JP5335717B2 - Resist composition arranging apparatus and pattern forming body manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve an imprint transfer shape and variance in residue thickness after imprinting by stabilizing a discharge when discretely arranging a resist composition using an inkjet method. <P>SOLUTION: A resist composition arrangement device that discretely arranges the resist composition to be used for the imprinting method on a substrate includes: a polymer content storage means of storing a polymer content of the resist composition; a resist discharging means of discharging the resist composition from a nozzle; and a driving waveform-adjusting means of changing a driving waveform for discharging the resist composition from the nozzle according to the polymer content. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a resist composition arranging device and a pattern forming body manufacturing method, and more particularly to a resist composition arranging device and a pattern forming body manufacturing method in which a nanoimprint resist composition is discretely arranged by an ink jet method.

  In recent years, nanoimprinting has been known as a technique for forming fine patterns. A wide range of applications such as semiconductors, electronic devices, hard disks, and optical films are envisaged for application development of nanoimprints. In particular, in areas such as semiconductors and patterned media, there is a high expectation of nanoimprinting for patterning in areas where the pattern width is 100 nm or less and the pattern aspect ratio is 2 or more for further performance improvement.

  An outline of the conventional imprint method is shown in FIGS.

  First, as shown in FIG. 20A, after applying a resist composition to a substrate 900 made of an arbitrary material, a resist layer 902 is formed by spin coating with a general-purpose spin coater. Next, the mold structure 910 on which the imprint pattern is formed is pressed from the resist layer 902 side.

  Next, as shown in FIG. 20B, after applying pressure from the state in which the mold structure 910 is pressed and patterning the resist layer 902 using the pattern of the mold structure 910 as a template, A curing process is performed so that the mold structure 910 is peeled off.

  In this way, a resist pattern (resist layer 902) is formed on the substrate 900 as shown in FIG. At this time, a thin film of the resist layer 902 remains as a remaining film 904 in a gap between the mold convex portion and the substrate 900 on which the resist layer 902 is formed.

  In the field of semiconductors and the like, in the process after pattern formation, the pattern is used as a resist, and the surface on the substrate side is processed by etching. Therefore, in order to further improve processing accuracy, the gap between the bottom surface of the nanoimprint pattern and the substrate is increased. It is necessary to reduce the thickness of the remaining film (residue) corresponding to the thickness of the film. Furthermore, it is necessary to achieve in-plane uniformity in these fine processings over the entire imprint surface.

  It has been proposed to form a resist layer using an ink jet method instead of spin coating. At this time, in order to improve the throughput and make the residual film (residue) uniform, the ink jet droplet density and the amount of ink droplets are changed according to the NIL (nanoimprint lithography) pattern, or the ink jet impact according to the NIL resist volatilization amount. It is known to change the droplet density and the droplet ejection amount.

  For example, in Patent Document 1, when a plurality of spaced droplets each having a corresponding unit volume are arranged on a region of a substrate, the total volume of the droplets in that region is to be formed in that region. A method of dispensing a volume of liquid onto a substrate, such as a function of the pattern volume, is disclosed.

  Further, for example, in Patent Document 2, an imprint material is applied by an inkjet method, but the applied imprint material is volatilized, and the amount of volatilization varies depending on the pattern density of the template used. And calculating the pattern density of the template from the template information including the depth, taking out the volatile compensation coating amount distribution corresponding to this pattern density, and taking out the volatile compensation coating amount distribution, the pattern filling portion coating amount distribution, An imprint having an application unit that calculates the imprint material application amount distribution by adding the remaining film thickness application amount distribution and applying the imprint material on the substrate based on the calculated imprint material application amount distribution. A system is disclosed.

Special table 2008-502157 gazette JP 2009-88376 A

  However, in the case of a curable monomer such as an imprint resist, depending on the storage environment, the monomers may be polymerized and polymerized to increase the viscosity. In addition, even if the polymer does not increase in viscosity, the length of the liquid column formed by the liquid ejected from the nozzle is increased in the ejection by ink jet, and the ejection speed is lowered or the ejection becomes unstable. It has been confirmed that there is an adverse effect that the landing positions vary.

  When the liquid column formed by the liquid discharged from the nozzle becomes long, mist is likely to be generated. And if mist generate | occur | produces, the generated mist will adhere to a nozzle surface and discharge will become unstable. Moreover, since mist adheres to a board | substrate at random, the device for not lengthening the liquid column which the liquid discharged from the nozzle forms is required.

  In addition, the dispersion of the landing position and the volume of the discharged liquid due to the mist adhering to the substrate will increase, resulting in an increase in the variation of the residual thickness after imprinting. There is a problem that it is not filled and may not be partially transferred.

  The present invention has been made in view of such circumstances, and when disposing a resist composition discretely using an ink jet method, the ejection is stabilized, the imprint transfer shape, and the residue thickness variation after imprinting. It is an object of the present invention to provide a resist composition arranging device and a pattern forming body manufacturing method capable of improving the resistance.

In order to achieve the above object, the invention according to claim 1 is characterized in that a mold having a pattern surface formed in a concavo-convex shape is formed on a resist layer formed by a resist composition arranged on a substrate. A pattern corresponding to the pattern of the mold that is pressed toward the resist layer side, is cured with respect to the resist composition, and peels off the interface between the pattern surface of the mold and the resist layer formed on the substrate A resist composition placement apparatus for discretely placing a resist composition used in an imprint method for forming a resist on a substrate, the polymer content storage means for storing the polymer content of the resist composition, and the resist composition A resist discharge means for discharging an object from a nozzle, and a drive waveform for discharging the resist composition from the nozzle according to the polymer content. A drive waveform adjusting means, possess that, the drive waveform includes a first pull drive waveform element for driving to draw the meniscus surface of the resist composition in the nozzle, the first pull drive waveform element Later, a push drive waveform element that is driven to discharge the resist composition from the nozzle, and a liquid column formed by the resist composition that is drawn from the nozzle again after the meniscus surface is drawn after the push drive waveform element. A second pulling drive waveform that is driven to cut a distance T2 between the rear end of the push driving waveform element and the tip of the second pulling drive waveform element, the polymer content being There is provided a resist composition placement device characterized in that the larger the number, the shorter .

  Accordingly, the drive waveform can be optimized according to the polymer content, and the ejection can be stabilized and the imprint transfer shape and the residue thickness variation can be improved.

  Thereby, the liquid column length in the discharge of the resist composition can be optimized according to the polymer content in the resist composition, the discharge can be stabilized, and the imprint transfer shape and the residue thickness variation can be improved. .

Further, as shown in claim 2 , in the driving waveform for discharging the resist composition, the size of the first pulling driving waveform element is reduced as the polymer content is increased. To do.

  Thereby, the liquid column length in the discharge of the resist composition can be optimized according to the polymer content in the resist composition, the discharge can be stabilized, and the imprint transfer shape and the residue thickness variation can be improved. .

Similarly, in order to achieve the above-mentioned object, the invention according to claim 3 provides a mold having a pattern surface formed in a concavo-convex shape on a resist layer formed by a resist composition disposed on a substrate. The pattern of the mold which presses the pattern surface toward the resist layer side, cures the resist composition, and peels the interface between the pattern surface of the mold and the resist layer formed on the substrate A resist composition placement device for discretely placing on a substrate a resist composition used in an imprint method for forming a pattern corresponding to the above, a polymer content storage means for storing the polymer content of the resist composition; , A resist discharge means for discharging the resist composition from the nozzle, and a discharge speed meter for measuring the discharge speed of the resist composition discharged from the nozzle Yes means, the speed change means changes the discharge speed in response to the polymer content, and the landing interval changing means for changing the landing interval of the resist composition landed on the substrate depending on the polymer content And a flight distance adjusting means for adjusting a flight distance until the resist composition discharged from the nozzle lands on the substrate, and the flight distance is shortened as the polymer content increases. providing a resist composition disposed apparatus characterized by the.

This makes it possible to determine the change in discharge volume due to the polymer content in the resist composition based on the discharge speed, to optimize the landing interval according to the discharge volume, and to apply a desired application amount. The residue thickness can be made constant without depending on the polymer content. Further, even if the discharge speed is low, landing position variation does not deteriorate, and imprint transfer shape and residue thickness variation are improved.

According to a fourth aspect of the present invention, the speed changing unit is configured to decrease the discharge speed as the polymer content increases.

According to a fifth aspect of the present invention, the landing interval changing means narrows the landing interval as the polymer content increases.

  This optimizes the discharge speed from the viewpoint of discharge stability (liquid column length), can improve the imprint transfer shape and residue thickness variation, can apply the desired application amount, and the residue thickness after imprint Can be made constant without depending on the polymer content.

Similarly, in order to achieve the above object, the invention according to claim 6 provides a mold having a pattern surface formed in a concavo-convex shape on a resist layer formed by a resist composition disposed on a substrate. The pattern of the mold which presses the pattern surface toward the resist layer side, cures the resist composition, and peels the interface between the pattern surface of the mold and the resist layer formed on the substrate A method of manufacturing a pattern forming body used in an imprint method for forming a pattern corresponding to the above: a step of storing a polymer content of the resist composition, a step of discharging the resist composition from a nozzle, and the nozzle wherein the step of driving waveforms for the resist composition to eject to change depending on the polymer content, only contains the drive waveform, registration in the nozzle from A first pulling drive waveform element that is driven to draw the meniscus surface of the toner composition, and a push drive waveform element that is driven to discharge the resist composition from the nozzle after the first pulling drive waveform element And a second pull drive waveform for driving the meniscus surface again after the push drive waveform element to drive the liquid column formed by the resist composition discharged from the nozzle, There is provided a method for producing a pattern forming body, characterized in that a distance T2 between a rear end of the push drive waveform element and a tip of the second pull drive waveform element is shortened as the polymer content increases .

Accordingly, the drive waveform can be optimized according to the polymer content, and the ejection can be stabilized and the imprint transfer shape and the residue thickness variation can be improved. Further, the length of the liquid column in discharging the resist composition can be optimized according to the polymer content in the resist composition, so that the discharging can be stabilized and the imprint transfer shape and residue thickness variation can be improved.

Similarly, in order to achieve the above object, the invention according to claim 7 provides a mold having a pattern surface formed in a concavo-convex shape on a resist layer formed by a resist composition disposed on a substrate. The pattern of the mold which presses the pattern surface toward the resist layer side, cures the resist composition, and peels the interface between the pattern surface of the mold and the resist layer formed on the substrate A method of manufacturing a pattern forming body used in an imprint method for forming a pattern corresponding to the above: a step of storing a polymer content of the resist composition, a step of discharging the resist composition from a nozzle, and the nozzle A step of measuring a discharge speed of the resist composition discharged from the liquid, and changing the discharge speed according to the polymer content, and the polymer Wherein the step of changing the landing interval of the resist composition, only contains further flying distance to the resist composition discharged from the nozzle land on the substrate to be landed on the substrate in accordance with the chromatic amount And a flight distance adjusting step for adjusting the distance, and the more the polymer content is increased, the shorter the flight distance is .

This makes it possible to determine the change in discharge volume due to the polymer content in the resist composition based on the discharge speed, to optimize the landing interval according to the discharge volume, and to apply a desired application amount. The residue thickness can be made constant without depending on the polymer content. Further, even if the discharge speed is low, landing position variation does not deteriorate, and imprint transfer shape and residue thickness variation are improved.

  As described above, according to the present invention, the drive waveform can be optimized according to the polymer content, and the ejection can be stabilized and the imprint transfer shape and the residue thickness variation can be improved.

It is a perspective view which shows schematic structure of an inkjet coating apparatus. It is a block diagram which shows schematic structure of a nanoimprint system. It is a block diagram which shows the outline of a resist supply system. It is a block diagram which shows the system configuration | structure of the control system of a nanoimprint system. It is a flowchart which shows operation | movement of an inkjet coating device. It is a flowchart which similarly shows operation | movement of an inkjet coating device. It is a diagram which shows the drive waveform (voltage waveform) of the drive signal applied to an actuator. (A)-(c) is a schematic diagram which shows the state of the resist in the nozzle corresponding to a drive waveform. (A), (b) is a diagram which shows the example of a waveform. It is a diagram which shows the example of a waveform. It is a diagram which shows the example of a waveform. It is a diagram which shows the example of a waveform. It is a diagram which shows the drive waveform (voltage waveform) of the drive signal applied to an actuator. (A), (b) is a schematic diagram which shows the state of the resist in the nozzle corresponding to a drive waveform. It is a diagram which shows the example of a waveform. It is a diagram which shows the example of a waveform. It is a diagram which shows the relationship between discharge speed and discharge volume. It is a table which shows the relationship between a polymer amount, discharge speed, etc. It is a table which shows the relationship between discharge speed, discharge volume, and landing interval. (A)-(c) It is explanatory drawing which shows the conventional imprint method.

  Hereinafter, with reference to the attached drawings, a resist composition arranging device and a method for producing a pattern forming body according to the present invention will be described in detail.

  FIG. 1 is a perspective view showing a schematic configuration of an ink jet coating apparatus as a resist composition arranging apparatus for discretely arranging resist compositions using an ink jet method.

  As shown in FIG. 1, the ink jet coating apparatus 10 of this embodiment includes a head holding and moving means that moves along a beam 16 that is passed between two columns 14 and 14 that are vertically set on a support base 12. An ink jet head 20 attached to a lower end of 18 via a rotatable stage, a work alignment means 22 attached to the head holding / moving means 18, and a support base 12 are provided on a substrate such as a semiconductor. Workpiece holding / moving means 24 for placing a work 26, nozzle face observing means 28 for observing the nozzle surface of the inkjet head 20, discharge state observing means 30 (30a, 30b), and maintenance for maintaining the nozzle face of the inkjet head 20 Means 32 and the like are included.

  The head holding / moving means 18 holds the ink jet head 20 at the tip, and moves the ink jet head 20 in the direction along the beam 16 (left-right direction in the figure). The head holding / moving means 18 is centered on the ejection direction from the ink jet head 20. A rotating stage for rotating and moving, and a moving means for moving in the discharge direction (vertical direction). Adjusting the flight distance until the resist composition discharged from the inkjet head 20 (hereinafter also referred to simply as “resist”) reaches the workpiece 26 by moving the inkjet head 20 in the discharge direction (vertical direction). Can do. Further, the landing interval of the resist composition landing on the workpiece 26 can also be adjusted by moving it in the direction along the beam 16 (left-right direction in the figure) or rotating it.

  A linear motor or the like is preferably exemplified as the moving means in the case of linear movement such as the moving means in the direction along the beam 16 or the moving means in the discharge direction. In order to perform accurate movement control, a linear encoder is provided as position detecting means. Further, a stepping motor or the like can be used as the rotating means, and an encoder is also installed as a position detecting means.

  The ink jet head 20 discharges a resist composition from a nozzle. The driving method of the inkjet head 20 is not particularly limited, and various methods such as a piezo method, a thermal method, and an electrostatic method can be adopted. However, in the case of this embodiment in which a nanoimprint resist composition is discharged, a piezo method in which adjustment of the droplet amount and discharge speed is easy is preferable. In this embodiment, a piezo method is employed. As will be described in detail later, by adjusting the driving waveform (voltage waveform) for driving the piezo (piezoelectric element) actuator according to the polymer content in the resist composition, the resist composition ejection speed and ejection The volume and the landing position on the workpiece 26 are adjusted.

  A resist supply system for supplying a resist composition to the inkjet head 20 will be described later.

  The workpiece alignment means 22 detects the position of the workpiece (substrate) 26 in order to adjust the position. The workpiece alignment means 22 includes an alignment camera that detects the alignment of the workpiece 26, a landing position detection camera that detects the landing position of the resist landed on the dummy workpiece for position detection, and the like.

  The work holding / moving means 24 moves by sucking and holding the work 26 and includes means for sucking the work 26. The adsorption method of the adsorption means is not particularly limited, and may be vacuum adsorption or electrostatic adsorption. The work holding / moving means 24 includes a moving means such as a linear motor that holds the work 26 and moves in a first direction and a second direction (xy direction) orthogonal thereto, and a linear encoder as a position detecting means. It has. The work holding / moving means 24 includes a rotating means such as a stepping motor that holds the work 26 and can rotate about a work normal direction parallel to the ejection direction of the inkjet head 20, and an encoder for position detection. I have.

  The nozzle surface observing means 28 is used to determine whether maintenance is necessary or to determine whether to replace the head by observing the nozzle surface of the inkjet head 20. The nozzle surface observation means 28 includes a light source, a lens, and a camera for observing the nozzle state. When observing the nozzle surface, the head holding / moving means 18 moves the inkjet head 20 directly above the nozzle surface observing means 28.

  The ejection state observation means 30 (30a, 30b) is for observing the flying state of the resist ejected from the nozzles of the inkjet head 20. The discharge state observation means 30 includes a light source, a lens, and a camera for observing the flight state.

  That is, the discharge state observing means 30 receives the detection light emitted by the light emitting means (light source) 30a by the light receiving means (camera) 30b, detects the change in light due to the resist composition flying in the detection light, and discharges it. Observe the condition and measure the discharge speed. When observing the discharge state, the discharge state observation means 30 or the inkjet head 20 is moved and observed so that the resist flies through the detection light.

  The maintenance means 32 is for keeping the state of the inkjet head 20 in good condition. Therefore, the maintenance unit 32 includes a wiper for cleaning the resist and the like attached to the nozzle surface, a cap for preventing the resist in the nozzle from drying. The cap is also used as a cap for removing foreign matters such as bubbles in the inkjet head 20 by sucking the resist from the nozzle.

  FIG. 2 shows a schematic configuration of the nanoimprint system.

  As shown in FIG. 2, the nanoimprint system 1 according to the present embodiment includes an inkjet coating apparatus 10, a NIL apparatus 40, substrate storage units 42 and 44, a substrate mounting unit 46, and load / unloading units 48a and 48b. The

  The substrate storage unit 42 stores a workpiece (substrate) 26 (not shown here, see FIG. 1) on which the resist composition is applied to the surface of the substrate by the inkjet coating apparatus 10. The workpiece 26 on which the resist is applied by the inkjet coating apparatus 10 is placed, and the substrate storage unit 44 is for placing the workpiece 26 that has been subjected to nanoimprint processing by the NIL device 40.

  The load / unload means 48a and 48b exchange the substrate 26 among the substrate storage unit 42, the substrate mounting unit 46, and the substrate storage unit 44, respectively.

  In the imprint method in the present embodiment, an imprint mold (not shown) having a pattern shape from the surface region side is applied to the resist composition (resist layer) coated on the work 26 by the inkjet coating apparatus 10. By applying pressure in the pressed state, a resist pattern in which the pattern shape of the mold is transferred as a mold is formed.

  The imprint mold (mold structure) is not particularly limited as long as it has a fine pattern shape, and can be appropriately selected according to the purpose.

  The resist pattern formed on the resist layer is transferred using the imprint mold as a mold, and has a pattern shape substantially similar to the fine pattern shape of the imprint mold (mold structure).

  The pitch interval between the convex portions of the mold structure is preferably 30 to 200 nm. Moreover, as a width | variety of a convex part, 15-60 nm is preferable. Furthermore, as a width | variety of a recessed part, 15-100 nm is preferable.

  From the viewpoint of ease of mold release after imprinting, the convex portion is preferably tapered from the base end side toward the pointed tip side. Moreover, as this taper angle, 70-88 degrees is preferable.

  In addition, there is no restriction | limiting in particular as an apparatus which pressurizes in the state which pressed the mold for imprints, According to the objective, it can select suitably.

  When peeling from the state where the imprint mold is pressed and pressed, the peeling time is generally about 10 to 15 seconds in the case of a pattern in a 2.5 mm disk, for example. According to the imprinting method to be used, peeling can be performed in 1 to 10 seconds without causing peeling failure, and productivity is improved.

  The pattern forming body of this embodiment forms a pattern shape by performing etching using a resist pattern formed by the imprint method as a mask. The pattern forming body is not particularly limited as long as the pattern shape is formed.

  Moreover, there is no restriction | limiting in particular as a structure of a pattern formation body, According to the objective, it can select suitably. For example, it suffices to have a pattern shape formed by etching using a resist pattern as a mask formed by an imprint method, and various layers can be selected as a layer to be etched.

  Examples of uses of the pattern forming body include semiconductors, devices, magnetic recording media, optical films, and imprint molds used in imprint processes for these purposes.

  FIG. 3 shows an outline of the resist supply system.

  As shown in FIG. 3, the resist supply system of the present embodiment is for supplying a resist composition from a resist supply tank 50 for storing the resist composition to the inkjet head 20, and each part is a conduit (tube). It is connected with.

  The resist supply tank 50 is a base tank for supplying a resist to the inkjet head 20, and is provided with a heating / cooling means (temperature adjusting means) 52 and a temperature sensor 54. In addition, a pump 56 is provided downstream of the resist supply tank 50 for pumping up the resist composition and feeding it to the inkjet head 20.

  Further, a filter 58 for removing polymer (impurities) and a deaeration device 60 for removing bubbles and dissolved gas are provided in the middle of the pipeline connecting the resist supply tank 50 and the inkjet head 20. The filter 58 is not particularly limited, but an ultra high molecular weight polyethylene (UPE) membrane or a nylon membrane is used. The filter mesh size of the filter 58 is preferably equal to or smaller than the nozzle diameter of the inkjet head 20. In addition, a liquid trap unit 62 and a pump 64 are connected to the deaeration device 60.

  In addition, a sub-tank 66 is provided in the pipe line A connecting the deaeration device 60 and the inkjet head 20, and another pipe B that bypasses the sub-tank 66 is provided, and a pump 68 is provided in the pipe B. is set up. Further, valves 70 and 72 are provided in the pipe A and the pipe B, respectively, and the pipes A and B can be switched by controlling the valves 70 and 72 to open and close. At the time of normal drawing, the valve 70 is opened and the valve 72 is closed and the resist composition is supplied from the pipe A. At the time of initial filling or purging, the valve 70 is closed and the valve 72 is opened to pass the pipe B.

  There is a membrane 67 in the subtank 66, and air is supplied and sucked by a pump 76 through a valve 74 to the space above the membrane 67 to control the pressure in the upper space of the membrane 67, thereby controlling the resist below the membrane 67. The pressure of the composition is controlled. Thereby, the meniscus pressure of the resist composition in the nozzle can be adjusted. The sub tank 66 is provided with a pressure sensor 80 for detecting the pressure of the resist composition.

  As described above, the sub tank 66 having the film 67 and provided with the pump 76 via the valve 74 has a function of a meniscus pressure adjusting means for adjusting the meniscus pressure of the resist composition in the nozzle.

  Further, the sub-tank 66 is provided with heating / cooling means (temperature adjusting means) 78 and a temperature sensor 82, and the sub-tank 66 and the resist supply tank 50 are configured such that the temperature can be adjusted independently. Yes.

  The ink jet head 20 is also provided with a heating / cooling means (temperature adjusting means) 84 and a temperature sensor 86, and the temperature of the resist can be controlled here.

  A cap 88 of the maintenance unit 32 is provided for the inkjet head 20 as a unit for preventing the nozzle from drying or preventing the resist viscosity from increasing near the nozzle. The cap 88 is moved from a predetermined retracted position to a maintenance position below the inkjet head 20 as necessary.

  The cap 88 can cover the nozzle surface of the inkjet head 20. Although not shown, the maintenance means 32 has a cleaning blade for wiping and cleaning the nozzle surface.

  During drawing or standby, when a specific nozzle is used less frequently and the resist viscosity in the vicinity of the nozzle increases, preliminary ejection is performed toward the cap 88 in order to discharge the resist whose viscosity has increased and deteriorated. Is called.

  In addition, if bubbles left behind by the filter 58 or the deaerator 60 are mixed in the nozzle or if the resist viscosity in the nozzle exceeds a certain level, the resist composition cannot be discharged by preliminary discharge. In this case, the cap 88 is applied to the nozzle surface of the ink jet head 20, the resist composition in the ink jet head 20 is sucked by the suction pump 90, and the resist composition removed by suction is recovered in the recovery tank 92.

  In addition, the valve 70 is closed and the valve 72 is opened to allow the pipe B to pass, the pump 68 is operated, the resist is forcibly sent to the ink-jet head 20, and the ink is discharged (purged) from the nozzles to generate bubbles and the like. Can also be removed.

  However, since such suction operation and purge operation are performed on the entire resist in the inkjet head 20, the resist consumption is large. Therefore, when the viscosity increase is small, it is preferable to perform preliminary discharge as much as possible. The cap 88 functions as a suction unit and also functions as a resist holder for preliminary ejection. Moreover, it is preferable that the inside of the cap 88 is divided into a plurality of regions corresponding to the nozzle rows by a partition wall, and the partitioned regions can be selectively sucked.

  FIG. 4 shows a system configuration of a control system of the nanoimprint system.

  The control system of the nanoimprint system includes a communication interface (communication I / F) 102, a system controller 104, an image memory 106, a print control unit 108, a head driver 110, an image buffer memory 112, a resist supply control unit 116, a maintenance control unit 118, An observation control unit 122, a load / unload control unit 124, an alignment control unit 126, a motor control unit 130, and the like are provided.

  The communication interface 102 is an interface unit that receives registration information sent from the host computer 100. As the communication interface 102, a serial interface such as USB, IEEE1394, Ethernet, and wireless network, and a parallel interface such as Centronics can be applied. In this part, a buffer memory for speeding up communication may be mounted.

  The registration information sent from the host computer 100 is taken into the system controller 104 via the communication interface 102 and temporarily stored in the image memory 106. The image memory 106 is storage means for temporarily storing resist information (including the resist polymer content) input via the communication interface 102, and information is read and written through the system controller 104. The image memory 106 is not limited to a memory made of a semiconductor element, and a magnetic medium such as a hard disk may be used.

  The system controller 104 is a control unit that controls each unit such as the communication interface 102, the image memory 106, the print control unit 108, and the head driver 110. The system controller 104 includes a central processing unit (CPU) and its peripheral circuits, and performs communication control with the host computer 100, read / write control of the image memory 106, etc., and a resist supply control unit 116 and maintenance control. A control signal for controlling each control unit such as the unit 118, the observation control unit 122, the load / unload control unit 124, the alignment control unit 126, and the motor control unit 130 is generated.

  The print control unit 108 performs various processing and correction processes for generating a print (drawing) control signal (drive waveform) from resist information including the polymer content in the image memory 106 according to the control of the system controller 104. And a control unit that supplies the generated print control signal (drive waveform) to the head driver 110.

  The print control unit 108 performs necessary signal processing, and controls the discharge amount and discharge timing of the resist composition of the inkjet head 20 via the head driver 110 based on the resist information. As will be described in detail later, the driving waveform for discharging the resist composition is changed (adjusted) according to the polymer content. Thereby, a desired dot size and dot arrangement of the resist composition that lands on the work 26 is realized.

  The print control unit 108 includes an image buffer memory 112, and data such as registration information and parameters is temporarily stored in the image buffer memory 112 during registration information processing in the print control unit 108. In FIG. 4, the image buffer memory 112 is shown in a mode associated with the print control unit 108, but it may also be used as the image memory 106. Furthermore, an aspect in which the print control unit 108 and the system controller 104 are integrated and configured with one processor is also possible.

  The head driver 110 drives the ink jet head 20 based on the drive waveform given from the print control unit 108, and discharges the resist composition from the ink jet head 20. The head driver 110 may include a feedback control system for keeping the head driving conditions constant.

  The resist supply controller 116 mainly drives each pump of the resist supply unit 114 (resist supply system shown in FIG. 3) to send the resist composition from the resist supply tank 50 to the inkjet head 20.

  The maintenance control unit 118 controls the maintenance unit 32. When maintenance is required, the cap of the maintenance unit 32 faces the nozzle surface of the inkjet head 20 to perform preliminary discharge or purge, or the cap is moved to the nozzle surface. The maintenance operation is performed by sucking the resist whose viscosity has been increased by applying the resist.

  The observation control unit 122 controls the observation unit 120 such as the nozzle surface observation unit 28 and the discharge state observation unit 30 (30a, 30b). The load / unload control unit 124 controls the load / unload unit 48 (48a, 48b). The alignment control unit 126 controls the alignment unit (work alignment unit) 22 to adjust the position of the work. The motor control unit 130 controls the motor unit 128 to drive the head holding / moving unit 18, the workpiece holding / moving unit 24, and the like.

  Next, the resist composition (curable composition for nanoimprint) used in the present embodiment will be described.

  First, a first example of the curable composition for nanoimprint will be described. The nanoimprint curable composition of the present embodiment includes at least a polymerizable monomer (Ax) having a polycyclic aromatic structure and a photopolymerization initiator (B). Usually, the curable composition used in the photo-nanoimprint method includes a polymerizable monomer having a polymerizable functional group and a photopolymerization initiator that initiates a polymerization reaction of the polymerizable monomer by light irradiation. If necessary, it further includes a solvent, a surfactant, an antioxidant, or the like. In the curable composition for nanoimprints of this embodiment, at least the polymerizable monomer (Ax) is included as a polymerizable monomer having a polymerizable functional group. The curable composition for nanoimprints of this embodiment contains a polymerizable monomer (Ax) having a polycyclic aromatic structure, so that a pattern excellent in mold releasability, etching resistance and solvent resistance can be obtained by the nanoimprint method. Can be formed.

(Polymerizable monomer)
-Polymerizable monomer (Ax)-
The polymerizable monomer (Ax) in this embodiment is a compound containing a polymerizable functional group. Examples of the polymerizable functional group include a cationic polymerizable functional group and a radical polymerizable functional group, and a radical polymerizable functional group is preferable. The cationic polymerizable functional group is preferably an epoxy group or an oxetane group. Examples of the radical polymerizable functional group include a functional group having an ethylenically unsaturated bond, and a (meth) acryl group, a vinyl group, and an allyl group are preferable. The number of polymerizable functional groups contained in the polymerizable monomer (Ax) in the present embodiment is preferably 1 to 4, and more preferably 1 to 2, from the viewpoints of curability and viscosity.

  The polymerizable monomer (Ax) in the present embodiment has a polycyclic aromatic structure, that is, a condensed polycyclic aromatic structure in which at least two ring structures are condensed. Therefore, the polycyclic aromatic structure does not include a ring assembly structure in which two or more single aromatic rings such as bisphenol are connected by a single bond or an organic connecting group. Further, in the present embodiment, “polycyclic aromatic” means not only those in which condensed rings such as naphthalene are all aromatic rings but also condensed aromatic rings and non-aromatic rings, for example, benzene and cyclohexane. 1,2,3,4-tetrahydronaphthalene structure and the like fused with each other. In addition, the polycyclic aromatic structure in the present embodiment is preferably 2 to 4 condensed ring structures, more preferably 2 to 3 condensed ring structures, and particularly preferably 2 condensed ring structures. preferable. The curable composition for nanoimprints does not contain a polymerizable monomer having a polycyclic aromatic structure, that is, all the polymerized compounds in the curable composition for nanoimprints have 1 or less ring aromatic structure. In the case of the compound, the deterioration of the pattern at the time of dry etching is large (that is, the resistance to dry etching is low), the solvent resistance at the time of pattern development is not sufficient, and the releasability between the mold and the pattern is also low. Therefore, these performances cannot be exhibited at a sufficiently high level at the same time. The curable composition for nanoimprinting of the present embodiment has good releasability from the mold even when a nanometer order pattern is formed.

  Examples of the polycyclic aromatic structure of the polymerizable monomer (Ax) in the present embodiment include hydrocarbon-based polycyclic aromatic structures such as naphthalene, anthracene, phenanthrene, pyrene, 1,2,3,4-tetrahydronaphthalene. In addition, examples include heteropolycyclic aromatic structures such as indole, carbazole, quinoline, and benzoisoquinoline. The polycyclic aromatic structure in the present embodiment is preferably a hydrocarbon-based polycyclic aromatic structure, more preferably a naphthalene structure or an anthracene structure, and particularly preferably a naphthalene structure.

  As carbon number of the polymerizable monomer (Ax) in this embodiment, 10-30 are preferable from a viewpoint of a viscosity and solvent resistance, 10-20 are more preferable, and 11-16 are especially preferable. The molecular weight of the polymerizable monomer (Ax) is preferably from 150 to 400, more preferably from 150 to 300, particularly preferably from 190 to 300, from the viewpoints of viscosity and solvent resistance.

  The polymerizable monomer (Ax) having a polycyclic aromatic structure is preferably a compound represented by the following formula (I).

(In formula (I), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, X represents a single bond or an organic linking group, and L has a substituent. A m-valent polycyclic aromatic group that may be present, and m represents an integer of 1 to 3.)
In the formula (I), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom. The alkyl group which may have a substituent is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of curability. As said alkyl group, a methyl group, an ethyl group, and a propyl group are preferable, More preferably, it is a methyl group. Preferred examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, an alkoxy group, and an acyloxy group.

Examples of the halogen atom as a substituent for R ¹ and the alkyl group include fluorine, chlorine, bromine and iodine atoms, and preferably a fluorine atom.

  In the formula (I), X represents a single bond or an organic linking group. Examples of the organic linking group include —O—, —C (═O) O—, —C (═O) NRx— (Rx represents a hydrogen atom or an organic group, and examples of the organic group include an aryl group and an alkyl group. Group is preferable), an alkylene group, and a linking group in which a plurality of these are combined is preferable, and —C (═O) O— and —C (═O) O-alkylene- are more preferable.

Moreover, in Formula (I), m shows the integer of 1-3, and 1 or 2 is preferable from a viscosity and sclerosing | hardenable viewpoint. When m is 2 or more, a plurality of X and R ¹ may be the same or different.

  In the formula (I), L represents an m-valent polycyclic aromatic group which may have a substituent. The polycyclic aromatic group means a group having the above-mentioned polycyclic aromatic structure, and is preferably a group having a naphthalene structure. Examples of the substituent for L include an alkyl group, an aryl group, a halogen atom, an acyloxy group, an alkoxycarbonyl group, a nitro group, and a cyano group.

  The polymerizable monomer (Ax) having a polycyclic aromatic structure in the present embodiment is more preferably a compound represented by the following formula (IA).

(In formula (IA), R ¹ represents a hydrogen atom, an optionally substituted alkyl group or a halogen atom, X represents a single bond or an organic linking group, and m represents an integer of 1 to 3. And R ^{2 represents} an organic substituent, and n represents an integer of 0 to 6.)
R ¹ , X, and m in formula (IA) have the same meanings as those in formula (I) described above, and the preferred ranges are also the same. When m is 2 or more, a plurality of X and R ¹ may be the same or different.

In formula (IA), R ² represents an organic substituent. As the organic substituent, an alkyl group, an aryl group, a halogen atom, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, and an alkoxy group are preferable.

In the formula (IA), n represents an integer of 0 to 6, and preferably 0 to 3. When n is 2 or more, a plurality of R ² may be the same or different. The compound represented by the formula (IA) is preferably a (meth) acrylic acid ester having a naphthalene structure or an acrylamide having a naphthalene structure, and particularly preferably a compound represented by the formula (IB). .

In formula (IB), Y represents a single bond or an alkylene group which may contain a hetero atom in the chain. Examples of the alkylene group include a methylene group, an ethylene group, and — (CH ₂ CH ₂ O) —, and a methylene group is preferable. Y is preferably a single bond or a methylene group from the viewpoints of etching resistance and solvent resistance. When m is 2 or more, a plurality of Y and R ¹ may be the same or different.

  The polymerizable monomer (Ax) is a compound represented by the following formula (IC) or (ID), has low viscosity and excellent compatibility with other components, and has mold filling properties. From the viewpoint of improvement, it is more preferable. When the mold filling property is improved, the mold is quickly filled with the curable composition without increasing the mold pressure during the mass production by the nanoimprint method, which is more preferable from the viewpoint of mold durability and throughput. .

In the formula (IB), R ¹ has the same meaning as in the above formula (IA), and the preferred range is also the same.

  Specific examples (compounds (I-1) to (I-29)) of the polymerizable monomer (Ax) in the present embodiment are shown below.

  The polymerizable monomer (Ax) used in the composition of the present embodiment can be synthesized by a conventional method. For example, the compound of formula (IB) can be synthesized by a general synthesis method of ester compounds. Specifically, a method of reacting a carboxylic acid and an alcohol as shown in the following Schme1 under an acid condition, a transesterification method of a carboxylic acid ester and an alcohol as shown in the following Scheme2, a carboxylic acid and a leaving group as shown in the following Scheme3 It can be synthesized by a method of reacting a compound having (preferably a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group) under basic conditions.

  From the viewpoint of curability, the total content of the polymerizable monomer in the curable composition for nanoimprinting of the present embodiment is preferably 50 to 99.5% by mass, and preferably 70 to 99% by mass in all components excluding the solvent. % Is more preferable, and 90 to 99% by mass is particularly preferable. The content of the polymerizable monomer (Ax) in the present embodiment is such that when the polymerizable monomer (Ax) is a compound having one polymerizable functional group, dry etching resistance, solvent resistance, pattern From the viewpoint of formability, 5 to 100% by mass is preferable among all polymerizable monomers, more preferably 20 to 100% by mass, and still more preferably 30 to 100% by mass. When the polymerizable monomer (Ax) is a compound having two polymerizable functional groups, the content of the polymerizable monomer (Ax) in this embodiment is 1 in all polymerizable monomers. -70 mass% is preferable, More preferably, it is 5-60 mass%, More preferably, it is 10-40 mass%. Further, when the polymerizable monomer (Ax) is a compound having three or more polymerizable functional groups, the content of the polymerizable monomer (Ax) in the present embodiment is the total polymerizable monomer. 1-70 mass% is preferable, More preferably, it is 3-50 mass%, More preferably, it is 5-40 mass%. That is, from the viewpoint of improving the composition viscosity, dry etching resistance, imprintability, curability, etc., particularly when the polymerizable monomer (Ax) has two or more polymerizable functional groups, the polymerizable monomer The body (Ax) and another polymerizable monomer different from the polymerizable monomer (Ax) described below are preferably used in combination.

-Other polymerizable monomers-
As described above, the nanoimprint curable composition of the present embodiment is further polymerizable as a polymerizable monomer for the purpose of improving the composition viscosity, dry etching resistance, imprint suitability, curability, and the like. Another polymerizable monomer different from the monomer (Ax) may be included. Examples of the other polymerizable monomer include a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups; a compound having an oxirane ring (epoxy compound); a vinyl ether compound; a styrene derivative; A compound having a fluorine atom; propenyl ether or butenyl ether can be exemplified, and a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups is preferable from the viewpoint of curability.

  The polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups (1 to 6 functional polymerizable unsaturated monomer) will be described.

  First, specific examples of the polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer) include 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2 -Hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxy Butyl (medium ) Acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) Cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) Acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isomyristyl (meth) ) Acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, Neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter “ ECH)) Modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meta ) Acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, Examples include styrene, α-methylstyrene, and acrylonitrile.

  Among these, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate, and adamantyl (meth) acrylate are preferably used in the present invention. It is done.

  It is also preferable to use a polyfunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups as the other polymerizable monomer.

  Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used in this embodiment include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di ( (Meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate , ECH-modified 1,6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) ) Acrylate, modified Sphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO Modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as “PO”) modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (Meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene) Recall) di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified Tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinyl ester Tylene urea and divinyl propylene urea are exemplified.

  Among these, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like are preferably used in this embodiment.

  Examples of the polyfunctional polymerizable unsaturated monomer having 3 or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meta) ) Acrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylol Propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) Acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) Examples include acrylate, pentaerythritol ethoxytetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.

  Examples of the compound having an oxirane ring (epoxy compound) include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycol, and polyglycidyl ethers of aromatic polyols. Examples include teters, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Examples of the compound having an oxirane ring (epoxy compound) that can be preferably used in this embodiment include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, Brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol Glycidyl ethers, polypropylene glycol diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; higher fatty acid Examples thereof include glycidyl esters.

  Among these, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo ( Product)). These can be used alone or in combination of two or more.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part 3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like can be synthesized.

  As another polymerizable monomer used in this embodiment, a vinyl ether compound may be used in combination.

  As the vinyl ether compound, known compounds can be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylol Propane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, tetra Tylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether , Trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1-to Scan [4- (2-vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

  Moreover, a styrene derivative can also be employ | adopted as another polymerizable monomer used by this embodiment. Examples of styrene derivatives include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, p-hydroxy. Examples include styrene.

  In addition, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Use compounds containing fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Can do.

  As another polymerizable monomer used in this embodiment, propenyl ether and butenyl ether can also be used. Examples of the propenyl ether or butenyl ether include 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene Carbonate or the like can be suitably applied.

  The preferred content of the other polymerizable monomers described above varies depending on the content of the polymerizable monomer in the present invention. For example, the total amount of the polymerizable monomers contained in the composition of the present invention is as follows. It is preferably included in the range of 0 to 90% by mass, more preferably in the range of 5 to 80% by mass, and still more preferably in the range of 10 to 50% by mass.

  Next, a preferred blend form of the polymerizable monomer (Ax) and other polymerizable monomers (hereinafter, these may be collectively referred to as “polymerizable unsaturated monomer”) in the present embodiment will be described. To do.

  The monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent and has an effect of reducing the viscosity of the nanoimprint curable composition of the present embodiment, and is based on the total amount of the polymerizable monomer. In addition, 15% by mass or more is preferably added, more preferably 20 to 80% by mass, still more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass.

  The monomer having two unsaturated bond-containing groups (bifunctional polymerizable unsaturated monomer) is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 80% by mass or less of the total polymerizable unsaturated monomer. Preferably, it is added in a range of 70% by mass or less. The ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 10 to 100% by mass, more preferably 30 to 95% by mass, and particularly preferably 50 to 90% by mass of the total polymerizable unsaturated monomer. % Is added. The ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably the total polymerizable unsaturated monomer. Is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered | hung by making the ratio of the polymerizable unsaturated monomer which has 3 or more of polymerizable unsaturated bond containing groups into 80 mass% or less, it is preferable.

  As a more preferable blend form of the polymerizable monomer (Ax) and other polymerizable monomers in the present embodiment, the monofunctional polymerizable monomer (Ax) is 20 to 90 in all polymerizable monomers. 0 to 50% by mass of a monofunctional polymerizable monomer other than the polymerizable monomer (Ax), 0 to 50% by mass, and a bifunctional and / or trifunctional polymerizable monomer other than the polymerizable monomer (Ax) 10 to 50% by mass, and a tetrafunctional or higher functional polymerizable monomer in an amount of 0 to 30% by mass. As the most preferable blend form, 40 to 80% by mass of the monofunctional polymerizable monomer (Ax), 0 to 40% by mass of the monofunctional polymerizable monomer other than the polymerizable monomer (Ax), This is a form containing 20 to 50% by mass of a bifunctional and / or trifunctional polymerizable monomer other than the polymerizable monomer (Ax) and 0 to 10% by mass of a tetrafunctional or higher functional monomer. Furthermore, in addition to the above blended form, the polymerizable monomer having an acrylate group as a polymerizable functional group is in the form of 90 to 100% by mass in the total polymerizable monomer. Thereby, photocurability, mold filling property, dry etching resistance, and mold releasability can be achieved at a high level.

(Photopolymerization initiator (B))
The nanoimprint curable composition of this embodiment contains a photopolymerization initiator. As the photopolymerization initiator used in the present embodiment, any compound can be used as long as it is a compound that generates an active species that polymerizes the above polymerizable monomer by light irradiation. The photopolymerization initiator is preferably a radical polymerization initiator that generates radicals by light irradiation, or a cationic polymerization initiator that generates acids by light irradiation, more preferably a radical polymerization initiator. It is determined appropriately according to the type of the polymerizable group. That is, the photopolymerization initiator in this embodiment is formulated with an activity with respect to the wavelength of the light source to be used, and generates appropriate active species according to the difference in the reaction format (for example, radical polymerization or cationic polymerization). It is necessary to use what In the present embodiment, a plurality of photopolymerization initiators may be used in combination.

  Content of the photoinitiator used for this embodiment is 0.01-15 mass% with respect to all the polymerizable monomers contained in a composition, for example, Preferably it is 0.1-12 mass %, More preferably 0.2 to 7% by mass. When using 2 or more types of photoinitiators, the total amount becomes the said range.

  When the content of the photopolymerization initiator is 0.01% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating strength tend to be improved, which is preferable. On the other hand, when the content of the photopolymerization initiator is 15% by mass or less, light transmittance, colorability, handleability and the like tend to be improved, which is preferable. Until now, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied for ink-jet compositions and dye- and / or pigment-containing liquid crystal display color filter compositions. A preferred photopolymerization initiator and / or photoacid generator addition amount for the curable composition for photo-nanoimprints is not reported. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the nanoimprint curable composition of the present embodiment, dyes and / or pigments are not essential components, and the optimum range of the photopolymerization initiator is in the fields of inkjet compositions, liquid crystal display color filter compositions, and the like. May be different.

  As the radical photopolymerization initiator used in the present embodiment, acylphosphine oxide compounds and oxime ester compounds are preferable from the viewpoints of curing sensitivity and absorption characteristics. As the photopolymerization initiator, for example, a commercially available initiator can be used. Examples of these include Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure (available from Ciba). (Registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane- 1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholinop Pan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide) , 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), Darocur (registered trader) Standard) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (R) 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO available from BASF -L (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methyl), available from ESACUR Nippon Siebel Hegner Phenylsulfur Honyl) propan-1-one, N-1414 Adeka optomer (registered trademark) N-1414 (carbazole phenone system), Adeka optomer (registered trademark) N-1717 (acridine system) available from Asahi Denka Co., Ltd. Adekaoptomer (registered trademark) N-1606 (triazine type), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1 manufactured by Sanwa Chemical Co., Ltd.) , 3,5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5, manufactured by Sanwa Chemical Co., Ltd.) -Triazine), MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical, manufactured by Midori Chemical AZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3 , 4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'- Methyl diphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxa Ton ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone , Methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) Phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1, 2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4 -(Dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

  In the present embodiment, “light” includes not only light in a wavelength region such as ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and electromagnetic waves, but also radiation. Examples of the radiation include microwaves, electron beams, EUV, and X-rays. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light with a plurality of different wavelengths (composite light). The exposure can be multiple exposure, and the entire surface can be exposed after forming a pattern for the purpose of increasing the film strength and etching resistance.

  The photopolymerization initiator used in this embodiment needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization and exposure. When the gas is generated, the mold is contaminated, so that the mold has to be frequently washed, and the photocurable composition is deformed in the mold, resulting in deterioration of the transfer pattern accuracy.

  In the nanoimprint curable composition of the present embodiment, the polymerizable monomer (A) is a radical polymerizable monomer, and the photopolymerization initiator (B) is a radical polymerization initiator that generates radicals by light irradiation. A radical polymerizable composition is preferred.

(Other ingredients)
The nanoimprint curable composition of the present embodiment is various in addition to the above polymerizable monomer (polymerizable monomer contained in the nanoimprint curable composition of the present embodiment) and the photopolymerization initiator (B). Depending on the purpose, other components such as a surfactant, an antioxidant, a solvent, and a polymer component may be contained within a range not impairing the effects of the present invention. The nanoimprint curable composition of the present invention preferably contains at least one selected from a fluorine surfactant, a silicone surfactant, a fluorine / silicone surfactant, and an antioxidant.

  Next, a second example of the curable composition for nanoimprint will be described.

The curable composition for imprints of the second example of this embodiment is a curable composition for imprints containing one or more polymerizable monomers and a photopolymerization initiator, and the imprint The curable composition for use contains at least one polymerizable monomer (Ax) represented by the following general formula (I) as the polymerizable monomer, and the following (A) and (B): Satisfy at least one of the conditions.
(A) The polymerizable monomer (Ax) represented by the following general formula (I) is contained in an amount of 45% by mass or more based on the total polymerizable monomer.
(B) The total content of the polymerizable monomer that is solid at 25 ° C. and the polymerizable monomer having a viscosity at 25 ° C. of 70 mPa · s or more is included in the curable composition for imprints. It is less than 50% by mass of the polymerizable monomer.

  The composition of the present embodiment only needs to satisfy either of the above conditions (A) or (B). However, when both of the conditions (A) and (B) are satisfied, the high aspect pattern formability is further improved. Improved and preferable.

  In addition, the curable composition usually used for the photoimprint method includes a polymerizable monomer having a polymerizable functional group, and a photopolymerization initiator that initiates a polymerization reaction of the polymerizable monomer by light irradiation. And further includes a solvent, a surfactant, an antioxidant, or the like as necessary. Moreover, when (meth) acrylate is used as the polymerizable monomer, acrylate is preferred to methacrylate.

  Hereinafter, the composition of this embodiment is demonstrated in order.

(Polymerizable monomer)
-Polymerizable monomer (Ax)-
The polymerizable monomer (Ax) is represented by the following general formula (I).

[In the formula, Ar represents a divalent or trivalent aromatic group which may have a substituent, X represents a single bond or an organic linking group, and R ¹ has a hydrogen atom or a substituent. Represents an optionally substituted alkyl group, and n represents 2 or 3. ]
In the general formula (I), Ar represents a divalent aromatic group (that is, an arylene group) when n = 2, and a trivalent aromatic group when n = 3. Examples of the arylene group include hydrocarbon-based arylene groups such as a phenylene group and a naphthylene group; heteroarylene groups in which indole, carbazole and the like are linked groups, preferably a hydrocarbon-based arylene group, and more preferably a viscosity. From the viewpoint of etching resistance, it is a phenylene group. The arylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, a cyano group, an alkoxycarbonyl group, an amide group, and a sulfonamide group.

  Examples of the organic linking group for X include an alkylene group, an arylene group, and an aralkylene group, which may contain a hetero atom in the chain. Among these, an alkylene group and an oxyalkylene group are preferable, and an alkylene group is more preferable. X is particularly preferably a single bond or an alkylene group.

R ¹ is a hydrogen atom or an alkyl group which may have a substituent, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. When R ¹ has a substituent, preferred substituents are not particularly limited, and examples thereof include a hydroxyl group, a halogen atom, an alkoxy group, and an acyloxy group.

  The n is 2 or 3, preferably 2.

  The polymerizable monomer (Ax) is preferably a polymerizable monomer represented by the following general formula (Ia) or (Ib) from the viewpoint of reducing the composition viscosity.

[Wherein, X ¹ and X ² each independently represents a single bond or an alkylene group which may have a substituent of 1 to 3 carbon atoms, and R ¹ has a hydrogen atom or a substituent. Represents a good alkyl group. ]
In the general formula (Ia), X ¹ is preferably a single bond or a methylene group, and more preferably a methylene group from the viewpoint of viscosity reduction.

The preferable range of X ^{2 is the same as} the preferable range of X ¹ .

Wherein R ¹ is as in formula (I) with R ¹ synonymous, and preferred ranges are also the same.

  When the polymerizable monomer (Ax) is liquid at 25 ° C., it is preferable that the generation of foreign matters can be suppressed even when the addition amount is increased.

  The polymerizable monomer (Ax) preferably has a viscosity at 25 ° C. of less than 70 mPa · s from the viewpoint of pattern formability, more preferably 50 mPa · s or less, and 30 mPa · s or less. Particularly preferred.

Specific examples of preferred polymerizable monomers (Ax) are shown. R ¹ has the same meaning as R ¹ in formula (I) and represents a hydrogen atom or an alkyl group which may have a substituent. R ¹ is preferably a hydrogen atom from the viewpoint of curability. The present invention is not limited to these specific examples.

  Among these, the compounds shown below are particularly preferable because they are liquid at 25 ° C., have low viscosity, and exhibit better curability.

In the curable composition for imprints of this embodiment, at least one of the following conditions (A) and (B) is satisfied.
(A) The polymerizable monomer (Ax) represented by the following general formula (I) is contained in an amount of 45% by mass or more based on the total polymerizable monomer.
(B) The total content of the polymerizable monomer that is solid at 25 ° C. and the polymerizable monomer having a viscosity at 25 ° C. of 70 mPa · s or more is included in the curable composition for imprints. It is less than 50% by mass of the polymerizable monomer.

  The content of the polymerizable monomer (Ax) in the case where the curable composition for imprints of the present embodiment satisfies the condition (A) is a total polymerizable single amount from the viewpoint of improving the temporal stability. It is 45 mass% or more with respect to a body, Preferably it exceeds 50 mass%, More preferably, it is 55 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more. When the polymerizable monomer (Ax) is liquid at 25 ° C. and has a content satisfying the condition (A), in addition to the stability over time and the dry etching resistance, the pattern formability is also improved. Is particularly preferred.

  When the polymerizable monomer (Ax) is solid at 25 ° C. or has a viscosity at 25 ° C. of 70 mPa · s or more and a content satisfying the condition (A), the polymerizable monomer ( The content of Ax) is preferably 45 to 70% by mass, more preferably more than 50% by mass and 70% by mass or less based on the total polymerizable monomer from the viewpoint of improving storage stability. It is especially preferable that it is 55-65 mass%.

  When the curable composition for imprints of the present embodiment satisfies the condition (A), it is also preferable to satisfy the condition (B).

  The content of the polymerizable monomer (Ax) in the case where the curable composition for imprints of the present embodiment satisfies the condition (B), the polymerizable monomer that is solid at 25 ° C. and 25 ° C. There is no particular limitation as long as the total content with the polymerizable monomer having a viscosity at 70 mPa · s or less is less than 50% by mass of the total polymerizable monomer contained in the curable composition for imprints. . From the viewpoint of curability and composition viscosity, the content of the polymerizable monomer (Ax) is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 20 to 100% in all components excluding the solvent. Mass% is particularly preferred.

  Further, when the composition of the present embodiment satisfies the condition (B), when the polymerizable monomer (Ax) is a compound having two polymerizable functional groups, the polymerizable monomer (Ax ) In the total polymerizable monomer is preferably 1 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably more than 50% by mass and 100% by mass or less.

  When the composition of the present embodiment satisfies the condition (B), when the polymerizable monomer (Ax) is a compound having three polymerizable functional groups, the polymerizable monomer (Ax ) In the total polymerizable monomer is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and still more preferably 10 to 60% by mass.

  In the curable composition for imprints of this embodiment, from the viewpoint of improving the composition viscosity, dry etching resistance, imprint suitability, curability, and the like, a polymerizable monomer (Ax) and polymerization are performed as necessary. It is preferable to use in combination with another polymerizable monomer described in the first example, which is different from the polymerizable monomer (Ax).

  As described above, the curable composition for imprints of the present embodiment is further polymerized as a polymerizable monomer for the purpose of improving the composition viscosity, dry etching resistance, imprint suitability, curability, and the like. Another polymerizable monomer different from the polymerizable monomer (Ax) may be included.

  The content of the other polymerizable monomer is the total content of the polymerizable monomer that is solid at 25 ° C. and the polymerizable monomer that has a viscosity of 70 mPa · s or higher at 25 ° C. If it is less than 50 mass% of all the polymerizable monomers contained in the said curable composition for imprints, there will be no restriction | limiting in particular. The preferred content of the other polymerizable monomer varies depending on whether the content of the polymerizable monomer (Ax) in the present invention and the conditions (A) and (B) are satisfied. The polymerizable monomer may contain 0 to 90% by mass, preferably 5 to 80% by mass, and more preferably 20 to 80% by mass.

  Next, a third example of the curable composition for nanoimprints, particularly a polymerizable monomer will be described.

(A) Polymerizable monomer (A) The polymerizable monomer contains at least two fluorine-containing groups selected from a fluoroalkyl group and a fluoroalkyl ether group, and at least two of the fluorine-containing groups are These are compounds separated by a linking group having 2 or more carbon atoms.

  The fluoroalkyl group is preferably a fluoroalkyl group having 2 or more carbon atoms, more preferably a fluoroalkyl group having 4 or more carbon atoms, and the upper limit is not particularly defined, but 20 or less is preferable. 8 or less is more preferable, and 6 or less is more preferable. Most preferably, it is a C4-C6 fluoroalkyl group. In addition, at least two of the fluoroalkyl groups preferably contain a trifluoromethyl group structure. By having a plurality of trifluoromethyl group structures, the effects of the present invention are exhibited even with a small addition amount (for example, 10% by mass or less), so that compatibility with other components is improved, and line edge roughness after dry etching is improved. Will improve.

From the same viewpoint, (A) a compound containing three or more trifluoromethyl group structures in the polymerizable monomer is also preferable. More preferred are compounds containing 3 to 9, more preferably 4 to 6 trifluoromethyl group structures. Examples of the compound containing three or more trifluoromethyl group structures include a branched fluoroalkyl group having two or more trifluoromethyl groups in one fluorine-containing group, such as —CH (CF ₃ ) ₂ group, —C (CF ₃ ) ₃ and a compound having a fluoroalkyl group such as —CCH ₃ (CF ₃ ) ₂ CH ₃ group are preferred.

As the fluoroalkyl ether group, those having a trifluoromethyl group are preferred, and those containing a perfluoroethyleneoxy group or a perfluoropropyleneoxy group are preferred. A fluoroalkyl ether unit having a trifluoromethyl group such as — (CF (CF ₃ ) CF ₂ O) — and / or a trifluoromethyl ether group having a trifluoromethyl group at the terminal thereof are preferred.

  (A) As for the number of all the fluorine atoms which a polymerizable monomer has, 6-60 pieces are preferable, More preferably, it is 9-40 pieces, More preferably, it is 12-40 pieces.

  (A) The polymerizable monomer has a fluorine content defined below, preferably 30 to 60%, more preferably 35 to 55%, and still more preferably 35 to 50%. By making the fluorine content within an appropriate range, mold contamination can be reduced and the line edge roughness after dry etching is improved. The fluorine content is represented by the following formula.

  (A) At least two of the fluorine-containing groups of the polymerizable monomer are separated by a linking group having 2 or more carbon atoms. That is, when the polymerizable monomer (A) has two fluorine-containing groups, the two fluorine-containing groups are separated by a linking group having 2 or more carbon atoms. (A) When the polymerizable monomer has three or more fluorine-containing groups, at least two of them are separated by a linking group having 2 or more carbon atoms, and the remaining fluorine-containing group has any bonding form. You may have. The linking group having 2 or more carbon atoms is a linking group having at least two carbon atoms that are not substituted with fluorine atoms.

  Examples of the functional group contained in the linking group having 2 or more carbon atoms include an alkylene group, an ester group, a sulfide group, and an arylene group, and it is more preferable to have at least an ester group and / or a sulfide group.

  The linking group having 2 or more carbon atoms is preferably an alkylene group, an ester group, a sulfide group, an arylene group, or a combination thereof.

  These groups may have a substituent within a range not departing from the gist of the present invention.

  (A) As a preferable example of the polymerizable monomer, a compound having a partial structure represented by the following general formula (I) can be given. By adopting a compound having such a partial structure, the pattern forming property is excellent and the temporal stability of the composition is good.

  In general formula (I), n represents an integer of 1 to 8, preferably an integer of 4 to 6.

  (A) Another preferred example of the polymerizable monomer is a compound having a partial structure represented by the following general formula (II). Of course, you may have both the partial structure represented by general formula (I), and the partial structure represented by general formula (II).

In general formula (II), R ² and R ³ each represent an alkylene group having 1 to 8 carbon atoms, and each preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group may have a substituent without departing from the spirit of the present invention.

m1 and m2 each represents 0 or 1, and at least one of m1 and m2 is 1. m3 represents an integer of 1 to 3, and is preferably 1 or 2. n represents an integer of 1 to 8, and an integer of 4 to 6 is preferable. When m3 is 2 or more, _{respectively,} -C _{n F 2n + 1} may be different may be the same.

  (A) The polymerizable monomer is preferably a polymerizable monomer represented by the following general formula (III).

(In the general formula (III), R ¹ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group, A represents an (a1 + a2) -valent linking group, a1 represents an integer of 1 to 6. a2 represents 2. represents 6 integer, ^{R 2} and ^{R 3} is .m1 and m2 each represents an alkylene group having 1 to 8 carbon atoms, 0 or 1, at least one of m1 and m2 is 1 .M3 is Represents an integer of 1 to 3. m4 and m5 each represents 0 or 1, at least one of m4 and m5 is 1, and when both m1 and m2 are 1, m4 is 1. n is Represents an integer of 1 to 8.)
R ¹ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

  A is a (a1 + a2) -valent linking group, preferably a linking group having an alkylene group and / or an arylene group, and may further contain a linking group containing a hetero atom. Examples of the linking group having a hetero atom include —O—, —C (═O) O—, —S—, and —C (═O) —. These groups may have a substituent within a range not departing from the gist of the present invention, but preferably do not have a substituent. A preferably has 2 to 50 carbon atoms, and more preferably 4 to 15 carbon atoms.

R ² , R ³ , m 1, m ² , m 3 and n have the same meanings as in the general formula (II), and preferred ranges are also the same.

  a1 is an integer of 1 to 6, preferably 1 to 3, and more preferably 1 or 2.

  a2 is an integer of 2 to 6, preferably 2 or 3, and more preferably 2.

  When a1 is 2 or more, each A may be the same or different.

When a2 is 2 or more, R ² , R ³ , m1, m2, m3, m4, m5 and n may be the same or different.

  The molecular weight of the polymerizable monomer (A) used in the present embodiment is preferably 500 to 2000. Moreover, the viscosity of the polymerizable monomer (A) used in the present embodiment is preferably 600 to 1500, and more preferably 600 to 1200.

Specific examples of the polymerizable monomer (A) used in the curable composition of the present embodiment are listed below, but the present invention is not limited to these. R ¹ in the following formula is any one of a hydrogen atom, an alkyl group, a halogen atom and a cyano group.

  The content of the polymerizable monomer (A) in the curable composition of the present embodiment is not particularly limited, but is 0.1% in the total polymerizable monomer from the viewpoints of curability and composition viscosity. -100 mass% is preferable, 0.2-50 mass% is more preferable, 0.5-20 mass% is further more preferable, 1-10 mass% is especially preferable.

  In the curable composition of this embodiment, from the viewpoint of improving the composition viscosity, dry etching resistance, imprint suitability, curability, and the like, (A) a polymerizable monomer and (A) polymerization as necessary. It is preferable to use in combination with a polymerizable monomer other than the polymerizable monomer. Examples of other polymerizable monomers include polymerizable unsaturated monomers having 1 to 6 ethylenically unsaturated bond-containing groups; compounds having an oxirane ring (epoxy compounds); vinyl ether compounds; styrene derivatives; A compound having an atom; propenyl ether or butenyl ether can be exemplified, and from the viewpoint of curability, a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups is preferable. This is the same as described in one example.

  As the content of the other polymerizable monomer described above, the preferable content of the other polymerizable monomer varies depending on the content of the polymerizable monomer (A) in the present invention. The total polymerizable monomer may contain 0 to 99.9% by mass, preferably 50 to 99.8% by mass, and more preferably 80 to 99.5% by mass.

  Next, the preferable blend form of (A) polymerizable monomer and other polymerizable monomer in the present embodiment will be described.

  The monofunctional polymerizable monomer is usually used as a reactive diluent and has an effect of lowering the viscosity of the curable composition of the present invention, and is 15 mass based on the total amount of the polymerizable monomer. % Or more, preferably 20 to 90% by mass, more preferably 25 to 85% by mass, and particularly preferably 30 to 80% by mass.

  The monomer having two polymerizable reactive groups (bifunctional polymerizable monomer) is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass of the total polymerizable monomer. It is added in the following range.

  The ratio of the monofunctional and bifunctional polymerizable monomers is preferably in the range of 10 to 100% by mass, more preferably 30 to 100% by mass, and particularly preferably 50 to 90% by mass of the total polymerizable monomer. Added.

  The ratio of the polyfunctional polymerizable monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass of the total polymerizable monomer. % Is added in a range of not more than%. Since the viscosity of a composition can be lowered | hung by making the ratio of the polymerizable monomer which has 3 or more polymerizable reactive groups into 80 mass% or less, it is preferable.

  Hereinafter, the operation of the resist composition placement device (inkjet coating device) according to the present invention will be described with reference to flowcharts.

  5 and 6 are flowcharts showing the operation of the ink jet coating apparatus 10.

  First, a resist composition is supplied to the resist supply tank 50 in step S100 of FIG. At this time, the polymer content in the resist is previously measured and known.

  The polymer content can be measured by a known method such as gel permeation chromatography, ultraviolet-visible absorptiometry, liquid chromatography, fluorescence analysis or chemiluminescence. Further, in a simple manner, a part of the resist solution to be ejected before being ejected can be taken out and mixed with a solvent such as methanol, and evaluation can be made based on the turbidity at that time and the ease of filter permeation of the resist.

  The resist information including the polymer content is automatically read or input to the host computer 100 by an operator.

  In step S102, the resist information including the polymer content input to the host computer 100 is stored in the image memory 106 via the communication interface 102 and the system controller 104.

  Next, in step S104, temperature control of each part of the inkjet coating apparatus 10 is started. That is, the heating / cooling means 52 of the resist supply tank 50, the heating / cooling means 78 of the sub tank 66, and the heating / cooling means 84 of the inkjet head 20 are controlled to control the temperature of each part.

  At this time, since an impurity such as a polymer is generated in the resist composition when the temperature rises, the temperature is lowered in the resist supply tank 50 where the resist is stored, while the ink jet head 20 close to discharging the resist. Controls to raise the temperature. The temperature of the sub tank 66 is appropriately set according to the application amount. When the coating amount per hour is small, the resist stays in the sub tank for a long time, so it is preferable to lower the temperature compared to the head. On the other hand, when the coating amount per time is large, it is preferable to control the temperature to be the same as the head from the viewpoint of the stability of the resist temperature in the head.

  Next, in step S106, maintenance is performed. In particular, when initial filling is performed or drawing is performed after a pause, a preliminary discharge of a resist having an increased viscosity is performed. However, this maintenance operation is not necessary unless particularly required.

  Next, in step S108, negative pressure adjustment is performed. As shown in FIG. 3, the negative pressure of the resist in the nozzles of the inkjet head 20 is adjusted by controlling the pressure in the space above the film 67 in the sub tank 66 by the pump 76. In this way, by controlling the pressure in the sub tank 66, the meniscus pressure of the resist in the nozzle is adjusted.

  Next, in step S110, drive waveform adjustment (waveform adjustment) is performed. The waveform is set in the print control unit 108 using the polymer content stored in step S102. Here, the waveform is readjusted. Here, the waveform is adjusted so as to obtain an appropriate speed according to the polymer content.

  Here, a little away from the flowchart, the waveform of the drive signal when the resist is discharged will be described.

  In the present embodiment, the resist discharge method of the inkjet head 20 is a piezo method as described above. That is, although not shown, the diaphragm that forms a part of the inner wall of the pressure chamber communicating with the nozzle is deformed by deformation of the piezoelectric element (actuator) to increase or decrease the volume of the pressure chamber. When increasing, the resist is filled in the pressure chamber, and when the volume of the pressure chamber decreases, the resist in the pressure chamber is discharged from the nozzle. In addition, by forming a pressure chamber with a piezoelectric element and applying a voltage to the piezoelectric element, the piezoelectric element is deformed using the shearing effect to increase or decrease the volume of the pressure chamber. The pressure chamber may be filled, and when the volume of the pressure chamber decreases, the resist in the pressure chamber may be discharged from the nozzle, and any other piezo type may be used.

  FIG. 7 shows a drive waveform (voltage waveform) of a drive signal applied to the actuator.

  The waveform shown in FIG. 7 includes a first pulling drive waveform element 302 that deforms the actuator to increase the pressure chamber volume, and a first pressure chamber that retains the volume of the pressure chamber increased by the first pulling drive waveform element 302. A pull-hold waveform element 304, a push-drive waveform element 306 that drives the actuator to reduce the pressure chamber volume, a push-hold waveform element 308 that holds the pressure chamber volume reduced by the push-drive waveform element 306, The second pulling drive waveform element 310 is configured to drive the actuator so as to increase the volume of the pressure chamber again.

  This drive waveform is configured to include a waveform element that is first pulled (first pull drive waveform element 302), then pressed (push drive waveform element 306), and further pulled (second pull drive waveform element 310). Pull pull-pull (pull-push-pull) that combines the first pulling action (pull action) and the subsequent one pushing action (push action) followed by a second pulling action (pull action) ) The resist in the pressure chamber is discharged from the nozzle by driving.

  This will be described with reference to the state of the resist in the nozzle. FIG. 8 schematically shows the state of the resist in the nozzle corresponding to the pull-push-pull drive waveform.

  FIG. 8A shows a state corresponding to the first pulling drive waveform element 302. When the volume of the pressure chamber increases by driving the actuator, the resist 202 in the nozzle 200 is pulled back inward (pressure chamber side), and the liquid level (meniscus) 202a of the resist 202 in the nozzle 200 is recessed. This state is held by the first pull holding waveform element 304.

  Next, FIG. 8B shows a state corresponding to the push drive waveform element 306. By driving the actuator, the volume of the pressure chamber is reduced, and the resist 202 in the nozzle 200 is pushed out to form the liquid column 202b. This state continues substantially by the push-hold waveform element 308, and the liquid column 202b extends. At this time, if the dent amount of the resist 202 meniscus in FIG. 8A is large, the liquid column 202b becomes elongated.

  Next, FIG. 8C shows a state corresponding to the second pulling drive waveform element 310. When the actuator is driven, the volume of the pressure chamber decreases again, the resist 202 pushed out from the nozzle 200 is pulled back to the nozzle 200 side, and a part of the liquid column 202b is torn off to fly as a droplet 204. The remaining liquid column 202b is pulled back into the nozzle 200.

  At this time, in the waveform of FIG. 7, the interval T1 between the front end of the first pull drive waveform element 302 and the front end of the push drive waveform element 306 is greater than the rear end of the push drive waveform element 306 and the second pull drive. There is no effect of tearing off the liquid column 202b unless it is larger than the interval (width of the push-holding waveform element 308) T2 (that is, T2 <T1) from the tip of the waveform element 310.

  Moreover, when there are many polymers in a resist, a liquid column will extend long and it will become easy to generate mist. Therefore, the more the polymer is, the faster the liquid column is pulled in, and it is necessary to tear off the liquid column earlier. Therefore, it is preferable to decrease T2 as the polymer content increases.

  If the viscosity of the liquid (resist) to be ejected is high, the normal pull-push waveform has a high viscosity, so there is almost no negative pressure that is torn off due to the pressure attenuation effect. A tearing negative pressure is generated, and a liquid droplet having a short liquid column can be discharged even if the viscosity is high.

  FIG. 9 shows an example of a waveform. The waveform in FIG. 9A is an example of a drive waveform in which the first pulling portion (V1) is reduced. FIG. 9B shows an example of a driving waveform in which the first pulling portion is eliminated.

  If the initial pulling of the drive waveform is large, the width of the liquid column when the liquid is ejected with the waveform is thinned by the amount. This tendency becomes more conspicuous as the viscosity increases. When the viscosity is high, if the first pulling portion is ejected in a large waveform, the liquid column becomes considerably thin and mist is likely to be generated.

  For this reason, since it is better to make the thickness of the liquid column thicker in order to make it difficult to generate mist, the first pulling portion of the waveform is reduced as in the waveform example shown in FIG. Alternatively, it may be preferable to eliminate the first pulling portion as in the waveform example shown in FIG.

  Further, as described above, since the liquid column is elongated when the amount of polymer is large, it is preferable to set the waveform so as to reduce the initial pull-in.

  Examples of other waveforms are shown in FIGS.

  In any of these examples, the rear end of the push drive waveform element 306 and the second pull drive waveform element 310 are larger than the interval T1 between the tip of the first pull drive waveform element 302 and the tip of the push drive waveform element 306. The distance T2 from the tip of the coil is reduced (T2 <T1), and after the push-hold waveform element, the second pulling drive waveform element and the period for holding it are twice T1, and the voltage value is changed variously. It is a thing.

  FIG. 13 shows another waveform example. This is obtained by greatly changing the size (potential difference) V1 of the first pulling drive waveform element 302 and the size (potential difference) V2 of the push drive waveform element 306 from the example shown in FIG. .

  In the example shown in FIG. 7, V1 and V2 are substantially the same size, but in the example shown in FIG. 13, V2 is considerably larger than V1. The waveform shown in FIG. 7 is suitable for ejecting small droplets, whereas the waveform shown in FIG. 13 is intended to eject relatively large droplets.

  FIG. 14 shows the state of the resist in the nozzle corresponding to the waveform of FIG. FIG. 14A shows the state of the resist 202 in the nozzle 200 corresponding to the first pulling drive waveform element 302. As shown in FIG. 13, in this case, since the size V1 of the first pulling drive waveform element 302 is not so large, the pulling amount of the resist 202 in the nozzle 200 in FIG. The amount of depression of the liquid surface 202a of the resist 202 is not so large.

  FIG. 14B shows the state of the resist 202 in the nozzle 200 corresponding to the push drive waveform element 306. The resist 202 is extruded to form a liquid column 202b. As described with reference to FIGS. 7 and 8, when the dent amount is large, the liquid column 202b formed by the extruded resist 202 is elongated. In this example, since the dent amount is small, the liquid column 202b becomes thick and short. Therefore, the waveform of FIG. 13 is suitable for discharging a relatively large droplet. At this time, although depending on the viscosity of the resist and the size of the droplet to be ejected, as shown in FIG. 13, it is preferable that V1 is about half or less of V2.

  15 and 16 show examples of waveforms set in this way. The waveform shown in FIG. 15 has a small pull-in waveform element before extrusion, but the waveform shown in FIG. 16 does not have an initial pull-in portion.

  In the present embodiment, the discharge speed is changed according to the polymer content. Therefore, a table such as a target speed for each polymer content is created by actually conducting an experiment in advance.

  FIG. 17 shows the relationship between the discharge speed and the discharge volume. This is a relationship between the discharge speed and the discharge volume obtained using DMP-2831 manufactured by Fujifilm Daimatics.

  The ejection speed is calculated by observing the flight state with a camera, and the volume is obtained by measuring the weight of the resist ejected by a certain amount and converting it from the number of ejected droplets and the resist density.

  FIG. 18 shows a table showing correspondence between polymer content, discharge speed, and the like. The table of FIG. 18 shows the discharge speed with respect to the polymer content, the interval T2 between the rear end of the push drive waveform element 306 and the front end of the second pull drive waveform element 310 shown in FIG. 7, and FIG. 9 (a) or FIG. It shows the correspondence of the magnitude (voltage difference) V1 of the first pulling portion of the waveform shown, and shows the optimum correspondence obtained by experiment.

  In FIG. 18, the polymer content decreases from low to medium to high, whereas the discharge rate decreases as the polymer content increases so that v1> v2> v3. At this time, with respect to the interval T2 between the rear end of the push drive waveform element 306 and the front end of the second pull drive waveform element 310, the polymer content becomes small → medium → large, whereas a1 T2 is decreased as the polymer content is increased so that> a2> a3. Further, with respect to the size V1 of the first pulling portion of the waveform, V1 is made smaller as the polymer content is larger, such as b1> b2> b3.

  Further, the discharge volume is determined by the discharge speed, and the optimum landing interval is determined according to the discharge volume. FIG. 19 shows a correspondence table of discharge speed, discharge volume, and landing interval.

  In FIG. 19, with respect to the discharge speed, v1> v2> v3, the discharge volume is c1> c2> c3, and the landing interval is d1> d2> d3.

  As described above, with reference to the tables of FIGS. 18 and 19, the discharge speed is determined from the polymer content, the discharge volume is determined from the discharge speed, and the landing interval is determined from the discharge volume.

  As a result, in this embodiment, the higher the polymer content, the slower the discharge speed and the smaller the discharge volume, so the landing interval is made smaller.

  Returning to the flowchart of FIG. 5 again, the operation of the inkjet coating apparatus 10 will be described.

  In step S112, discharge is performed on the cap or the dummy work (dummy substrate), the discharge state is observed by the discharge state observation means 30, and discharge adjustment is performed according to the observation result.

  That is, the drive waveform is adjusted so that the discharge speed measured by the discharge state observing means 30 becomes the discharge speed and the landing interval corresponding to the polymer content obtained from the tables of FIG. 18 and FIG.

  In the next step S114, it is determined whether or not the discharge speed calculated by the discharge observation is OK. If OK (Yes), the process proceeds to the next step S116. If No, the process returns to step S106 to perform the maintenance operation.

  In step S116, the flight distance (TD) is adjusted according to the ejection speed calculated above. This is because the landing position deviation changes depending on the discharge speed. In other words, when the discharge speed is low, the flight time until landing becomes long, and the landing deviation is likely to be affected by flying bend due to disturbance or the like. Therefore, the flight distance is shortened to adjust the landing deviation to be small.

  The flying distance is adjusted by moving the inkjet head 20 up and down by the head holding and moving means 18 as described above.

  Next, substrate drawing conditions are set in step S118, droplet ejection is performed on the dummy workpiece in step S120, and the droplet ejection result on the dummy workpiece is observed by the workpiece alignment means 22 in step S122.

  In step S124, it is determined whether the shape and position of the droplet ejection result on the observed workpiece are OK.

  If the shape and position are No in step S124, maintenance is performed in step S126, adjustment is performed, and droplets are ejected onto the dummy workpiece again in step S120.

  On the other hand, if the shape and position are OK (Yes) in step S124, the process proceeds to the next step S128, the work (substrate) 26 is loaded, and alignment is performed in step S130.

  Next, the process proceeds to step S132 in FIG. 6, and drawing is performed on the work 26, and a resist is applied (arranged) at a predetermined position in accordance with preset data.

  Here, the drawing on the workpiece 26 is performed by relatively scanning the inkjet head 20 and the workpiece 26. The scanning method is not particularly limited, and various scanning patterns can be applied.

  For example, when the inkjet head 20 is a line head having a width of the workpiece 26, the inkjet head 20 may be fixed and the workpiece 26 may be scanned in a predetermined direction (uniaxial), or similarly, the inkjet head 20 may be fixed. Then, the workpiece 26 may be scanned in the XY directions.

  In the case where the inkjet head 20 is a line head having a width of the workpiece 26, the workpiece 26 is fixed and the inkjet head 20 is scanned in a predetermined direction (one axis) in contrast to the above. Alternatively, the inkjet head 20 may be scanned in the XY directions.

  In particular, when the inkjet head 20 does not have the width of the workpiece 26, the workpiece 26 may be fixed and the inkjet head 20 may be scanned in the XY directions. Furthermore, both the inkjet head 20 and the workpiece 26 may be scanned together.

  As described above, as a scanning method, the head may be scanned, the workpiece may be scanned, or both of them may be scanned. The inkjet head 20 may also be a line type head or a serial type head.

  When drawing is completed, the ink jet head 20 is moved to the standby position in the next step S134, the work 26 is unloaded in step S136, and is conveyed to the next NIL apparatus.

  In step S138, it is determined whether or not the processing of the workpiece 26 is the last. If the determination in step S138 is No, that is, if it is not the last time, it is determined in step S140 whether or not there is a change in the drawing conditions for the next workpiece 26. If there is no change, the process returns to step S120 in FIG.

  On the other hand, if the determination in step S138 is Yes, that is, if it is determined that the processing of the workpiece 26 is already the last, the inkjet head 20 is moved to the storage position in the next step S142, and in step S144, the inkjet head Then, the nozzle surface of 20 is capped, and then the temperature control is finished in step S146, and all operations of the inkjet coating apparatus 10 are finished.

  As described above in detail, according to the present embodiment, the length of the liquid column in ejection is shortened, and the generation of mist can be suppressed. In addition, it is possible to improve the variation in landing position, stabilize the transferred shape after imprinting, and further reduce the variation in residue thickness.

  Further, in the present embodiment, even if the discharge speed is reduced, by shortening the flight distance, it is possible to improve landing position variation and to stabilize the transferred shape after imprinting.

  As mentioned above, although the resist composition arrangement | positioning apparatus of this invention and the manufacturing method of the pattern formation body were demonstrated in detail, this invention is not limited to the above example, In the range which does not deviate from the summary of this invention, various improvement is carried out. It goes without saying that or may be modified.

  DESCRIPTION OF SYMBOLS 10 ... Inkjet coating apparatus (resist composition arrangement | positioning apparatus), 12 ... Support stand, 20 ... Inkjet head, 22 ... Work alignment means, 24 ... Work holding movement means, 26 ... Work (substrate), 28 ... Nozzle surface observation means, 30 (30a, 30b) ... discharge state observation means, 32 ... maintenance means, 40 ... NIL apparatus, 42, 44 ... substrate storage part, 46 ... substrate mounting part, 48a, 48b ... load / unload means, 50 ... resist supply Tank 52, Heating / cooling means 54, Temperature sensor 56, Pump 58, Filter 60, Deaerator 62 62 Liquid trap unit 64 Pump 66 Sub tank 67 67 Membrane 68 Pump 70 72, 74 ... valve, 78 ... heating / cooling means, 80 ... pressure sensor, 82 ... temperature sensor, 84 ... heating / cooling means, 86 ... temperature sensor, DESCRIPTION OF SYMBOLS 8 ... Cap, 90 ... Suction pump, 92 ... Collection tank, 100 ... Host computer, 102 ... Communication interface, 104 ... System controller, 106 ... Image memory, 108 ... Print control part, 110 ... Head driver, 112 ... Image buffer memory , 114 ... resist supply unit, 116 ... resist supply control unit, 118 ... maintenance control unit, 120 ... observation unit, 122 ... observation control unit, 124 ... load unload control unit, 126 ... alignment control unit, 128 ... motor unit, 130: Motor controller

Claims (7)

A resist layer formed by a resist composition disposed on a substrate is pressed against a mold having a pattern surface formed in a concavo-convex shape with the pattern surface facing the resist layer side, against the resist composition The resist composition used in the imprint method for forming a pattern corresponding to the pattern of the mold that peels off the interface between the pattern surface of the mold and the resist layer formed on the substrate is discretely formed on the substrate. A resist composition placement device to be placed in
Polymer content storage means for storing the polymer content of the resist composition;
Resist discharge means for discharging the resist composition from a nozzle;
Driving waveform adjusting means for changing a driving waveform for discharging the resist composition from the nozzle according to a polymer content;
I have a,
The drive waveform includes a first pull drive waveform element that drives to draw a meniscus surface of the resist composition in the nozzle;
After the first pulling drive waveform element, a push drive waveform element that drives to discharge the resist composition from the nozzle;
A second pull drive waveform for driving the meniscus surface again after the push drive waveform element to drive the liquid column formed by the resist composition discharged from the nozzle;
Comprising
The resist composition arranging device , wherein a distance T2 between a rear end of the push drive waveform element and a front end of the second pull drive waveform element is shortened as the polymer content increases . In the drive waveform for discharging the resist composition, the size of the first pull drive waveform element, the resist composition according to claim 1, wherein the higher the polymer content, characterized in that reduced Placement device. A resist layer formed by a resist composition disposed on a substrate is pressed against a resist layer, and a mold having a pattern surface formed in a concavo-convex shape is pressed against the resist layer side. The resist composition used in the imprint method for forming a pattern corresponding to the pattern of the mold that peels off the interface between the pattern surface of the mold and the resist layer formed on the substrate is discretely formed on the substrate. A resist composition placement device to be placed in
Polymer content storage means for storing the polymer content of the resist composition;
Resist discharge means for discharging the resist composition from a nozzle;
A discharge speed measuring means for measuring a discharge speed of the resist composition discharged from the nozzle;
Wherein said speed changing means changing the discharge speed, and have a landing interval changing means for changing the landing interval of the resist composition landed on the substrate depending on the polymer content depending on the polymer content,
Furthermore, it is provided with a flight distance adjusting means for adjusting a flight distance until the resist composition discharged from the nozzle lands on the substrate, and the flight distance is shortened as the polymer content increases. A resist composition placement device characterized by the above. 4. The resist composition arranging device according to claim 3 , wherein the speed changing means slows the discharge speed as the polymer content increases. The resist composition arranging device according to claim 3 or 4 , wherein the landing interval changing means narrows the landing interval as the polymer content increases. A resist layer formed by a resist composition disposed on a substrate is pressed against a mold having a pattern surface formed in a concavo-convex shape with the pattern surface facing the resist layer side, against the resist composition A pattern forming body used in an imprinting method for forming a pattern corresponding to a pattern of a mold that peels off an interface between a pattern surface of the mold and a resist layer formed on the substrate. ,
Storing the polymer content of the resist composition;
Discharging the resist composition from a nozzle;
Changing the driving waveform for discharging the resist composition from the nozzle according to the polymer content;
Only including,
The drive waveform includes a first pull drive waveform element that drives to draw a meniscus surface of the resist composition in the nozzle;
After the first pulling drive waveform element, a push drive waveform element that drives to discharge the resist composition from the nozzle;
A second pull drive waveform for driving the meniscus surface again after the push drive waveform element to drive the liquid column formed by the resist composition discharged from the nozzle;
Comprising
A method of manufacturing a pattern forming body, characterized in that a distance T2 between a rear end of the push drive waveform element and a front end of the second pull drive waveform element is shortened as the polymer content increases . A resist layer formed by a resist composition disposed on a substrate is pressed against a resist layer, and a mold having a pattern surface formed in a concavo-convex shape is pressed against the resist layer side. A pattern forming body used in an imprinting method for forming a pattern corresponding to a pattern of a mold that peels off an interface between a pattern surface of the mold and a resist layer formed on the substrate. ,
Storing the polymer content of the resist composition;
Discharging the resist composition from a nozzle;
Measuring the discharge speed of the resist composition discharged from the nozzle;
Changing the ejection speed according to the polymer content, and changing the landing interval of the resist composition landing on the substrate according to the polymer content;
Only including,
Furthermore, a flight distance adjustment step for adjusting a flight distance until the resist composition discharged from the nozzle lands on the substrate is provided, and the flight distance is shortened as the polymer content increases. A process for producing a pattern forming body characterized by the above.

Images