JP5282077B2 - Substrate surface modification method, program, computer storage medium, and substrate surface modification apparatus - Google Patents

Abstract

The present invention is a method for modifying the surface of a substrate such that the adhesiveness between the surface of the substrate and an object to be bonded thereto is improved. The surface of the substrate is modified by supplying a surface modification solution such as a tertiary alcohol, an alkaline solution or a hydrogen peroxide solution to the surface of a substrate while irradiating the surface of the substrate with ultraviolet rays, and by imparting a large amount of hydroxyl groups to the surface of the substrate. The surface of the substrate begins to be irradiated with ultraviolet rays while the surface modification solution is being supplied.

Description

  The present invention relates to a surface modification method, a program, a computer storage medium, and a substrate surface modification apparatus for modifying the surface of a substrate.

  For example, in a semiconductor device manufacturing process, for example, a photolithography process is performed on a semiconductor wafer (hereinafter referred to as “wafer”) to form a predetermined resist pattern on the wafer.

  When the resist pattern described above is formed, the resist pattern is required to be miniaturized in order to achieve higher integration of the semiconductor device. In general, the limit of miniaturization in the photolithography process is about the wavelength of light used for the exposure process. For this reason, it has been advancing to shorten the wavelength of exposure light. However, there are technical and cost limitations to shortening the wavelength of the exposure light source, and it is difficult to form a fine resist pattern on the order of several nanometers, for example, only by the method of advancing the wavelength of light. is there.

  Therefore, in recent years, it has been proposed to form a fine resist pattern on a wafer by using a so-called imprint method instead of performing a photolithography process on the wafer. In this method, a template (sometimes called a mold or a mold) having a fine pattern on the surface is pressure-bonded to the resist surface formed on the wafer, then peeled off, and the pattern is directly transferred to the resist surface. (Patent Document 1).

JP 2009-43998 A

  On the surface of the template used in the above-described imprinting method, a release agent having liquid repellency with respect to the resist is usually formed in order to make the template easy to peel from the resist.

  When forming a release agent on the surface of the template, first, after cleaning the surface of the template, the release agent is applied to the surface of the template. Next, the release agent is adhered to the surface of the template so that the release agent to be formed has a predetermined contact angle and can exhibit a liquid repellency function with respect to the resist. Specifically, the release agent and the template surface are chemically reacted, that is, the release agent molecule and the hydroxyl group on the template surface are bonded by dehydration condensation. Of the components contained in the release agent, a component having liquid repellency with respect to the resist, such as a fluoride component, is adsorbed on the surface of the template. Thereafter, the unreacted portion of the release agent is removed, and a release agent having a predetermined film thickness is formed on the surface of the template. The unreacted part of the release agent means a part other than the part where the release agent is chemically reacted with the surface of the template.

  In the case where a release agent is formed as described above, it is necessary that many hydroxyl groups exist on the surface of the template in order for the release agent to sufficiently adhere to the template surface. However, for example, when sufficient pretreatment is not performed on the surface of the template, or when the material of the template surface is a material that hardly forms a hydroxyl group, the number of hydroxyl groups formed on the surface of the template is reduced. . In such a case, the release agent could not be sufficiently adhered to the template surface.

  This invention is made | formed in view of this point, and it aims at modifying the surface of a board | substrate and improving the adhesiveness of the surface of the said board | substrate, and a coupling | bonding target object.

  In order to achieve the above object, the present invention is a method for modifying a surface of a substrate, wherein a surface modifying solution is supplied to the surface of the substrate while irradiating the surface of the substrate with ultraviolet rays, It is characterized by adding a hydroxyl group to the surface.

  According to the present invention, since the surface of the substrate is irradiated with ultraviolet rays, the surface of the substrate can be activated. And since a surface modification liquid is supplied to the surface of the said board | substrate, activating the surface of a board | substrate, a large amount of hydroxyl groups can be provided to the surface of a board | substrate. Since the surface of the substrate can be sufficiently modified in this way, the adhesion between the surface of the substrate and the object to be bonded can be improved when the surface of the substrate and the object to be bonded are chemically bonded thereafter.

  As the surface modifying liquid, an optimal liquid can be selected depending on the material of the surface of the substrate. The surface modification liquid may be a tertiary alcohol, an alkaline solution, or a hydrogen peroxide solution. As a result of intensive studies by the inventors, it was found that a large amount of hydroxyl groups can be imparted to the surface of the substrate regardless of the material of the surface of the substrate, particularly when a tertiary alcohol or an alkaline solution is used as the surface modifying solution. Further, it was found that when hydrogen peroxide water is used as the surface modification liquid, a large amount of hydroxyl groups can be imparted to the surface of the substrate, particularly if the material of the substrate surface is tungsten.

  During the irradiation of the ultraviolet ray on the surface of the substrate, the supply of the surface modifying liquid to the surface of the substrate may be started.

  Further, the irradiation of the ultraviolet light onto the surface of the substrate may be started in a state in which the surface modifying liquid is supplied between the surface of the substrate and a support plate arranged to face the surface. . In such a case, the support plate may transmit the ultraviolet light.

  The substrate may be a template on which a transfer pattern is formed and a resist pattern is formed by transferring the transfer pattern to a resist film on another substrate.

  According to another aspect of the present invention, there is provided a program that runs on a computer of a control unit that controls the surface modification apparatus in order to cause the surface modification apparatus to execute the substrate surface modification method.

  According to another aspect of the present invention, a readable computer storage medium storing the program is provided.

  According to another aspect of the present invention, there is provided a surface modification apparatus for modifying the surface of a substrate, the ultraviolet irradiation unit for irradiating the surface of the substrate with ultraviolet rays, and the surface modification for imparting a hydroxyl group to the surface of the substrate. A surface modifying liquid supply unit configured to supply a liquid; and the ultraviolet irradiation unit and the surface modifying liquid supply unit configured to supply the surface modifying liquid to the surface of the substrate while irradiating the surface of the substrate with the ultraviolet light. And a control unit for controlling.

  The surface modification liquid may be a tertiary alcohol, an alkaline solution, or a hydrogen peroxide solution.

  The control unit controls the ultraviolet irradiation unit and the surface modifying liquid supply unit so as to start supplying the surface modifying liquid to the surface of the substrate while the surface of the substrate is irradiated with the ultraviolet light. May be.

  The surface modification apparatus has a support plate disposed to face the surface of the substrate, and the control unit is supplied with the surface modification liquid between the surface of the substrate and the support plate. You may control the said ultraviolet irradiation part and the said surface modification liquid supply part so that the irradiation of the said ultraviolet-ray to the surface of the said substrate may be started in a state. In such a case, the support plate may transmit the ultraviolet light.

  The substrate may be a template on which a transfer pattern is formed and a resist pattern is formed by transferring the transfer pattern to a resist film on another substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the surface of a board | substrate can be modify | reformed and the adhesiveness of the surface of the said board | substrate and a coupling | bonding object can be improved.

It is a top view which shows the outline of a structure of the template processing apparatus concerning this Embodiment. It is a side view which shows the outline of a structure of the template processing apparatus concerning this Embodiment. It is a side view which shows the outline of a structure of the template processing apparatus concerning this Embodiment. It is a perspective view of a template. It is a longitudinal cross-sectional view which shows the outline of a structure of a surface modification unit. It is a top view which shows the outline of a structure of a holding member. It is a cross-sectional view which shows the outline of a structure of a surface modification unit. It is a longitudinal cross-sectional view which shows the outline of a structure of a rinse unit. It is the flowchart which showed each process of the template process. It is explanatory drawing which showed typically the state of the template in each process of template processing, (a) shows a mode that the surface of a template is wash | cleaned, (b) is the said template, irradiating the surface of a template with an ultraviolet-ray. (C) shows a state in which the surface modification liquid is supplied to the surface of the template, and (c) shows a state in which a mold release agent is applied to the surface of the template while irradiating the surface of the template with ultraviolet rays. A mode that the mold release agent was formed into a film is shown. It is a longitudinal cross-sectional view which shows the outline of a structure of the surface modification unit concerning other embodiment. It is explanatory drawing which showed typically the state of the template in each process of the template process concerning other embodiment, (a) shows a mode that the surface of a template is wash | cleaned, (b) is the surface of a template, and support (C) shows a state in which the surface modifying liquid is supplied to the surface of the template, and a state in which the surface modifying liquid is supplied to the surface of the template. ) Shows a state in which a release agent is formed on the template. It is explanatory drawing which shows a mode that an ultraviolet-ray is irradiated to the surface from the back surface side of a template. It is a longitudinal cross-sectional view which shows the outline of a structure of a washing | cleaning unit. It is a cross-sectional view which shows the outline of a structure of a washing | cleaning unit. It is a top view which shows the outline of a structure of the imprint system provided with the template processing apparatus concerning this Embodiment. It is a longitudinal cross-sectional view which shows the outline of a structure of the imprint unit. It is a cross-sectional view which shows the outline of a structure of an imprint unit. It is the flowchart which showed each process of the imprint process. It is explanatory drawing which showed typically the state of the template and wafer in each process of an imprint process, (a) shows a mode that the resist liquid was apply | coated on the wafer, (b) shows the resist film on a wafer. (C) shows a state in which a resist pattern is formed on a wafer, and (d) shows a state in which a remaining film on the wafer is removed.

  Embodiments of the present invention will be described below. FIG. 1 is a plan view schematically showing the configuration of the template processing apparatus 1 according to the present embodiment. 2 and 3 are side views showing an outline of the configuration of the template processing apparatus 1.

In the template processing apparatus 1 of the present embodiment, a template T as a substrate having a rectangular parallelepiped shape and having a predetermined transfer pattern C formed on the surface is used as shown in FIG. Hereinafter, the transfer pattern C means the side of the template T which is formed with the surface T _1, the surface T ₁ opposite to the surface of the backside T _2. For the template T, a transparent material capable of transmitting light such as visible light, near ultraviolet light, and ultraviolet light, such as quartz glass, is used.

Template processing unit 1 includes a plurality as shown in FIG. 1, for example, five of the template T or transferring, between the outside and the template processing apparatus 1 with the cassette unit, carrying out a template T the template cassette C _T The template loading / unloading station 2 and the processing station 3 including a plurality of processing units for performing predetermined processing on the template T are integrally connected.

The template loading / unloading station 2 is provided with a cassette mounting table 10. The cassette mounting table 10 can mount a plurality of template cassettes _{CT in a line} in the X direction (vertical direction in FIG. 1). That is, the template carry-in / out station 2 is configured to be capable of holding a plurality of templates T.

The template carry-in / out station 2 is provided with a template carrier 12 that can move on a conveyance path 11 extending in the X direction. The template transport body 12 is also movable in the vertical direction and the vertical direction (θ direction), and can transport the template T between the template cassette _CT and the processing station 3.

  The processing station 3 is provided with a transport unit 20 at the center thereof. Around the transport unit 20, for example, four processing blocks G1 to G4 in which various processing units are arranged in multiple stages are arranged. A first processing block G1 and a second processing block G2 are arranged in this order from the template loading / unloading station 2 side on the front side of the processing station 3 (X direction negative direction side in FIG. 1). A third processing block G3 and a fourth processing block G4 are arranged in this order from the template loading / unloading station 2 side on the back side of the processing station 3 (X direction positive direction side in FIG. 1). A transition unit 21 for delivering the template T is disposed on the template loading / unloading station 2 side of the processing station 3.

  The transport unit 20 has a transport arm that holds and transports the template T and is movable in the horizontal direction, the vertical direction, and the vertical direction. And the conveyance unit 20 can convey the template T with respect to the various processing units mentioned later and the transition unit 21 which are arrange | positioned in the processing blocks G1-G4.

The first processing block G1, and supplies the plurality of liquid processing units, as shown in FIG. 2, for example while irradiating ultraviolet rays to the surface T ₁ of the template T, the surface modification liquid to the surface T ₁ of the template T surface modification apparatus surface modifying unit 30 as, while irradiating ultraviolet rays on the surface T ₁ of the template T, superimposed from the coating unit 31 is lower for applying a release agent to the surface T ₁ of the said template T in two stages in order It has been. Similarly, in the second processing block G2, the surface modification unit 32 and the coating unit 33 are stacked in two stages in order from the bottom. In addition, chemical chambers 34 and 35 for supplying various processing liquids to the liquid processing unit are provided at the lowermost stages of the first processing block G1 and the second processing block G2, respectively.

  In the third processing block G3, as shown in FIG. 3, a plurality of liquid processing units, for example, rinse units 40 and 41 for rinsing the release agent on the template T are stacked in two stages in order from the bottom. Similarly, in the fourth processing block G4, the rinsing units 42 and 43 are stacked in two stages in order from the bottom. In addition, chemical chambers 44 and 45 for supplying various processing liquids to the liquid processing unit are provided at the lowermost stages of the third processing block G3 and the fourth processing block G4, respectively.

  Next, the configuration of the surface modification units 30 and 32 described above will be described. As shown in FIG. 5, the surface modification unit 30 includes a processing container 100 in which a loading / unloading port (not shown) for the template T is formed on the side surface.

  A gas supply port 101 for supplying an inert gas such as nitrogen gas toward the inside of the processing container 100 is formed on the ceiling surface of the processing container 100. A gas supply source 103 that supplies nitrogen gas is connected to the gas supply port 101 via a gas supply pipe 102.

  An exhaust port 104 for exhausting the atmosphere inside the processing container 100 is formed on the bottom surface of the processing container 100. An exhaust pump 106 that evacuates the atmosphere inside the processing container 100 is connected to the exhaust port 104 via an exhaust pipe 105.

  A holding member 110 that holds and rotates the template T is provided at the center in the processing container 100. A central portion of the holding member 110 is depressed downward, and an accommodating portion 111 for accommodating the template T is formed. A groove portion 111 a smaller than the outer shape of the template T is formed in the lower portion of the housing portion 111. Therefore, in the accommodating part 111, the inner peripheral part of the lower surface of the template T is not in contact with the holding member 110 by the groove part 111a, and only the outer peripheral part of the lower surface of the template T is supported by the holding member 110. As shown in FIG. 6, the accommodating portion 111 has a substantially rectangular planar shape that conforms to the outer shape of the template T. A plurality of projecting portions 112 projecting inward from the side surface are formed in the accommodating portion 111, and the template T accommodated in the accommodating portion 111 is positioned by the projecting portions 112. Further, when the template T is transferred from the transfer arm of the transfer unit 20 to the storage unit 111, there are four notches 113 on the outer periphery of the storage unit 111 in order to avoid the transfer arm from interfering with the storage unit 111. It is formed in the place.

  As shown in FIG. 5, the holding member 110 is attached to the cover body 114, and a rotation driving unit 116 is provided below the holding member 110 via a shaft 115. By this rotation drive unit 116, the holding member 110 can rotate around the vertical at a predetermined speed and can move up and down.

  Around the holding member 110, there is provided a cup 120 that receives and collects the surface modifying liquid scattered or dropped from the template T. Connected to the lower surface of the cup 120 are a discharge pipe 121 for discharging the recovered surface modification liquid and an exhaust pipe 122 for exhausting the atmosphere in the cup 120.

  As shown in FIG. 7, a rail 130 extending along the Y direction (left and right direction in FIG. 7) is formed on the X direction negative direction (downward direction in FIG. 7) side of the cup 120. For example, the rail 130 is formed from the outside of the cup 120 in the Y direction negative direction (left direction in FIG. 7) to the outside in the Y direction positive direction (right direction in FIG. 7). An arm 131 is attached to the rail 130.

The arm 131 supports a surface modifying liquid nozzle 132 as a surface modifying liquid supply unit that supplies a surface modifying liquid to the surface T ₁ of the template T. The arm 131 is movable on the rail 130 by the nozzle driving unit 133. Thereby, the surface modifying liquid nozzle 132 can move from the standby part 134 installed on the outer side of the cup 120 on the positive side in the Y direction to above the center part of the template T in the cup 120. Further, the arm 131 can be moved up and down by a nozzle driving unit 133 and the height of the surface modifying liquid nozzle 132 can be adjusted. Note that the surface modification liquid, material is used which can impart hydroxyl groups on the surface T ₁ of the template T as described later. In the present embodiment, for example, t-pentyl alcohol, which is a tertiary alcohol, is used as the material of the surface modification liquid.

An ultraviolet irradiation unit 140 that irradiates the surface T _{1 of the} template T with ultraviolet rays (xenon excimer UV) having a wavelength of, for example, 172 nm is provided on the ceiling surface in the processing container 100 and above the holding member 110. Ultraviolet irradiation unit 140 is, for example opposite the surface T ₁ of the template T held by the holding member 110 is disposed so as to cover the surface T ₁ the entire surface.

For example, a cleaning liquid nozzle that injects a cleaning liquid, for example, an organic solvent, may be provided in the groove 111 a of the holding member 110. By spraying the cleaning liquid onto the back surface T _{2 of the} template T from the cleaning liquid nozzle, the back surface T ₂ can be cleaned.

  In addition, since the structure of the surface modification unit 32 is the same as that of the surface modification unit 30 mentioned above, description is abbreviate | omitted.

  Moreover, the structure of the coating units 31 and 33 has the structure which replaced the surface modification liquid nozzle 132 with the mold release agent nozzle in the surface modification unit 30 mentioned above. The release agent nozzle can supply the release agent onto the template T. In addition, since the other structure of the coating units 31 and 33 is the same as that of the surface modification unit 30, description is abbreviate | omitted. As the release agent material, a material having liquid repellency with respect to a resist film on the wafer, which will be described later, for example, a fluorine-carbon compound is used.

  Next, the structure of the rinse units 40-43 mentioned above is demonstrated. The rinse unit 40 includes a processing container 150 having a loading / unloading port (not shown) for the template T formed on the side surface as shown in FIG.

  An immersion tank 151 in which the template T is immersed is provided on the bottom surface in the processing container 150. In the immersion tank 151, a rinse liquid for rinsing the release agent on the template T, for example, an organic solvent is stored.

A holding part 152 that holds the template T is provided on the ceiling surface in the processing container 150 and above the immersion tank 151. Holding portion 152, the outer peripheral portion of the rear surface _{T 2} of the template T has a chuck 153 for holding suction. Template T has a surface T ₁ is held on the chuck 153 to face upward. The chuck 153 can be moved up and down by a lifting mechanism 154. And the template T is immersed in the organic solvent stored by the immersion tank 151 in the state hold | maintained at the holding | maintenance part 152, and the mold release agent on the said template T is rinsed.

The holding unit 152 includes a gas supply unit 155 provided above the template T held by the chuck 153. The gas supply unit 155 can spray an inert gas such as nitrogen or a gas gas such as dry air downward, that is, the surface T ₁ of the template T held by the chuck 153. Thus, it is possible to dry the surface T ₁ of the rinsing template T in the immersion bath 151. The rinse unit 40 is connected to an exhaust pipe (not shown) for exhausting the internal atmosphere.

  In addition, since the structure of the rinse units 41-43 is the same as that of the structure of the rinse unit 40 mentioned above, description is abbreviate | omitted.

  The template processing apparatus 1 is provided with a control unit 160 as shown in FIG. The control unit 160 is a computer, for example, and has a program storage unit (not shown). The program storage unit controls the transfer of the template T between the template loading / unloading station 2 and the processing station 3, the operation of the drive system in the processing station 3, and the like, and executes template processing to be described later in the template processing apparatus 1. The program to be stored is stored. This program is recorded on a computer-readable storage medium such as a computer-readable hard disk (HD), flexible disk (FD), compact disk (CD), magnet optical disk (MO), memory card, or the like. Or installed in the control unit 160 from the storage medium.

  The template processing apparatus 1 according to the present embodiment is configured as described above. Next, template processing performed in the template processing apparatus 1 will be described. FIG. 9 shows the main processing flow of this template processing, and FIG. 10 shows the state of the template T in each step.

First, the template carrier 12, the template T is taken from the template cassette C _T on the cassette mounting table 10, it is transported to the transition unit 21 in the processing station 3 (step A1 in FIG. 9). At this time, in the template cassette C _T, the template T, the surface T ₁ of the transfer pattern C is formed is accommodated so as to face upward, the template T in this state is conveyed to the transition unit 21.

Thereafter, the template T is transported to the surface modification unit 30 by the transport unit 20 and transferred to the holding member 110. Subsequently, nitrogen gas is supplied into the processing container 100 from the gas supply port 101. At this time, the atmosphere inside the processing container 100 is exhausted from the exhaust port 104, and the inside of the processing container 100 is replaced with a nitrogen gas atmosphere. Thereafter, ultraviolet from the ultraviolet irradiation unit 140 to the surface T ₁ the entire surface of the template T as shown in FIG. 10 (a) are irradiated. The organic surface T ₁ of the template T is removed, the surface T ₁ of the said template T is cleaned (step A2 in FIG. 9).

Thereafter, the surface modifying liquid nozzle 132 is moved to above the center of the template T and the template T is rotated. Then, while irradiating the high energy ultraviolet light surface T ₁ of the template T from continuing the ultraviolet irradiation unit 140, as shown in FIG. 10 (b), the surface modification liquid surface modification on the template T during rotation from nozzles 132 Supply liquid M. That is, during the irradiation of ultraviolet light, initiates the supply of the surface modification fluid M to the surface T ₁ of the template T. Supply surface reforming liquid M diffuses to the surface T ₁ the entire surface of the template T by the centrifugal force.

Here, when the inventors diligently examined, it was found that when the surface T _{1 of the} template T was irradiated with ultraviolet rays, the surface T ₁ was activated. When a surface modification liquid M that is t-pentyl alcohol is supplied to the activated surface T ₁ of the template T made of quartz glass, a large amount of hydroxyl groups (OH groups) are imparted to the surface T _1. I understood. Thus, the surface _{T 1} of the template T is reformed (Step A3 in FIG. 9). In this step A3, the inside of the processing container 100 is maintained in a nitrogen gas atmosphere. Further, after the surface T ₁ is modified, after the ultraviolet irradiation from the ultraviolet irradiation unit 140 and the supply of the surface modifying liquid M from the surface modifying liquid nozzle 132 are stopped, the template T is continuously rotated, and the template T T to the surface _{T 1} shaken dry and the.

Note that the surface modification liquid M, can select the optimum solution by the material of the surface T ₁ of the template T. In the present embodiment, tertiary alcohol (t-pentyl alcohol) is used as the surface modifying liquid M for the template T which is quartz glass, but other combinations will be described later.

  Thereafter, the template T is transported to the coating unit 31 by the transport unit 20 and transferred to the holding member 110. Subsequently, nitrogen gas is supplied into the processing container 100 from the gas supply port 101. At this time, the atmosphere inside the processing container 100 is exhausted from the exhaust port 104, and the inside of the processing container 100 is replaced with a nitrogen gas atmosphere.

Thereafter, the release agent nozzle is moved to above the center of the template T and the template T is rotated. Then, while irradiating ultraviolet rays to the surface T ₁ of the template T from the ultraviolet irradiation unit 140, as shown in FIG. 10 (c), supplies the release agent S on the template T during rotation from the release agent nozzle. That is, during the irradiation of ultraviolet light, initiates the supply of the release agent S on the surface T ₁ of the template T. Supplied release agent S is diffused on the template T by the centrifugal force is applied to the surface T ₁ the entire surface of the template T (step A4 in FIG. 9). After the coating, after stopping the supply of the release agent S from the irradiation and a release agent nozzle of ultraviolet rays from the ultraviolet irradiation unit 140, by subsequently rotating the template T, drying finishing off surface T ₁ of the said template T .

In this step A4, by ultraviolet rays are irradiated, binding of the hydroxyl groups of oxygen and hydrogen on the surface T ₁ of the template T is cut. Then, thus immediately after the coupling of the hydroxyl groups are cleaved, the surface T ₁ and a release agent molecules of the template T is bonded by dehydration condensation. Further, the ultraviolet irradiated to the surface T ₁ of the template T, adjoining the releasing agent molecules are bonded to each other by dehydration condensation. Thus, the chemical reaction between the surface T _{1 of the} template T and the release agent S is promoted, and the adhesion between the surface T _{1 of the} template T and the release agent S is improved.

Thereafter, the transport unit 20 transports the template T to the rinse unit 40 and holds the template T in the holding unit 152. Subsequently, the holding unit 152 is lowered, and the template T is immersed in the organic solvent stored in the immersion tank 151. When a predetermined time elapses, only the unreacted part of the release agent S, that is, only the part other than the part where the release agent S chemically reacts with the surface T _{1 of the} template T and adheres to the surface T ₁ is peeled off. At this time, since the release agent S on the surface T ₁ of the template T in the step A4 above is in close contact with the release agent S distance from the surface T ₁ of the predetermined template T will not be peeled off. Further, the contact angle of the release agent S on the template T is a predetermined angle, for example, 110 degrees or more, and the release agent S has sufficient liquid repellency with respect to a resist film to be described later. The mold function can be demonstrated. Thus, as shown in FIG. 10D, the release agent S along the transfer pattern C is formed on the template T with a predetermined film thickness (step A5 in FIG. 9). Then, raise the holding portion 152 blows air gas to the template T from the gas supply unit 155, drying the surface T _1.

Thereafter, the transport unit 20, the template T is carried to the transition unit 21 and returned to the template cassette _{C T} by the template carrier 12 (step A6 in FIG. 9). Thus a series of template processing in template processing apparatus 1 is completed, the surface T ₁ of the template T, the release agent S along the shape of the transfer pattern C is formed in a predetermined thickness.

According to the above embodiment, in step A3, since the irradiation of ultraviolet rays on the surface T ₁ of the template T, it can activate the surface T _1. Then, while activating the surface T ₁ of the template T, since the supply surface modification liquid M on the surface T _1, can be given a large amount of hydroxyl groups on the surface T ₁ of the template T. Since the surface T ₁ of the template T can be sufficiently modified to, then when the surface T ₁ and the release agent S of the template T is a chemical bond, the adhesion between the surface T ₁ and the release agent S Can be improved.

  In the above embodiment, the tertiary alcohol surface modifying liquid M is used for the quartz glass template T. However, an optimal liquid is selected as the surface modifying liquid M depending on the material of the substrate surface. Can do. The material of the surface of the substrate refers to the material of the substrate itself when the substrate itself is exposed on the surface, and the film on the surface of the substrate when the film is formed on the surface of the substrate. Refers to the material.

As a result of extensive studies by the inventors, it has been found that, for example, the above-described tertiary alcohol is capable of imparting a large amount of hydroxyl groups to the surface of a substrate made of various materials, not limited to quartz glass. For example, it has been found that even when the surface of the substrate is titanium (Ti), tungsten (W), alumina (Al ₂ O ₃ ), or diamond-like carbon (DLC), a large amount of hydroxyl groups can be imparted to the surface of the substrate. In this case, since the surface of the substrate can be sufficiently modified, the adhesion between the surface of the substrate and the object to be bonded can be improved. For example, the substrate as in the above embodiment is a template T, when binding objects of the release agent S, it is possible to improve the adhesion between the surface T ₁ and the release agent S of the template T, away The contact angle of the mold S can be improved to, for example, 110 degrees or more.

Similarly, it was found that even when an alkaline solution such as ammonia is used as the surface modification liquid M, a large amount of hydroxyl groups can be imparted to the surface of the substrate regardless of the material of the surface of the substrate. In such a case, the surface of the substrate is etched by supplying an alkaline solution to the surface of the substrate. A large amount of hydroxyl groups is imparted to the surface of the substrate by further supplying an alkaline solution while irradiating the etched surface of the substrate with ultraviolet rays. Then, for example, a substrate is the template T as described in the above embodiment, when bond object of the release agent S, it is possible to improve the adhesion between the surface T ₁ and the release agent S of the template T The contact angle of the release agent S can be improved to, for example, 110 degrees or more.

Further, it has been found that when hydrogen peroxide is used as the surface modification liquid M, the surface of the substrate can be sufficiently modified, particularly when the material of the substrate surface is tungsten. In such a case, the surface of the substrate is etched by supplying hydrogen peroxide water to the surface of the substrate. A large amount of hydroxyl groups are imparted to the surface of the substrate by further supplying hydrogen peroxide water while irradiating the etched surface of the substrate with ultraviolet rays. Then, for example, a substrate is the template T as described in the above embodiment, when bond object of the release agent S, it is possible to improve the adhesion between the surface T ₁ and the release agent S of the template T The contact angle of the release agent S could be improved to a high contact angle of, for example, 118 degrees.

In the above embodiment, the modification of the surface T ₁ of the template T by the surface modification liquid M and the application of the release agent S to the surface T ₁ are the surface modification units 30 and 32 and the coating unit 31, respectively. , 33 is performed in another unit, but may be performed in one unit. In such a case, for example, both the surface modifying liquid nozzle 132 and the release agent nozzle are provided in the surface modifying unit 30. Then, the surface T ₁ of the template T can be modified with the surface modifying liquid M and the release agent S can be applied to the surface T ₁ without moving the template T in one unit. Therefore, the throughput of template processing can be improved. In addition, the configuration of the template processing apparatus 1 can be simplified.

In the above embodiment, the supply of the surface modifying liquid M to the surface T _{1 of the} template T is started during the irradiation with ultraviolet rays in the step A3. However, the surface modifying liquid M is applied to the surface T _{1 of the} template T. in the supplied state, it may start the irradiation of ultraviolet rays to the surface T ₁ of the template T.

  In such a case, for example, the surface modification unit 30 shown in FIG. 11 is used to perform the step A3. The surface modification unit 30 has a processing container 200 in which a loading / unloading port (not shown) for the template T is formed on the side surface.

  A gas supply port 201 for supplying an inert gas, for example, nitrogen gas, is formed on the ceiling surface of the processing container 200 toward the inside of the processing container 200. A gas supply source 203 that supplies nitrogen gas is connected to the gas supply port 201 via a gas supply pipe 202. The inside of the processing container 200 may be supplied with a mixed gas of nitrogen gas and water vapor.

  An exhaust port 204 for exhausting the atmosphere inside the processing container 200 is formed on the bottom surface of the processing container 200. An exhaust pump 206 that evacuates the atmosphere inside the processing container 200 is connected to the exhaust port 204 via an exhaust pipe 205.

On the bottom surface in the processing container 200, a mounting table 210 on which the template T is mounted is provided. Template T has a surface T ₁ is placed on the top surface of the mounting table 210 to face upward. In the mounting table 210, raising / lowering pins 211 are provided for supporting the template T from below and raising / lowering it. The elevating pin 211 can be moved up and down by the elevating drive unit 212. A through hole 213 that penetrates the upper surface in the thickness direction is formed on the upper surface of the mounting table 210, and the elevating pin 211 is inserted through the through hole 213.

An ultraviolet irradiation unit 220 that irradiates the surface T _{1 of the} template T with ultraviolet rays having a wavelength of, for example, 172 nm is provided on the ceiling surface in the processing container 200 and above the mounting table 210. Ultraviolet irradiation unit 220 is opposed to the surface T ₁ of the mounting template T, for example, on the mounting table 210 is disposed so as to cover the surface T ₁ the entire surface.

A support plate 221 is disposed between the mounting table 210 and the ultraviolet irradiation unit 220. Support plate 221, for example, opposed to the surface T ₁ of the mounting template T on the table 210 through a predetermined gap, and is arranged so as to cover the surface T ₁ the entire surface. The support plate 221 can be moved in the processing container 200 by a moving mechanism (not shown). Further, the support plate 221 is made of a transparent material that can transmit ultraviolet rays, and quartz glass of the same material as the template T is used in the present embodiment.

Inside processing chamber 200, supplies a surface modification liquid M between the surface T ₁ of the template T is mounted on the mounting table 210 supporting plate 221, surface modification of the surface modification liquid supply unit A quality liquid nozzle 230 is disposed. The surface modifying liquid nozzle 230 is disposed so that, for example, the supply port 230a at the lower end thereof faces obliquely downward. The surface modifying liquid nozzle 230 is supported by the arm 231. A movement mechanism (not shown) is attached to the arm 231, and the surface modifying liquid nozzle 230 can be inside the processing container 200.

  In addition, since the structure of the surface modification unit 32 is the same as that of the surface modification unit 30 mentioned above, description is abbreviate | omitted. The other configuration of the template processing apparatus 1 is the same as the configuration of the template processing apparatus 1 of the above embodiment, and a description thereof will be omitted.

  Next, template processing performed in the template processing apparatus 1 of the present embodiment will be described. FIG. 12 shows the state of the template T in each step of template processing. Note that the template processing flow in the present embodiment is the same as the processing flow shown in FIG.

First, the template _T in the template cassette CT on the cassette mounting table 10 is transported to the transition unit 21 by the template transport body 12 (step A1 in FIG. 9).

Thereafter, the template T is transported to the surface modification unit 30 by the transport unit 20. The template T carried into the surface modification unit 30 is transferred to the lifting pins 211 and placed on the placing table 210. Subsequently, nitrogen gas is supplied into the processing container 200 from the gas supply port 201. At this time, the atmosphere inside the processing container 200 is exhausted from the exhaust port 204, and the inside of the processing container 200 is replaced with a nitrogen gas atmosphere. Thereafter, as shown in FIG. 12A, ultraviolet rays are irradiated from the ultraviolet irradiation unit 220 to the entire surface T _{1 of the} template T. The organic surface T ₁ of the template T is removed, the surface T ₁ of the said template T is cleaned (step A2 in FIG. 9).

Thereafter, the ultraviolet irradiation from the ultraviolet irradiation unit 220 is temporarily stopped, and the support plate 221 is moved so that the surface T1 of the template T and the support plate 221 face _{each other} with a predetermined gap as shown in FIG. Deploy. Then, the surface modifying liquid M is supplied from the surface modifying liquid nozzle 230 between the surface T _{1 of the} template T and the support plate 221. Supply surface reforming liquid M diffuses between the surface T ₁ and the support plate 221 of the template T by the capillary phenomenon. Subsequently, as shown in FIG. 12C, ultraviolet rays are irradiated downward from the ultraviolet irradiation unit 220 in a state where the surface modification liquid M is supplied between the surface T _{1 of the} template T and the support plate 221. The ultraviolet rays pass through the support plate 221 and are irradiated on the entire surface T _{1 of the} template T. In this step A3, the inside of the processing container 200 is maintained in a nitrogen gas atmosphere. By this step A3, a large amount of hydroxyl groups is applied to the surface T ₁ of the template T, the surface T ₁ is reformed (Step A3 in FIG. 9). After modification of the surface T _1, after stopping the surface modification liquid supply M from irradiation and surface reforming liquid nozzle 230 of the ultraviolet from the ultraviolet irradiation unit 220, for example such as nitrogen inert gas or the like dry air by blowing gas gas on the surface T ₁ of the template T, thereby drying the surface T _1. Note that aspects of the modification of the surface T ₁ of the template T is to omit the detailed description is the same as the surface modification in the step A3 of the above-described embodiment.

Thereafter, the transport unit 20, the template T is transported to the coating unit 31, while irradiating ultraviolet rays to the surface T ₁ of the template T, and supplies the release agent S on the template T during rotation. Supplied release agent S is diffused on the template T by the centrifugal force is applied to the surface T ₁ the entire surface of the template T (step A4 in FIG. 9). Since step A4 is the same as step A4 in the above embodiment, detailed description thereof is omitted.

  Thereafter, the transport unit 20 transports and rinses the template T to the rinse unit 40, and the release agent S along the transfer pattern C is formed on the template T with a predetermined film thickness as shown in FIG. A film is formed (step A5 in FIG. 9). Since step A5 is the same as step A5 in the above embodiment, detailed description thereof is omitted.

Thereafter, the transport unit 20, the template T is carried to the transition unit 21 and returned to the template cassette _{C T} by the template carrier 12 (step A6 in FIG. 9). Thus a series of template processing in template processing apparatus 1 is completed, the surface T ₁ of the template T, the release agent S along the shape of the transfer pattern C is formed in a predetermined thickness.

Also in this embodiment, the same effect as that of the above embodiment can be enjoyed. In other words step A3, while irradiating ultraviolet rays to the surface T ₁ of the template T, since the supply surface modification liquid M on the surface T ₁ of the said template T, applying a large amount of hydroxyl groups on the surface T ₁ of the template T Can do.

In step A3 of this embodiment, had been fed the surface modification solution M between the surface T ₁ and the support plate 221 of the template T by use of a capillary phenomenon, the supply of the surface modification fluid M The method is not limited to this. For example, the surface modification liquid M may be pressed between the surface T _{1 of the} template T and the support plate 221.

Further, in step A3 of this embodiment, when supplying the surface modification solution M between the surface T ₁ and the support plate 221 of the template T, it has been temporarily stopped irradiation of ultraviolet rays from the ultraviolet irradiation unit 220 However, the ultraviolet irradiation may be continued. That is, in the process A2 and the process A3, the ultraviolet irradiation from the ultraviolet irradiation unit 220 may be continuously performed.

In the above embodiments, the ultraviolet in the step A3, but the ultraviolet surface T ₁ of the template T from the support plate 221 side had been irradiated, the surface T ₁ from the rear T ₂ side of the template T as shown in FIG. 13 May be irradiated. In order to irradiate ultraviolet rays in this way, in the surface modification unit 30, the top and bottom arrangement of the template T and the support plate 221 may be reversed, that is, the template T may be arranged above the support plate 221. Or you may arrange | position the ultraviolet irradiation part 220 arrange | positioned at the ceiling surface of the processing container 200 under the template T. FIG.

In such a case, the ultraviolet rays irradiated from the rear surface T ₂ side of the template T as shown in FIG. 13, passes through the template T, is applied to the surface T ₁ of the said template T. Thus while irradiating ultraviolet rays to the surface T ₁ of the template T, the surface modification liquid M is supplied onto the template T. Then, the surface T ₁ of the template T can be given a large amount of hydroxyl groups, the surface T ₁ can be sufficiently modified.

According to the present embodiment, the front surface T ₁ is irradiated with ultraviolet rays from the back surface T ₂ side of the template T, so that the ultraviolet rays are not disturbed by the surface modification liquid M and the surface T _{1 of the} template T and the surface modification. It reaches the interface of the liquid M. For this reason, the ultraviolet rays are irradiated to the surface T _{1 of the} template T without being attenuated by the surface modification liquid M. Therefore, it is possible to efficiently modify the surface T ₁ of the template T.

In the above embodiment, the cleaning of the surface T ₁ of the template T in Step A2 has been done in the surface reforming unit 30 for step A3, may be performed in a separate cleaning unit. This cleaning unit is arranged in any of the processing blocks G1 to G4 of the template processing apparatus 1, for example.

  In this case, as shown in FIGS. 14 and 15, the cleaning unit 240 includes a processing container 250 having a loading / unloading port (not shown) for the template T formed on the side surface.

A chuck 251 for attracting and holding the template T is provided in the processing container 250. Chuck 251, the surface _{T 1} of the template T to face upward, suction-holds the rear surface _{T 2.} A chuck driving unit 252 is provided below the chuck 251. The chuck driving unit 252 is provided on the bottom surface in the processing container 250 and is mounted on a rail 253 extending along the Y direction. The chuck 251 can move along the rail 253 by the chuck driving unit 252.

  An ultraviolet irradiation unit 254 that irradiates the template T held by the chuck 251 with ultraviolet rays is provided on the ceiling surface in the processing container 250 and above the rail 253. The ultraviolet irradiation unit 254 extends in the X direction as shown in FIG.

The template T conveyed to the cleaning unit 240 is sucked and held by the chuck 251. Subsequently, the template T is moved along the rails 253 by the chuck driving unit 252, and the template T is irradiated with ultraviolet rays from the ultraviolet irradiation unit 254. In this way, the entire surface T _{1 of the} template T is irradiated with ultraviolet rays, and the surface T _{1 of the} template T is cleaned.

  In the above embodiment, the surface modification liquid M is supplied onto the rotating template T in the surface modification unit 30. For example, the surface modification liquid M extends in the width direction of the template T and has a slit-like supply port on the lower surface. The surface modifying liquid M may be supplied onto the template T using the surface modifying liquid nozzle on which is formed. In such a case, the surface modifying liquid M is supplied from the supply port while moving the surface modifying liquid nozzle in the side direction of the template T.

  In the rinse unit 40 of the above embodiment, the mold release agent S is rinsed by immersing the template T in the organic solvent stored in the immersion tank 151. However, the surface modification shown in FIGS. A rinse unit having the same configuration as the unit 30 may be used. In such a case, instead of the surface modifying liquid nozzle 132 of the surface modifying unit 30, a rinsing liquid nozzle for supplying an organic solvent as a rinsing liquid for the release agent S onto the template T is used.

And in this rinsing unit, an organic solvent is supplied to the template T during rotation, to rinse the surface T ₁ the entire surface of the template T. When a predetermined time elapses, only the unreacted portion of the release agent S is peeled off, and the release agent S along the transfer pattern C is formed on the template T. Then, after stopping the supply of the organic solvent, it continues to further rotate the template T, drying finishing off the surface T _1. In this way, the release agent S on the template T is rinsed.

In the above embodiment, the release agent S is applied to the surface T ₁ while irradiating the surface T ₁ of the template T with ultraviolet rays in the step A4. However, the surface T _{1 of the} template T and the release agent are applied. The method for adhering S is not limited to this. For example, after applying the release agent S to the surface T _{1 of the} template T, the release agent S may be heated. Alternatively, after applying the release agent S on the surface T ₁ of the template T, alcohol may be applied onto the release agent S. In any case, it can be brought into close contact with the surface T ₁ and the release agent S of the template T.

  In the above embodiment, the template T is transported by the transport unit 20 in the processing station 3, but the template T may be transported on a transport roller using a so-called flat flow format. In such a case, the surface modification unit, the coating unit, and the rinse unit are arranged in this order in the processing station 3. And the template T carried out from the template carrying in / out station 2 is sequentially conveyed by these processing units by conveyance using a conveyance roller. In each processing unit, a predetermined process is performed on the template T being conveyed. When the release agent S is formed on the template T in this way, the template T is returned to the template loading / unloading station 2 and a series of template processing is completed. In this case, since predetermined processing is performed during the conveyance of the template T in each processing unit, the throughput of the template processing can be further improved.

The template processing apparatus 1 of the above embodiment may be arranged in the imprint system 300 as shown in FIG. The imprint system 300 includes an imprint unit 310 that forms a resist pattern on a wafer W as another substrate using the template T, and a plurality of, for example, 25 wafers W in the cassette unit. A wafer loading / unloading station 311 for loading / unloading the wafer W and loading / unloading the wafer W to / from the wafer cassette _CW . An interface station 312 for transferring the template T is arranged between the template processing apparatus 1 and the imprint unit 310. The imprint system 300 has a configuration in which the template processing apparatus 1, the interface station 312, the imprint unit 310, and the wafer carry-in / out station 311 are integrally connected.

The wafer loading / unloading station 311 is provided with a cassette mounting table 320. The cassette mounting table 320 can mount a plurality of wafer cassettes _CW in a row in the X direction (vertical direction in FIG. 16). That is, the wafer carry-in / out station 311 is configured to be capable of holding a plurality of wafers W.

The wafer carry-in / out station 311 is provided with a wafer carrier 322 that can move on a conveyance path 321 extending in the X direction. The wafer carrier 322 is also movable in the vertical direction and around the vertical direction (θ direction), and can carry the wafer W between the wafer cassette _CW and the imprint unit 310.

  The wafer carry-in / out station 311 is further provided with an alignment unit 323 for adjusting the orientation of the wafer W. The alignment unit 323 adjusts the orientation of the wafer W based on the position of the notch portion of the wafer W, for example.

  The interface station 312 is provided with a template transport body 331 that moves on a transport path 330 extending in the X direction. A reversing unit 332 for inverting the front and back surfaces of the template T is disposed on the positive direction side of the transport path 330 in the X direction, and a plurality of templates T are temporarily stored on the negative direction side of the transport path 330 in the X direction. A buffer cassette 333 is disposed. The template transport body 331 is also movable in the vertical direction and around the vertical direction (θ direction), and can transport the template T between the processing station 3, the reversing unit 332, the buffer cassette 333, and the imprint unit 310.

  In the processing station 3 of the template processing apparatus 1, a transition unit 334 for delivering the template T is disposed on the interface station 312 side of the transport unit 20.

  Next, the configuration of the above-described imprint unit 310 will be described. As shown in FIG. 17, the imprint unit 310 has a processing container 340 in which a loading / unloading port (not shown) for the template T and a loading / unloading port (not shown) for the wafer W are formed on the side surfaces.

  A wafer holder 341 on which the wafer W is placed and held is provided on the bottom surface in the processing container 340. The wafer W is placed on the upper surface of the wafer holder 341 so that the surface to be processed faces upward. In the wafer holding part 341, elevating pins 342 for supporting the wafer W from below and elevating it are provided. The elevating pin 342 can be moved up and down by the elevating drive unit 343. A through hole 344 that penetrates the upper surface in the thickness direction is formed on the upper surface of the wafer holding portion 341, and the elevating pins 342 are inserted through the through holes 344. The wafer holding unit 341 can be moved in the horizontal direction and can be rotated around the vertical by a moving mechanism 345 provided below the wafer holding unit 341.

  As shown in FIG. 18, a rail 350 extending along the Y direction (left and right direction in FIG. 18) is provided on the negative side in the X direction (downward direction in FIG. 18) of the wafer holder 341. The rail 350 is formed, for example, from the outer side of the wafer holding portion 341 on the Y direction negative direction (left direction in FIG. 18) to the outer side on the Y direction positive direction (right direction in FIG. 18). An arm 351 is attached to the rail 350.

  The arm 351 supports a resist solution nozzle 352 that supplies a resist solution onto the wafer W. The resist solution nozzle 352 has, for example, an elongated shape along the X direction that is the same as or longer than the diameter dimension of the wafer W. For example, an ink jet type nozzle is used as the resist solution nozzle 352, and a plurality of supply ports (not shown) formed in a line along the longitudinal direction are formed below the resist solution nozzle 352. The resist solution nozzle 352 can strictly control the resist solution supply timing, the resist solution supply amount, and the like.

  The arm 351 is movable on the rail 350 by the nozzle driving unit 353. As a result, the resist solution nozzle 352 can move from the standby unit 354 installed on the outer side of the wafer holding unit 341 on the positive side in the Y direction to above the wafer W on the wafer holding unit 341, and further the surface of the wafer W The top can be moved in the radial direction of the wafer W. The arm 351 can be moved up and down by a nozzle driving unit 353, and the height of the resist solution nozzle 352 can be adjusted.

A template holder 360 that holds the template T as shown in FIG. 17 is provided on the ceiling surface in the processing container 340 and above the wafer holder 341. That is, the wafer holding unit 341 and the template holding unit 360 are arranged so that the wafer W placed on the wafer holding unit 341 and the template T held on the template holding unit 360 face each other. Furthermore, the template holding portion 360 has a chuck 361 for holding adsorb outer peripheral portion of the rear surface T ₂ of the template T. The chuck 361 is movable in the vertical direction and rotatable about the vertical by a moving mechanism 362 provided above the chuck 361. As a result, the template T can rotate up and down in a predetermined direction with respect to the wafer W on the wafer holder 341.

  The template holding unit 360 includes a light source 363 provided above the template T held by the chuck 361. The light source 363 emits light such as visible light, near ultraviolet light, and ultraviolet light, and the light from the light source 363 passes through the template T and is irradiated downward.

  The imprint system 300 according to the present embodiment is configured as described above. Next, an imprint process performed in the imprint system 300 will be described. FIG. 19 shows the main processing flow of this imprint process, and FIG. 20 shows the state of the template T and wafer W in each step of this imprint process.

First, the template T is transported from the template carry-in / out station 2 to the processing station 3 by the template carrier 12 (step B1 in FIG. 19). In the processing station 3, (step B2 in FIG. 19) cleaning the surface T ₁ of the template T, the surface modification solution M modification of the surface T ₁ by the supply of the illumination and the surface T ₁ of the ultraviolet light to the surface T ₁ ( step B3 of FIG. 19), step B4 of irradiation of ultraviolet rays to the surface _{T 1} and application of the release agent S on the surface _{T 1} (Fig. 19), rinsing of the release agent S (step B5 in FIG. 19) is successively performed, the release agent S is formed on the surface T ₁ of the template T. In addition, since these processes B2-B5 are the same as the processes A2-A5 in the said embodiment, detailed description is abbreviate | omitted.

The template T on which the release agent S is formed is transported to the transition unit 334. Subsequently, the template T is transported to the reversing unit 332 by the template transport body 331 of the interface station 312 and the front and back surfaces of the template T are reversed. That is, the rear surface T ₂ of the template T is directed upwards. Thereafter, the template T is transported to the imprint unit 310 by the template transport body 331 and is sucked and held by the chuck 361 of the template holding unit 360.

In this way, template processing is performed on the template T at the processing station 3, and the template T is being transferred to the imprint unit 310. At the wafer carry-in / out station 311, the wafer transfer body 322 causes the wafer cassette C _W on the cassette mounting table 320 to The wafer W is taken out and transferred to the alignment unit 323. Then, the alignment unit 323 adjusts the orientation of the wafer W based on the position of the notch portion of the wafer W. Thereafter, the wafer W is transferred to the imprint unit 310 by the wafer transfer body 322 (step B6 in FIG. 19). In the wafer carry-in / out station 311, the wafers _W in the wafer cassette _CW are accommodated so that the surface to be processed faces upward. In this state, the wafers W are carried to the imprint unit 310.

  The wafer W carried into the imprint unit 310 is transferred to the lift pins 342 and is placed and held on the wafer holding unit 341. Subsequently, after aligning the wafer W held by the wafer holding unit 341 by moving it to a predetermined position in the horizontal direction, the resist solution nozzle 352 is moved in the radial direction of the wafer W, as shown in FIG. As shown, a resist solution is applied onto the wafer W to form a resist film R (step B7 in FIG. 19). At this time, the controller 160 controls the supply timing and supply amount of the resist solution supplied from the resist solution nozzle 352. That is, in the resist pattern formed on the wafer W, the amount of the resist solution applied to the portion corresponding to the convex portion (the portion corresponding to the concave portion in the transfer pattern C of the template T) is large, and the portion corresponding to the concave portion ( The resist solution is applied so that the amount of the resist solution applied to a portion corresponding to the convex portion in the transfer pattern C is small. Thus, the resist solution is applied on the wafer W in accordance with the aperture ratio of the transfer pattern C.

When the resist film R is formed on the wafer W, the wafer W held by the wafer holder 341 is moved to a predetermined position in the horizontal direction for alignment, and the template T held by the template holder 360 is used. Is rotated in a predetermined direction. Then, the template T is lowered to the wafer W side as shown by the arrow in FIG. Template T is lowered to a predetermined position, the surface T ₁ of the template T is pressed against the resist film R on the wafer W. The predetermined position is set based on the height of the resist pattern formed on the wafer W. Subsequently, light is emitted from the light source 363. The light from the light source 363 passes through the template T and is irradiated onto the resist film R on the wafer W, as shown in FIG. 20B, whereby the resist film R is photopolymerized. In this way, the transfer pattern C of the template T is transferred to the resist film R on the wafer W to form the resist pattern P (step B8 in FIG. 19).

Thereafter, the template T is raised as shown in FIG. 20C to form a resist pattern P on the wafer W. At this time, since the surface T ₁ of the template T release agent S is coated, never resist on the wafer W adheres to the surface T ₁ of the template T. Thereafter, the wafer W is transferred to the wafer carrier 322 by the lift pins 342, transferred from the imprint unit 310 to the wafer carry-in / out station 311 and returned to the wafer cassette _CW (step B9 in FIG. 19). Note that a thin resist residual film L may remain in the recesses of the resist pattern P formed on the wafer W. For example, the residual film L outside the imprint system 300 as shown in FIG. The film L may be removed.

The above steps B6 to B9 (portions surrounded by dotted lines in FIG. 19) are repeatedly performed to form resist patterns P on the plurality of wafers W using one template T, respectively. During this period, it repeats the step B1~B5 described above, forming the release agent S on the surface T ₁ of the plurality of templates T. The template T on which the release agent S is formed is stored in the buffer cassette 333 of the interface station 312.

  Then, when Steps B6 to B9 are performed on a predetermined number of wafers W, the used template T is unloaded from the imprint unit 310 by the template transfer body 331 and transferred to the reversing unit 332 (step of FIG. 19). B10). Subsequently, the template transport body 331 transports the template T in the buffer cassette 333 to the imprint unit 310. Thus, the template T in the imprint unit 310 is exchanged. Note that the timing for exchanging the template T is set in consideration of deterioration of the template T and the like. The template T is also replaced when a different resist pattern P is formed on the wafer W. For example, the template T may be exchanged each time the template T is used once. Further, for example, the template T may be exchanged for each wafer W, or the template T may be exchanged for each lot, for example.

The used template T conveyed to the reversing unit 332 has its front and back surfaces reversed. Thereafter, the template conveyor 331, the transport unit 20, the template carrier 12, the template T is returned to the template cassette _{C T.} Thus, in the imprint system 300, the predetermined resist pattern P is continuously formed on the plurality of wafers W while the template T is continuously replaced.

  Since the imprint system 300 of the above embodiment includes the template processing apparatus 1, the template T is deposited on the imprint unit 310 while the release agent S is formed on the template T in the imprint system 300. Can be supplied continuously. Accordingly, for example, even when the resist pattern P is formed on the plurality of wafers W before the template T deteriorates, the template T in the imprint unit 310 can be exchanged continuously and efficiently. Therefore, the predetermined resist pattern P can be continuously formed on the plurality of wafers W. This also enables mass production of semiconductor devices.

When in the above embodiment, although the surface T ₁ was modified in order to adhere the surfaces T ₁ and the release agent S templates T as a substrate, the present invention is to modify the surface of another substrate It can also be applied to.

  For example, in recent years, semiconductor devices have been highly integrated, and it has been proposed to use a three-dimensional integration technique in which the semiconductor devices are three-dimensionally stacked. In this three-dimensional integration technique, for example, semiconductor wafers (hereinafter referred to as “wafers”) as two substrates are joined. In such a case, the hydroxyl groups formed on the wafers are bonded together by dehydration, whereby the wafers are firmly bonded. Therefore, in order to strengthen the bonding between the wafers, for example, oxygen plasma is irradiated onto the wafer to form a larger amount of hydroxyl groups on the wafer. However, in this case, the oxygen plasma may cause physical damage or charge-up damage on the wafer surface. In this regard, when the surface modification liquid is supplied while irradiating the surface of the wafer with ultraviolet rays as in the present invention, a large amount of hydroxyl groups can be imparted to the surface of the wafer. Therefore, according to the present invention, the surface of the wafer can be modified without damaging the surface of the wafer, and the present invention is useful for bonding such wafers.

  The present invention can also be applied to a case where the substrate is another substrate such as an FPD (Flat Panel Display) or a photomask mask reticle.

  Furthermore, the present invention can be applied to the case where the substrate is bonded to another target bond, for example, another silane coupling agent. That is, by adding a large amount of hydroxyl group to the surface of the substrate, the bonding between the surface of the substrate and the silane coupling agent is promoted.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious for those skilled in the art that various modifications or modifications can be conceived within the scope of the idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood.

DESCRIPTION OF SYMBOLS 1 Template processing apparatus 30, 32 Surface modification unit 31, 33 Application | coating unit 40-43 Rinse unit 132 Surface modification liquid nozzle 140 Ultraviolet irradiation part 160 Control part 220 Ultraviolet irradiation part 221 Support plate 230 Surface modification liquid nozzle C Transfer pattern M surface modification solution P resist pattern R resist film S mold release agent T template W wafer

Claims (18)

A method for modifying the surface of a substrate,
A method for modifying a surface of a substrate, wherein a surface modification liquid is supplied to the surface of the substrate while irradiating the surface of the substrate with ultraviolet rays to impart a hydroxyl group to the surface of the substrate. The substrate surface modification method according to claim 1, wherein the surface modification solution is a tertiary alcohol. The substrate surface modification method according to claim 1, wherein the surface modification solution is an alkaline solution. The substrate surface modification method according to claim 1, wherein the surface modification solution is a hydrogen peroxide solution. The surface modification of the substrate according to claim 1, wherein supply of the surface modification liquid to the surface of the substrate is started while the surface of the substrate is irradiated with the ultraviolet rays. Method. Irradiation of the ultraviolet rays onto the surface of the substrate is started in a state where the surface modification liquid is supplied between the surface of the substrate and a support plate arranged to face the surface. The method for modifying the surface of a substrate according to any one of claims 1 to 4. The substrate surface modification method according to claim 6, wherein the support plate transmits the ultraviolet light. 8. The substrate according to claim 1, wherein a transfer pattern is formed on a surface of the substrate, and the substrate is a template for transferring the transfer pattern to a resist film on another substrate to form a resist pattern. The surface modification method for a substrate according to any one of the above. A program that operates on a computer of a control unit that controls the surface modification device in order to cause the surface modification device to execute the substrate surface modification method according to claim 1. A readable computer storage medium storing the program according to claim 9. A surface modification device for modifying the surface of a substrate,
An ultraviolet irradiation unit for irradiating the surface of the substrate with ultraviolet rays;
A surface modification liquid supply unit for supplying a surface modification liquid for imparting hydroxyl groups to the surface of the substrate;
A control unit for controlling the ultraviolet irradiation unit and the surface modification liquid supply unit so as to supply the surface modification liquid to the surface of the substrate while irradiating the surface of the substrate with the ultraviolet light. An apparatus for modifying the surface of a substrate. The substrate surface modification apparatus according to claim 11, wherein the surface modification liquid is a tertiary alcohol. The substrate surface modification apparatus according to claim 11, wherein the surface modification solution is an alkaline solution. The substrate surface modification apparatus according to claim 11, wherein the surface modification solution is hydrogen peroxide solution. The control unit controls the ultraviolet irradiation unit and the surface modifying liquid supply unit so as to start supplying the surface modifying liquid to the surface of the substrate while the surface of the substrate is irradiated with the ultraviolet light. The apparatus for modifying a surface of a substrate according to claim 11, wherein: Having a support plate arranged facing the surface of the substrate;
The control unit starts the irradiation of the ultraviolet rays on the surface of the substrate in a state where the surface modification liquid is supplied between the surface of the substrate and the support plate. The surface modification apparatus for a substrate according to any one of claims 11 to 14, wherein the surface modification liquid supply unit is controlled. The substrate surface modification apparatus according to claim 16, wherein the support plate transmits the ultraviolet light. The substrate is a template for forming a resist pattern by forming a transfer pattern on a surface and transferring the transfer pattern to a resist film on another substrate. The substrate surface modifying apparatus as described.

Images