JP4147247B2 - Method for reducing pitch of fine concavo-convex lattice and fine concavo-convex lattice member obtained thereby - Google Patents

Description

  The present invention relates to a fine concavo-convex lattice pitch reduction method and a fine concavo-convex lattice member obtained thereby.

  With the recent development of photolithography technology, it has become possible to form patterns with a very narrow pitch. If a pattern having such a narrow pitch, particularly a light wavelength level pitch, can be formed, members and products having such a narrow pitch pattern can be used not only in the semiconductor field but also in the optical field. it can. In particular, in the optical field, members and products having a fine concavo-convex grating with a pitch of 100 nm or less are widely used, and demands for such members and products are increasing.

However, the present situation is that it is impossible to realize a fine concavo-convex grating with a pitch of 100 nm or less in a large area of the order of cm ² or more.

The present invention has been made in view of the above points, and the pitch of the fine concavo-convex lattice that can realize a fine concavo-convex lattice having a pitch of 100 nm level or less, which has not been realized so far, in a large area of the order of cm ² or more. An object is to provide a reduction method and a fine concavo-convex lattice member obtained thereby.

  The method for reducing the pitch of the fine concavo-convex grid of the present invention includes a step of heating a stretched member having a fine concavo-convex grid having a pitch of 0.01 to 100 μm on the surface to a temperature at which a material constituting the stretched member softens, A step of uniaxially stretching the stretched member in a direction substantially parallel to the longitudinal direction in a state where the width of the stretched member in a direction substantially orthogonal to the longitudinal direction of the concavo-convex lattice is free, and a temperature at which the material is cured And a step of cooling the stretched member.

According to this method, the length of the stretched member is increased by subjecting the stretched member having a fine concavo-convex lattice with a pitch of 0.01 to 100 μm to the surface, and the width direction is reduced accordingly. . As a result, it is possible to realize a fine concavo-convex lattice having a pitch of 100 nm or less, which could not be realized until now, in a large area of the order of cm ² or more.

According to the method for reducing the pitch of the fine concavo-convex grid of the present invention, the pitch before and after stretching of the fine concavo-convex grid is p ₀ and p ₁ , respectively, and the height of the fine concavo-convex grid before and after stretching is h ₀ and h ₁ , respectively. Then, it is preferable to perform uniaxial stretching so that the reduction ratio r (= (h ₁ / h ₀ ) / (p ₁ / p ₀ )) satisfies 0.3 <r <1.5.

  Further, according to the method for reducing the pitch of the fine concavo-convex lattice of the present invention, it is preferable that the stretched member is made of a thermoplastic resin. This thermoplastic resin is selected in consideration of the glass transition point during uniaxial stretching and the melting point during transfer. In this case, it is preferable to perform uniaxial stretching within a temperature range in which the storage elastic modulus of the thermoplastic resin is 10 MPa to 2000 MPa. Further, the thermoplastic resin is an amorphous resin, and uniaxial stretching is performed in a temperature range of Tg-10 ° C. to Tg + 20 ° C. with respect to the glass transition temperature Tg measured by the differential thermal analyzer of the amorphous resin. Is preferred. Moreover, according to the pitch reduction method of the fine concavo-convex grid of the present invention, it is preferable that the stretched member is uniaxially stretched in a state where a fluid exists on the surface of the fine concavo-convex grid.

  The method for reducing the pitch of a fine concavo-convex grid according to the present invention has a fine concavo-convex grid with a pitch of 0.01 μm to 100 μm on the surface, and applies fluid to the side of the stretched member made of thermoplastic resin where the fine concavo-convex grid exists. Heating the side of the stretched member where the fine concavo-convex grid is not present to a temperature at which the thermoplastic resin is softened, and uniaxially stretching the stretched portion in a direction substantially parallel to the longitudinal direction of the concavo-convex grid; And cooling the stretched portion to a temperature at which the thermoplastic resin is cured.

  The fine concavo-convex lattice member of the present invention is manufactured by the above method.

  The method for producing a metal member of the present invention includes a step of obtaining a stretched member having a fine concavo-convex grid by the above method, a step of conducting the side of the stretched member having the concavo-convex lattice, and a metal on a conductive surface. A step of forming a layer; and a step of removing the stretched member to obtain the metal member. The metal member of the present invention is manufactured by the above method. In addition, the transfer member of the present invention was obtained by the steps of obtaining a metal member having a fine concavo-convex lattice on the surface by the method and the step of transferring the fine concavo-convex lattice to a transferred member using the metal member. It is characterized by that.

According to the present invention, since the stretched member having a fine concavo-convex lattice with a pitch of 0.01 to 100 μm on the surface is subjected to uniaxial stretching, the length of the stretched member is increased, and the width direction is reduced accordingly. As a result, it is possible to realize a fine concavo-convex lattice having a pitch of 100 nm or less, which could not be realized until now, in a large area of the order of cm ² or more.

Currently, there is an interference exposure method as a technique for forming a narrow pitch pattern. This interference exposure method is a technique of patterning using interference fringes when two-beam interference exposure is performed at an angle θ formed with the normal direction of the resist surface using a laser light source having a wavelength of λ nm. The pitch p of the interference fringes is expressed by p = λ / 2sinθ. Therefore, in principle, a pitch less than half the wavelength cannot be created. Further, lasers that can be used for interference exposure are limited to TEM ₀₀ mode lasers. Examples of the ultraviolet laser capable of TEM ₀₀ mode laser oscillation include an argon laser, a fourth harmonic of a YAG laser, and the like. For example, even if interference fringes are formed at an angle of 90 ° using a laser with a wavelength of 266 nm, the pitch is 133 nm. Therefore, the interference fringes that can be produced by interference exposure are limited to those having a pitch of 133 nm. The present inventors paid attention to this point, and found that a stretched member having a pitch exceeding 100 nm was produced by interference exposure, and the pitch was made 100 nm by stretching this, and the present invention was reached.

That is, the essence of the present invention is that a stretched member having a fine concavo-convex grid with a pitch of 0.01 μm to 100 μm on the surface is uniaxially stretched in a direction substantially parallel to the longitudinal direction of the concavo-convex grid and has a pitch of 100 nm level or less. This is to realize a fine concavo-convex lattice with a large area of the order of cm ² or more.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
In the fine concavo-convex grid pitch reduction method of the present invention, a stretched member having a fine concavo-convex grid with a pitch of 0.01 μm to 100 μm on the surface is heated to a temperature at which the material constituting the stretched member softens, The stretched member is uniaxially stretched in a direction substantially parallel to the longitudinal direction with the width of the stretched member in a direction substantially orthogonal to the longitudinal direction of the lattice being set free, and the material is cured while maintaining the stretched state. The member to be stretched is cooled to a temperature at which it is performed.

  The pitch of the fine concavo-convex lattice of the stretched member is set in the range of 0.01 μm to 100 μm, but can be appropriately changed according to the required pitch of the fine concavo-convex lattice and the draw ratio. That is, this range can be changed without departing from the object and effect of the present invention.

  The stretched member refers to a member to which the uniaxial stretching process of the present invention is applied, and examples thereof include a plate-like body, a film-like body, and a sheet-like body. The thickness and size of the stretched member are not particularly limited as long as uniaxial stretching is possible. The stretched member is preferably made of a thermoplastic resin. Thereby, a uniaxial stretching process can be performed easily. As thermoplastic resins, polyvinyl chloride resin, acrylic resin, styrene resin, polyarylate resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polyetherimide resin, polyether sulfone resin, polysulfone resin, polyether Amorphous resins such as ketone resins, crystalline resins such as polyethylene resins, polypropylene resins, polyethylene terephthalate resins, polybutylene terephthalate resins, wholly aromatic polyester resins, polyacetal resins, polyamide resins, and polyether ether ketone resins Can be mentioned. Moreover, what mixed the said resin can also be used.

As a method of forming a fine concavo-convex lattice on a stretched member, a pattern is formed using an interference exposure method in which exposure is performed using interference fringes formed by irradiating laser light of a specific wavelength from two directions of angle θ. A method of transferring a pattern with a formed mold (stamper) can be used. As a transfer method, a hot press method or the like can be used. As a laser that can be used for interference exposure, a TEM ₀₀ mode laser can be used. Examples of the ultraviolet laser capable of laser oscillation in the TEM ₀₀ mode include an argon laser (wavelengths 364 nm, 351 nm, and 333 nm) and a fourth harmonic wave (wavelength 266 nm) of a YAG laser. The wavelength and incident angle of the laser beam used for interference exposure are appropriately set according to the pitch of the fine concavo-convex grating to be formed.

  In the uniaxial stretching process in the present invention, the width direction of the stretched member (direction perpendicular to the longitudinal direction of the fine concavo-convex lattice) is free with respect to the stretched member, and the stretching process is performed in one direction in the longitudinal direction of the stretched member. It is a method to do. As an apparatus for performing this uniaxial stretching process, an apparatus for performing a normal uniaxial stretching process can be used. In this uniaxial stretching treatment, the stretched member is heated to a temperature at which the material constituting the stretched member, for example, the thermoplastic resin is softened, and the stretched member is uniaxially stretched in a direction substantially parallel to the longitudinal direction of the fine concavo-convex lattice. The member to be stretched is cooled to a temperature at which the material is cured while maintaining the stretched state. By such a uniaxial stretching process, a fine concavo-convex lattice with a 100 nm pitch level can be realized. Further, the heating condition and the cooling condition are appropriately determined according to the material constituting the stretched member.

The stretching ratio in the uniaxial stretching treatment is such that the pitch before and after stretching of the fine concavo-convex lattice is p ₀ and p _1, and the height of the fine concavo-convex lattice before and after stretching is h ₀ and h ₁ , respectively (FIG. 1C). , (D)), and the reduction ratio r (= (h ₁ / h ₀ ) / (p ₁ / p ₀ )) is preferably set such that 0.3 <r <1.5. 8 <r <1.1 is particularly preferred. In order to obtain a reduction ratio r of 1.0 or more, it is preferable to use a member to be stretched that has a stretching strain in a direction perpendicular to the stretching direction. Thereby, uniaxial stretching can be performed while the shape of the fine concavo-convex lattice is kept good. When the volume of the stretched member is constant and the width direction and the thickness direction are uniformly reduced by stretching, the stretching ratio x = (L ₁ / L ₀ ) (L ₁ : length after stretching, L ₀ : Between the length before stretching) and the pitch (p ₀ , p ₁ ) and height (h ₀ , h ₁ ) before and after stretching, p ₁ = p ₀ / x ^1/2 (formula 1), h ₁ = h ₀ / x ^1/2 (Formula 2) The draw ratio is appropriately determined according to the target pitch.

Further, in the uniaxial stretching treatment, when the member to be stretched is made of a thermoplastic resin, it is preferable to perform uniaxial stretching at an almost limit temperature (a state as hard as possible) at which the cured thermoplastic resin can be stretched. That is, when the member to be stretched is stretched in a relatively high elastic modulus region (low temperature) as will be described later, results (theoretical values) close to the above formulas 1 and 2 are obtained, but are relatively low. When the member to be stretched is stretched in the elastic modulus region, p ₁ is close to the theoretical value, but h ₁ is lower than the theoretical value. Therefore, it is preferable to stretch the member to be stretched in a relatively high elastic modulus region (low temperature). In this case, in order to prevent whitening and breakage of the resin, it is preferable to perform stretching over a relatively slow time. For example, the strain rate is preferably 0.5% / second to 5% / second, and particularly preferably 0.5% / second to 2% / second. Thereby, uniaxial stretching can be performed while the shape of the fine concavo-convex lattice is kept good. It is preferable to perform the uniaxial stretching process within a temperature range in which the storage elastic modulus E of the thermoplastic resin is 10 MPa to 2000 MPa. When the dynamic viscoelasticity measurement is performed, values of storage elastic modulus and loss elastic modulus are obtained. The storage elastic modulus in this specification refers to the storage elastic modulus obtained in the dynamic viscoelasticity measurement.

  Further, when the stretched member is made of a thermoplastic resin, when the thermoplastic resin is an amorphous resin, the temperature is Tg-10 ° C. to Tg + 20 ° C. with respect to the glass transition temperature Tg of the amorphous resin. It is preferable to perform uniaxial stretching in a range, and it is particularly preferable to perform uniaxial stretching in a temperature range of Tg + 3 ° C. to Tg + 8 ° C. The glass transition temperature in the present invention is the onset temperature of the temperature-heat flow graph obtained when the temperature is raised at 20 ° C./min in the differential thermal scanning calorimeter (DSC) measurement for the thermoplastic resin. If there are multiple temperatures, the highest temperature is selected. In the amorphous resin, there is a temperature range R in which the elastic modulus changes rapidly as shown in FIG. This temperature range R varies depending on the selected amorphous resin, but exists in the range of Tg-10 ° C. to Tg + 20 ° C. obtained by the DSC measurement. Therefore, in consideration of resin whitening or breakage, when the uniaxial stretching is performed in the temperature range R of Tg-10 ° C. to Tg + 20 ° C., which is a range in which the elastic modulus rapidly decreases as the temperature rises, Uniaxial stretching can be performed while maintaining a good shape.

  Further, in the uniaxial stretching treatment, when the stretched member is made of a thermoplastic resin, the fluid is present on the surface of the fine concavo-convex lattice, that is, the fine concavo-convex lattice is wet with the fluid. The stretching member is preferably uniaxially stretched. The fluid is preferably a fluid that has high wettability with the material constituting the member to be stretched, does not dissolve the member to be stretched, does not swell greatly, and has low volatility at the stretching temperature. In the presence of such a fluid, since the fluid flows into the concave portions of the fine concavo-convex lattice and stretching is performed, the stretching is performed in a state where the fluid is prevented from contacting the convex portions. Thereby, uniaxial stretching can be performed while the shape of the fine concavo-convex lattice is kept good. As such a fluid, a viscous liquid such as silicone oil or silicone surfactant satisfying the above conditions can be used. In particular, a water-soluble silicone surfactant is preferable from the viewpoint of simplification of washing because it can be easily removed by washing with water.

  When the member to be stretched is uniaxially stretched in the presence of a fluid having affinity (wetting property) with the thermoplastic resin, the member to be stretched may be uniaxially stretched in the fluid. A fluid may be applied to the side where the concavo-convex grid exists, and uniaxial stretching may be performed in a temperature-controlled oven. Alternatively, a fluid may be applied to the stretched member, and the stretched member may be subjected to a uniaxial stretching process while heating only the stretched portion. In this case, for example, a fluid is applied to the side of the stretched member made of thermoplastic resin on the side where the fine concavo-convex grid exists, and the side of the stretched member where the fine concavo-convex grid does not exist is heated. The film is uniaxially stretched in a direction substantially parallel to the longitudinal direction. In these cases, the temperature of the fluid, the temperature of the oven, etc. are set to the heating temperature of the uniaxial stretching process.

  As for the shape of the stretched member that is uniaxially stretched, when the width W in the direction substantially perpendicular to the stretching direction is constant, the longer length L in the stretching direction is less likely to prevent reduction in the width W direction during stretching. preferable. The ratio W / L between the width W and the length L of the stretched member before stretching is preferably 1 or less, and particularly preferably 0.8 or less.

  Next, using the method for reducing the pitch of the fine concavo-convex grid of the present invention, a method for producing a fine concavo-convex grid member having a fine concavo-convex grid, a metal member, and a transfer member having the fine concavo-convex grid transferred using the metal member explain.

  1A to 1F are cross-sectional views for manufacturing a fine concavo-convex lattice member and a metal member having a fine concavo-convex lattice by using the pitch concavo-convex method of the fine concavo-convex lattice according to one embodiment of the present invention. .

  First, the metal mold | die (stamper) 1 which has the fine uneven | corrugated lattice 1a of 0.01-100 micrometers pitch on the surface shown to Fig.1 (a) is prepared. The stamper 1 applies a resist material on a glass substrate by spin coating to form a resist layer, exposes the resist layer using an interference exposure method, and develops the resist layer. Thereby, a resist layer having a fine concavo-convex lattice with a pitch of 0.01 to 100 μm is obtained. Next, nickel is sputtered onto the resist layer to make the resist layer conductive. Subsequently, nickel electroplating is performed on the sputtered nickel to form a nickel plate. Then, the stamper 1 which has the fine uneven | corrugated grating | lattice of a 0.01-100 micrometer pitch on the surface can be produced by peeling a nickel plate from a glass plate and removing a resist layer from a nickel plate.

  The stamper 1 can be used for the next hot press as it is, but the cross-sectional shape of the fine concavo-convex grid formed on the resist layer includes a portion that can be undercut at the time of mold release after pattern transfer such as a hot press. When it becomes difficult to release the mold, the shape is once transferred to a transfer member made of a thermoplastic resin or an ultraviolet curable resin, and the stamper 1 is manufactured by conducting a conductive process and electroplating using the transfer member. . In this way, when the transfer member is released, the transfer member in the undercut portion is appropriately deformed, and the undercut portion is eliminated or reduced, so that the release property can be improved. In addition, as a manufacturing method of the stamper 1, it is not limited to the said method, You may use another method.

  Next, as shown in FIG. 1 (a), the member 2 to be stretched is pressed against the fine concavo-convex grid 1a side of the stamper 1 by a process such as hot pressing, and as shown in FIG. The pattern of the fine concavo-convex lattice 1a is transferred to the surface. In addition, the to-be-stretched member 2 can be produced by injection molding, extrusion molding, etc., when a constituent material is a thermoplastic resin. Then, when the stamper 1 is removed, as shown in FIG. 1C, the stretched member 2 having the fine concavo-convex lattice 2a to which the fine concavo-convex lattice 1a of the stamper 1 is transferred is obtained.

  Next, as shown in FIG. 1D, the stretched member 2 is subjected to a uniaxial stretching process in which the width direction is free. That is, the stretched member 2 shown in FIG. 2A is uniaxially stretched in the arrow direction (direction substantially parallel to the longitudinal direction of the fine concavo-convex lattice 2a). At this time, the material constituting the stretched member 2 is heated to a temperature at which the material is softened, the stretched member 2 is uniaxially stretched in a direction substantially parallel to the longitudinal direction of the fine concavo-convex lattice 1a, and the material is kept in a stretched state. The stretched member 2 is cooled to a curing temperature. In addition, these heating temperature and cooling temperature are suitably set with the material which comprises the to-be-stretched member 2. FIG.

By this uniaxial stretching treatment, the stretched member 2 becomes longer in the arrow direction, and the width direction is reduced accordingly. As a result, as shown in FIG. 2 (b), a stretched member (stretched member) 2 ′ having a fine concavo-convex lattice 2a ′ at a pitch of 100 nm or less is obtained. In addition, about a draw ratio, it sets suitably based on the pitch of the fine uneven | corrugated lattice of the to-be-stretched member to prepare, and the pitch of the fine uneven | corrugated lattice of the extending | stretching member required. For example, the stretching ratio is 6 times and the pitch is reduced to about 1/2. For example, the pitch of the fine concavo-convex grid 1a (p ₀₎ is at 250 nm, by stretching 6 times, the pitch of the fine concavo-convex grid 2a '(p _{1) is, p 1 = p 0/6} 1/2 = 250 /2.449≈100. In this way, it is possible to manufacture a fine concavo-convex lattice member having a fine concavo-convex lattice having a pitch of 100 nm or less, which could not be realized until now. Such a fine concavo-convex lattice member can be applied to an alignment film used in a liquid crystal display device, a (structurally birefringent type) retardation plate, and the like.

  Next, the metal member 3 is obtained using the extending member 2 '. In this case, first, the side of the extending member 2 ′ having the fine concavo-convex grid 2 a ′ is made conductive. For example, a metal film is formed on the extending member 2 ′ by a vapor deposition method, a sputtering method, an electroless plating method, or the like, thereby making the side of the extending member 2 ′ having the fine uneven lattice 2 a ′ conductive. Thereafter, a metal layer is formed on the conductive surface. Examples of the method for forming the metal layer include an electroplating method. There is no restriction | limiting in particular in the thickness of a metal layer, According to the use of the metal member 3, it sets suitably. Thereby, as shown in FIG.1 (e), the metal member 3 is formed on the extending | stretching member 2 '.

  Next, by removing the extending member 2 ′ from the metal member 3, as shown in FIG. 1 (f), the metal member 3 having the fine concavo-convex lattice 3 a having a pitch of 100 nm or less can be obtained. In the case of removing the extending member 2 ′ from the metal member 3, the extending member 2 is removed using a method of peeling the metal member 3 from the extending member 2 ′ or a solvent in which the material constituting the extending member 2 ′ is soluble. For example, a method of dissolving 'to leave the metal member 3 can be used.

  Since the metal member 3 obtained in this way has a fine concavo-convex lattice 3a with a pitch of 100 nm or less, using this as a master mold, a fine concavo-convex lattice 3a with a pitch of 100 nm or less is used. It is possible to easily manufacture members and products having That is, a master mold composed of the metal member 3 is pressed against a member to be transferred, or an ultraviolet curable resin is applied to the master mold and then cured by irradiating with ultraviolet rays to release, or a thermosetting resin. After applying to the master mold, the fine concavo-convex lattice can be transferred by heat-curing and releasing. Thereby, it is possible to obtain a member or product having the fine concavo-convex lattice 3a having a pitch of 100 nm or less.

Next, examples performed for clarifying the effects of the present invention will be described.
(Example 1)
A nickel stamper having a fine concavo-convex grating with a pitch (p ₀ ) of 250 nm and a fine concavo-convex height (h ₀ ) of 200 nm on the surface was prepared. This fine concavo-convex lattice was a striped lattice shape of periodic sine waves. Using this nickel stamper, the surface shape was transferred to a polystyrene resin plate having a thickness of 500 μm by a hot press method. The glass transition temperature (Tg) of this polystyrene resin was 94 ° C. The storage elastic modulus E of the polystyrene resin at 100 ° C. was 1120 MPa.

Specifically, the hot press was performed as follows. First, the inside of the press system was evacuated, and the nickel stamper and the polystyrene resin plate were heated to 190 ° C. After the nickel stamper and the polystyrene resin plate reached 190 ° C., the fine uneven lattice of the nickel stamper was transferred to the polystyrene resin plate at a press pressure of 20 kg / cm ² and a press time of 4 minutes. Further, the nickel stamper and the polystyrene resin plate were cooled to 40 ° C. while the press pressure was maintained at 20 kg / cm ² , then the vacuum was released, and then the press pressure was released. At this time, the nickel stamper and the polystyrene resin plate were easily released when the press pressure was released. The thickness of the polystyrene resin plate after pressing was about 350 μm. Further, when the surface shape of the polystyrene resin plate was observed with a field emission scanning electron microscope, it was confirmed that the striped lattice shape of the periodic sine wave formed on the nickel stamper was faithfully transferred.

  Next, the polystyrene resin plate to which the striped lattice shape of the periodic sine wave was transferred was cut into a 30 mm × 25 mm rectangle with a cutter knife to obtain a stretching sample. At this time, it was cut out so that the longitudinal direction of 30 mm × 25 mm and the longitudinal direction of the striped lattice were substantially parallel to each other.

  Next, both ends 5 mm in the longitudinal direction of the stretching sample were fixed with a chuck of a stretching machine, and the stretching sample was immersed in a silicone oil bath whose temperature was adjusted to 100 ° C. for 3 minutes. Thereafter, the film was stretched for 4 minutes at a speed of 2.5 cm / min (initial strain rate of 125% / min). After 15 seconds, the sample for stretching was taken out from the silicone oil bath. As a result, the stretching sample is free in the width direction and stretched 6 times in the uniaxial direction. The stretching sample taken out from the silicone oil bath was immersed in silicone oil at room temperature while maintaining the stretched state, and quickly cooled to a temperature at which the polystyrene resin was cured. The stretched sample that had been stretched was constricted toward the center, and the portion with the smallest width was 10 mm. The area where the width was 10 mm was about 40% of the whole.

When the surface of the stretched sample that had been stretched was observed with a field emission scanning electron microscope, the pitch (p ₁ ) was 100 nm, and the height (h ₁ ) of the striped lattice shape of the periodic sine wave Was 74 nm, and the striped lattice shape of the periodic sine wave was maintained. The width / height reduction ratio r (= (h ₁ / h ₀ ) / (p ₁ / p ₀ )) is (74/200) / (100/250) = 0.925, and the period of the polystyrene resin surface It was found that the concavo-convex shape of the sine wave striped lattice was reduced to be similar to the shape before stretching. That is, a fine concavo-convex lattice with a pitch of 100 nm level could be realized.

(Example 2)
In the same manner as in Example 1, a striped lattice shape of a periodic sine wave was press-transferred using a nickel stamper, the pitch (p ₀ ) was 250 nm, and the height (h ₀ ) of the striped lattice was 200 nm. A polystyrene resin plate having a thickness of about 350 μm and a striped lattice shape of a certain periodic sine wave was produced. This polystyrene resin plate was cut into a 30 mm × 20 mm rectangle with a cutter knife and used as a sample for stretching. At this time, it was cut out so that the longitudinal direction of 30 mm × 20 mm and the longitudinal direction of the striped lattice were substantially parallel to each other.

  Silicone oil is applied to the surface of the stretching sample on which the periodic sine wave fringe-like lattice shape has been transferred, and then the both ends 5 mm in the longitudinal direction of the stretching sample are fixed to 100 ° C. with a chuck of a stretching machine. A temperature-controlled SUS304 cylindrical container was pressed against the non-transferred side surface of the periodic sine wavy grid for 3 minutes. Thereafter, the sample for stretching was stretched for 4 minutes at a speed of 2.5 cm / min (initial strain rate of 125% / min) while the cylindrical container of SUS304 was pressed, and then the surface of SUS304 was pressed against the sample. The state was held for 15 seconds, and then the SUS container was removed from the sample surface. As a result, the stretching sample is free in the width direction and stretched 6 times in the uniaxial direction. The sample for stretching, from which the SUS container was removed from the surface, was immersed in silicone oil at room temperature while maintaining the stretched state, and quickly cooled to a temperature at which the polystyrene resin was cured. The stretched sample that had been stretched was constricted toward the center, and the portion with the smallest width was 10 mm.

When the surface of the stretched sample that had been stretched was observed with a field emission scanning electron microscope, the pitch (p ₁ ) was 100 nm, and the height (h ₁ ) of the striped lattice shape of the periodic sine wave Was 75 nm, and the striped lattice shape of the periodic sine wave was maintained. The width / height reduction ratio r (= (h ₁ / h ₀ ) / (p ₁ / p ₀ )) is (75/200) / (100/250) = 0.940, and the period of the polystyrene resin surface It was found that the concavo-convex shape of the sine wave striped lattice was reduced to be similar to the shape before stretching. That is, a fine concavo-convex lattice with a pitch of 100 nm level could be realized.

(Example 3)
In the same manner as in Example 1, a striped lattice shape of periodic sine waves was press-transferred using a nickel stamper, the pitch (p ₀ ) was 230 nm, and the height of the striped lattice (h ₀ ) was 250 nm. A polystyrene resin plate having a thickness of about 400 μm and a striped lattice shape of a certain periodic sine wave was produced. This polystyrene resin plate was cut into a 200 mm × 320 mm rectangle with a cutter knife, and used as a sample for stretching. At this time, it was cut out so that the longitudinal direction of 200 mm × 320 mm and the longitudinal direction of the striped lattice were substantially parallel to each other.

  A silicone-based surfactant (GE Toshiba Silicone TSF4452) is thinly spray-applied to the surface of the stretching sample on which the periodic sine-wave fringe lattice shape is transferred, and then the entire surface is wetted uniformly. Both ends 10 mm in the longitudinal direction of the sample were fixed with a chuck of a stretching machine, and in this state, the stretching machine was placed in a hot air oven whose temperature was adjusted to 100 ± 1 ° C. Then, after standing for 10 minutes, when the sample for stretching was stretched 4 times at a speed of 3 mm / sec (initial strain rate 1% / sec), the stretching was terminated, and after stretching, the distance between chucks of the stretching machine was maintained. In 20 seconds, the stretching sample was taken out into an environment at room temperature and cooled. The stretched sample, which had been stretched, had a substantially uniform width at about 1/3 of the central portion, and the width was 100 mm.

When the surface of the stretched sample that had been stretched was observed with a field emission scanning electron microscope, the pitch (p ₁ ) was 115 nm, and the height (h ₁ ) of the striped lattice shape of the periodic sine wave Was 120 nm, and the striped lattice shape of the periodic sine wave was maintained. The width / height reduction ratio r (= (h ₁ / h ₀ ) / (p ₁ / p ₀ )) is (120/250) / (115/230) = 0.960, and the period of the polystyrene resin surface It was found that the concavo-convex shape of the sine wave striped lattice was reduced to be similar to the shape before stretching. That is, a fine concavo-convex lattice with a pitch of 100 nm level could be realized.

  The present invention is not limited to the embodiment described above, and can be implemented with various modifications. For example, the dimensions, materials, and the like in the above-described embodiment are illustrative, and can be changed as appropriate. In addition, various modifications can be made without departing from the scope of the present invention.

(A)-(f) is sectional drawing which manufactures the fine uneven | corrugated lattice member and metal member which have a fine uneven | corrugated lattice using the pitch reduction method of the fine uneven | corrugated lattice which concerns on one embodiment of this invention. (A), (b) is a figure for demonstrating the uniaxial stretching in the pitch reduction method of the fine uneven | corrugated grating | lattice which concerns on one embodiment of this invention. It is a characteristic view which shows the relationship between the elasticity modulus and temperature in a thermoplastic resin.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stamper 1a, 2a, 2a ', 3a Fine uneven | corrugated lattice 2 Stretched member 2' Stretched member 3 Mold

Claims (9)

  A step of heating a stretched member having a fine concavo-convex lattice with a pitch of 0.01 μm to 100 μm on the surface to a temperature at which a material constituting the stretched member softens, and the direction in a direction substantially orthogonal to the longitudinal direction of the concavo-convex lattice A step of uniaxially stretching the stretched member in a direction substantially parallel to the longitudinal direction with the width of the stretched member being free, and a step of cooling the stretched member to a temperature at which the material is cured. A method for reducing the pitch of a fine concavo-convex lattice, characterized by: When the pitch of the fine concavo-convex lattice before and after stretching is p ₀ and p ₁ and the height of the fine concavo-convex lattice before and after stretching is h ₀ and h ₁ , respectively, the reduction ratio r (= (h ₁ / h _0). 2. The method for reducing the pitch of a fine concavo-convex lattice according to claim 1, wherein uniaxial stretching is performed so that () / (p ₁ / p ₀ )) satisfies 0.3 <r <1.5.   3. The method for reducing the pitch of a fine concavo-convex lattice according to claim 1, wherein the stretched member is made of a thermoplastic resin.   The method for reducing the pitch of a fine concavo-convex lattice according to claim 3, wherein uniaxial stretching is performed within a temperature range in which the storage elastic modulus of the thermoplastic resin is 10 MPa to 2000 MPa.   The thermoplastic resin is an amorphous resin, and uniaxial stretching is performed in a temperature range of Tg-10 ° C. to Tg + 20 ° C. with respect to a glass transition temperature Tg measured by a differential thermal analyzer of the amorphous resin. The method for reducing the pitch of the fine concavo-convex grating according to claim 3 or 4.   6. The method for reducing the pitch of a fine concavo-convex grid according to claim 1, wherein the member to be stretched is uniaxially stretched in a state where a fluid is present on the surface of the fine concavo-convex grid.   A step of providing a fluid to a side of the stretched member having a fine concavo-convex grid having a pitch of 0.01 μm to 100 μm on the surface and made of a thermoplastic resin, and the fine concavo-convex grid of the stretched member The side where no thermoplastic resin exists is heated to a temperature at which the thermoplastic resin is softened, the stretched portion is uniaxially stretched in a direction substantially parallel to the longitudinal direction of the concavo-convex lattice, and the stretching is performed to a temperature at which the thermoplastic resin is cured. And a step of cooling the portion.   A fine concavo-convex lattice member having a fine concavo-convex lattice on the surface, which is manufactured by the method according to claim 1.   A step of obtaining a stretched member having a fine concavo-convex lattice by the method according to any one of claims 1 to 7, a step of conducting a side of the stretched member having the concavo-convex lattice, A method for producing a metal member having a fine concavo-convex lattice, comprising: forming a metal layer on the surface; and removing the stretched member to obtain the metal member.

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