetrates the drive arm 75. It is inserted into the opening 76 and then comes into contact with the bottom surface of the mold holding device 58 that is detachably disposed on the drive arm 75. The elevating member 94 of the elevating device 92 is further raised, whereby the mold holding device 58 is separated from the drive arm 75 and approaches the substrate holding device 52. The lifting device 92 stops the lifting member 94 while the resin material 5 filled in the mold 1 held by the mold holding device 58 is in contact with the imprint substrate 7. To prevent the mold holding device 58 from being displaced on the front end surface 94a of the elevating member 94, for example, the bottom surface of the mold holding device 58 and the front end surface 94a of the elevating member 94 are detachable so as to be detachable. Alternatively, a chuck mechanism or the like may be provided.
In this way, the resin material 5 is cured in a state where the resin material 5 is in contact with the imprint substrate 7. Thereafter, the elevating member 94 of the elevating device 92 is lowered, the mold 1 is pulled away from the cured resin material 5, the elevating member 94 is further lowered, and the mold holding device 58 is disposed at a predetermined position of the drive arm 75, and the drive arm 75. By pulling the elevating member 94 from the through opening 76, the transfer to the imprint substrate 7 is completed.

  In such an imprint apparatus 51, a mold for performing the imprint method of the present invention, a substrate for imprint, and a base material for filling are used (a mold in which the contact angle of the resin material 5 is θm, and this contact). A base material for filling having a contact angle θj of the resin material 5 satisfying a relation of θm <θj with respect to the angle θm is held in the mold holding portion 58 and the filling base material holding portion 55, respectively. By holding the imprint substrate having the contact angle θk of the resin material 5 that satisfies the relationship θk <θm with respect to the contact angle θm of the material 5, high mechanical accuracy is required. High-precision imprint transfer can be performed stably without any problems. Further, the supply mechanism 61 and the filling mechanism 71 corresponding to the three base material holding devices 55A, 55B, 55C arranged on the three sides of the substrate holding device 52 are provided with a time difference in the order of 55A → 55B → 55C, for example. Thus, the imprint transfer onto the substrate 7 can be performed with high efficiency.

In the imprint apparatus 51 of the present invention, the filling base material 21 for carrying out the imprint method of the present invention described with reference to FIG. 4 can also be used. FIG. 13 is a diagram for explaining the filling substrate holding device 55 of such an imprint apparatus, and corresponds to FIG. In this case, the holding member 56 constituting the filling substrate holding device 55 includes a supply channel 57a that can be connected to the supply port 22 of the filling substrate 21, and this supply channel 57a. Is connected to a resin material supply device (not shown) via a transfer pipe 57b.
In such an imprint apparatus, the filling substrate holding device 55 functions as the filling mechanism 71 and also as the supply mechanism 61. That is, as shown in FIG. 13, when the drive arm 75 positions the mold holding device 58 below the filling substrate holding device 55 (55B), the filling substrate holding device 55B is driven (not shown). It descends in the Z-axis direction by the apparatus and approaches the mold 1 so as to provide a predetermined gap. Next, resin is supplied from a supply device (not shown) through the transfer pipe 57b, the supply flow path 57a, and the supply port 22 of the filling base material 21, and the supplied resin material is formed on the surface 1a of the mold 1. It fills between the surfaces 21a of the base material 21 for filling. Thereafter, the filling substrate holding device 55 (55B) is raised in the Z-axis direction by a driving device (not shown), the filling substrate 21 is pulled away from the mold 1, and the resin material 5 remains in the mold 1. The drive arm 75 can be moved up and down in the Z-axis direction while maintaining its axial direction, and the mold holding device 85 held on the drive arm 75 is raised in the direction of the base material holding device 55 (55B) for filling, You may make the mold 1 approach the surface 21a of the base material 21 for filling.

The above-described embodiments of the imprint apparatus are examples, and the present invention is not limited to these embodiments. For example, the arrangement position and the number of arrangement of the filling base material holding device with respect to the substrate holding device 52 are not limited to the illustrated example.
Further, the drive arm 75 and the lifting device 92 may function as the positioning mechanism 81 by fixing the substrate holding device 52 and allowing the driving arm 75 and the lifting device 92 to move in the XY directions. If the imprint on the imprint substrate is one imprint on a single substrate, the positions of the substrate holding device 52, the drive arm 75, and the lifting device 92 are set in advance. The positioning mechanism 81 may not be provided.

Next, the present invention will be described in more detail by showing more specific examples.
[Example 1]
First, a mold was produced using quartz glass having a thickness of 6.35 mm. This mold had a concavo-convex structure pattern having a size of 25 mm × 25 mm, a depth of 100 nm, and a line / space of 50 nm / 50 nm.
Next, a mold release agent (HMDS manufactured by Kanto Chemical Co., Inc.) was applied to the surface having the pattern of the concavo-convex structure of the mold to form a mold release agent layer. The contact angle θm of the resin material described later with respect to the mold having the release agent layer thus formed was 60 °. The contact angle was measured by dropping the resin material from the microsyringe onto the object at a temperature of 25 ° C., a humidity of 30% and atmospheric pressure, and 20 seconds later, contact angle measuring instrument (CA-Z manufactured by Kyowa Interface Science Co., Ltd.) Type).

(Supply process)
A photocurable resin material having the following composition is 50 μm in 500 rows × 500 rows (250,000 places in total) so that the drop amount of one drop is 5 pL on the surface of the mold having the concavo-convex structure pattern prepared as described above. It was dripped at a pitch. The resin material was dropped using an ink jet apparatus.
(Composition of photocurable resin material)
・ Isobornyl acrylate: 38% by weight
・ Ethylene glycol diacrylate: 20% by weight
・ Butyl acrylate: 38% by weight
2-Hydroxy-2-methyl-1-phenyl-propan-1-one
... 2% by weight
・ 2-Perfluorodecylethyl acrylate: 1% by weight
・ Methyl perfluorooctanolate: 1% by weight

(Filling process)
A quartz plate having a thickness of 1 mm was prepared as a base material for filling, and a release agent (Optool DSX manufactured by Daikin Industries, Ltd.) was applied to one surface to form a release agent layer. As a result of measuring the contact angle θj of the resin material with respect to the surface having the release agent layer of the filling base material in the same manner as described above, it was 100 ° and was 30 ° or more larger than the contact angle θm.
The surface on which the release agent layer of the base material for filling was formed was brought close to the mold supplied with the resin material as described above. Here, the gap with the base material for filling in the non-relief structure region of the mold (the part where the uneven structure is not formed) was set to 0.05 μm.

(Separation process)
Subsequently, the base material for filling and the mold were separated, and the resin material was left on the mold side.

(Pushing process)
A silicon substrate having a thickness of 0.8 mm was prepared as an imprint substrate. As a result of measuring the contact angle θk of the resin material to the substrate in the same manner as described above, it was 20 °, which was 30 ° or more smaller than the contact angle θm.
The imprint substrate was brought close to the mold and pressed against the resin material filled in the mold.

(Release process)
In the state where the resin material filled in the mold and the substrate are in contact as described above, the illumination optical system of the imprint apparatus irradiates parallel light (ultraviolet light having a peak wavelength of 365 nm) on the mold side under the condition of 100 mJ / cm ^2. did. As a result, the photocurable resin material was cured to form a resin layer. Thereafter, the mold was pulled away from the cured resin layer to complete imprint transfer.

About the sample formed in this way, the defect rate was measured as follows, and the results are shown in Table 1 below.
(Defect rate measurement)
The formed pattern region was observed at five locations with an optical microscope, and the ratio of the area where the peeling of the resin layer or the pattern defect could be confirmed was measured within one observation location (1.0 mm × 1.0 mm). Therefore, it means that there are many defects, so that this defect rate is large, and in this invention, it determines with a defect rate being less than 0.1 as a practical use level.

[Example 2]
The mold release agent (HMDS manufactured by Kanto Chemical Co., Inc.) is diluted and applied, and the contact angle θm of the resin material to the mold is set to 40 °, and the mold release agent (HMDS manufactured by Kanto Chemical Co., Ltd.) is applied. Imprint transfer was performed in the same manner as in Example 1 except that the contact angle θj of the resin material with respect to the filling substrate was set to 60 °.
For the sample thus formed, the defect rate was measured in the same manner as in Example 1, and the results are shown in Table 1 below.

[Example 3]
After diluting and applying a release agent (HMDS manufactured by Kanto Chemical Co., Inc.), SPM cleaning was performed to set the contact angle θm of the resin material to the mold to 30 °. Also, the release agent (Kanto Chemical Co., Ltd.) Imprint transfer was carried out in the same manner as in Example 1 except that HMDS manufactured and manufactured and the contact angle θj of the resin material with respect to the filling substrate was 40 °.
For the sample thus formed, the defect rate was measured in the same manner as in Example 1, and the results are shown in Table 1 below.

[Comparative Example 1]
After supplying the resin material to the mold in the same manner as in Example 1, the imprint transfer was completed by performing the pressing process and the releasing process in Example 1 without performing the filling process and the separating process in Example 1.
For the sample thus formed, the defect rate was measured in the same manner as in Example 1, and the results are shown in Table 1 below.

[Comparative Example 2]
Imprint transfer was carried out in the same manner as in Example 1 except that the release agent layer was not formed on the filling substrate and the filling substrate having a resin material contact angle θj of 30 ° was used.
For the sample thus formed, the defect rate was measured in the same manner as in Example 1, and the results are shown in Table 1 below.

[Comparative Example 3]
Imprint transfer was performed in the same manner as in Example 1 except that a mold release agent layer was not formed on the mold and a mold having a resin material contact angle θm of 15 ° was used.
For the sample thus formed, the defect rate was measured in the same manner as in Example 1, and the results are shown in Table 1 below.

As shown in Table 1, it was confirmed that in the imprint methods in Examples 1 to 3, the defect rate was low and good imprint transfer was performed.
On the other hand, in the imprint method in Comparative Example 1, defects that seem to be caused by the entry of air (bubbles) in filling the resin material into the mold were observed, and it was confirmed that the practical level was not satisfied. .
Moreover, in the imprint method in the comparative example 2, in the separation step after the filling step, a defect that seems to be caused by a part of the resin material being taken on the filling base material is seen, and the practical level is not satisfied. It was confirmed.
Further, in the imprint method in Comparative Example 3, it was confirmed that in the mold release process, defects that seem to be caused by part of the resin layer being taken by the mold were observed, and the practical level was not satisfied.

  It can be used for microfabrication using nanoimprint technology.

DESCRIPTION OF SYMBOLS 1 ... Mold 2 ... Recessed part 5 ... Resin material 7 ... Substrate for imprint 11, 21 ... Base material for filling 22 ... Supply hole 13, 23 ... Suction hole 14, 24 ... Groove 51 ... Imprint apparatus 52 ... Mold holding apparatus 55 ... Substrate holding device for filling 58 ... Substrate holding device 61 ... Supply mechanism 71 ... Filling mechanism 81 ... Positioning mechanism 91 ... Transfer mechanism

Claims (13)

A supply step of supplying a resin material to at least one of the surface having the concavo-convex structure region of the mold and the base material for filling;
A filling step of filling the resin material between the surface having the concavo-convex structure region of the mold and the base material for filling;
A separation step in which the resin material is uncured or incompletely cured, and the filling base and the mold are separated to leave the resin material on the mold side;
A pressing step of bringing the substrate for imprinting into contact with the resin material;
A mold release step of separating the mold from the resin material,
Between the contact angle θm of the resin material to the mold, the contact angle θj of the resin material to the filling base material, and the contact angle θk of the resin material to the imprint substrate, θk <θm < An imprint method characterized in that the relationship θj is established.   The imprint method according to claim 1, wherein a difference between the contact angle θj and the contact angle θm is 30 ° or more, and a difference between the contact angle θm and the contact angle θk is 30 ° or more.   The imprint method according to claim 1, wherein a resin material is dropped onto the mold in the supplying step, and the mold and the filling base material are brought close to each other in the filling step.   As the filling base material, one having at least one supply hole on the surface facing the mold is used, and the resin material is supplied between the mold and the filling base material from the supply hole. The imprint method according to claim 1, wherein the imprint method is performed.   As the base material for filling, a material having a groove on the surface facing the mold is used, and the resin material is filled between the mold and the base material for filling by utilizing the capillary phenomenon of the groove. The imprint method according to any one of claims 1 to 4, wherein the imprint method is characterized in that:   The base material for filling is provided with a plurality of suction holes at the peripheral portion of the surface facing the mold, and the resin material is placed between the mold and the base material for filling while sucking from the suction holes. 6. The imprint method according to claim 1, wherein filling is performed.   The imprint method according to claim 6, wherein a surplus portion of the resin material is sucked and collected from the suction hole.   In the separation step, the filling material and the mold are pulled apart with the resin material in an uncured state or an incompletely cured state. How to print. A mold holding device for holding a mold, a substrate holding device for holding a substrate for imprinting, and a filling substrate holding device for holding a filling substrate. wood holding device Ri disjunction can der against mold held a filling base material held in the mold holding apparatus,
A supply mechanism for supplying a resin material to at least one of the surface having the concavo-convex structure region of the mold held by the mold holding device and the filling base material held by the filling base material holding device;
The resin material is filled between the surface having the concavo-convex structure region of the mold and the filling base material, and the filling base material and the filling material when the resin material is in an uncured state or an incompletely cured state imprint apparatus according to claim Rukoto and a charging mechanism for separating the mold. A positioning mechanism to position the mold resin material held in the mold holding apparatus is filled, to a desired imprint portion of the substrate for imprinting held by the substrate holding apparatus,
The imprint apparatus according to claim 9, further comprising: a transfer mechanism that allows the mold holding apparatus and the substrate holding apparatus to be separated from each other.   The imprint apparatus according to claim 9 or 10, wherein the substrate holding apparatus is movable in two orthogonal directions within a holding surface for holding the imprint substrate. The imprint apparatus according to any one of claims 9 to 11, wherein the supply mechanism includes means for supplying a resin material to a surface of the mold having a concavo-convex structure region. The said supply mechanism has a means for supplying the resin material to the hole for supply of the base material for filling hold | maintained at the said base material holding device for filling , The any one of Claim 9 thru | or 11 characterized by the above-mentioned. the imprint apparatus according to any.

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