JP5408649B2 - Method for producing endless pattern - Google Patents

Description

  The present invention relates to a method for producing an endless pattern capable of forming an endless mold, a method for manufacturing a resin pattern molded product using the endless mold, an endless mold obtained by these manufacturing methods, a resin pattern molded product, and an optical element.

  In the nanoimprint technology, a roller transfer method has been attracting attention as a technology development for further improving efficiency, cost reduction, and large area.

  As a conventional manufacturing method of a mold used in the roller transfer method, there are a method of winding a film having a fine pattern such as plating or resin around a cylindrical substrate, a method of machining, a method of laser processing, and the like.

  However, the winding method has a problem that seams occur. In the method by machining, since the machining tool is worn, the shape changes when machining for a long time, and only a groove-like pattern can be formed. In the laser processing method, the beam diameter cannot be reduced to the nano order, and it is difficult to produce an endless mold having a nano order pattern.

  On the other hand, as an electron beam irradiation method, a method of irradiating an electron beam while rotating a disk (for example, see Non-Patent Document 1) or a method of irradiating an electron beam on a curved surface (for example, see Non-Patent Document 2). Has been proposed.

M. KATSUMURA, M. SATO, K. HASHIMOTO, Y. HOSODA, O. KASONO, H. KITAHARA, M. KOBAYASHI, T. IIDA and K. KURIYAMA, Jpn. J. Appl. Phys., Vol. 44, No 5B, 2005, pp. 3578-3582. K. YAMAZAKI, T. YAMAGUCHI and H. NAMATSU, Jpn. J. Appl..Phys., Vol. 43, No. 8B, 2004, pp.L 1111-L 1113.

A first object of the present invention is to provide a method for producing an endless pattern applicable to an endless mold or the like by irradiation with an electron beam or an ion beam.
Moreover, the 2nd subject of this invention is providing the manufacturing method of the resin pattern molded product which uses the said endless mold as a type | mold of a nanoimprint.
Furthermore, the third object of the present invention is to provide an endless mold, a resin pattern molded product, and an optical element obtained by these production methods.

  As a result of intensive studies to solve these problems, the present inventors have solved the problems by the following invention.

<1> a step of rotating a substrate that is endless in the circumferential direction and hardened or solubilized by irradiation with an electron beam or an ion beam in a rotation direction;
Irradiating an electron beam or an ion beam with a predetermined angle of incidence angle is taken as 0 °, the substrate when irradiated toward the axis of rotation of the substrate,
Removing a part of the substrate by the irradiation or by development after the irradiation;
It is a manufacturing method of the endless pattern which has.

<2> a step of rotating a substrate endless in the circumferential direction and provided with a film that is cured or solubilized by irradiation with an electron beam or an ion beam in a rotation direction;
Irradiating an electron beam or an ion beam at a predetermined angle to the film when an incident angle when irradiating toward the rotation axis of the substrate is 0 ° ;
Removing a part of the film by the irradiation or by development after the irradiation;
It is a manufacturing method of the endless pattern which has.

<3> The method for producing an endless pattern according to <1> or <2>, wherein the electron beam or the ion beam is irradiated while rotating the substrate in a rotation direction.

<4> Drawing a pattern by adjusting at least one of a scanning direction and a scanning speed of the electron beam or ion beam, a moving direction and a moving speed of the substrate, and a rotating direction and a rotating speed of the substrate. The method for producing an endless pattern according to <3>, which is characterized in that
It is.

<5> The method for producing an endless pattern according to <1> or <2>, wherein the substrate is not rotated during irradiation with the electron beam or ion beam.

<6> The endless pattern according to any one of <1> to <5>, wherein an incident angle of the electron beam or ion beam to the substrate is 30 ° or more and 80 ° or less. This is a manufacturing method.

<7> The method for producing an endless pattern according to <6>, wherein an incident angle of the electron beam or ion beam with respect to the substrate is 40 ° or more and 80 ° or less.

<8> When the incident angle of the electron beam or ion beam with respect to the substrate is plus in the rotation direction of the substrate and minus in the reverse rotation direction, the incidence angle is −30 ° or more and less than 0 °, or from 0 ° The method for producing an endless pattern according to any one of the above items < 1> to <5 > , which is largely + 30 ° or less .

  ADVANTAGE OF THE INVENTION According to this invention, the endless pattern (endless mold) which can be used for roll nanoimprint etc. can be provided. Moreover, the manufacturing method of the resin pattern molded product which uses an endless mold as a type | mold of nanoimprint can be provided. Furthermore, an endless mold, a resin pattern molded product, and an optical element can be provided.

It is a figure explaining the irradiation method of the electron beam or ion beam in a continuous irradiation method. It is a figure explaining the incident angle of a beam, (a) is a figure when irradiating the beam B toward the center O of a cylindrical board | substrate, (b) is a radius from the center to the irradiation position of a beam. It is a figure when shifting and irradiating parallel to a direction (+/- Y). It is a figure when irradiating a beam with respect to a cylindrical substrate from diagonally. It is a figure explaining the drawing method of the L & S pattern in a continuous irradiation method, (a) is a bitmap pattern, (b) is a figure showing a mode that it irradiates while rotating, (c) is sectional drawing of the obtained pattern It is. It is a figure explaining the irradiation method for forming the pattern of a three-dimensional shape, (a) is a figure which shows an irradiation pattern, (b) is a figure which shows the three-dimensional shape obtained. It is a figure explaining the irradiation method when producing a helical pattern. (A)-(e) is a figure explaining a series of operation of the joint irradiation method. It is a figure explaining the production process of a resin pattern molded product. It is a SEM photograph of the pattern obtained in Example 1, (a) 10 rpm, (b) 100 rpm, (c) 500 rpm, (d) 1000 rpm, (e) Is an SEM photograph when irradiation is performed while rotating at a rotational speed of 2000 rpm and (f) at a rotational speed of 3000 rpm. It is a graph which shows the relationship between the processing line width of the pattern obtained in Example 1, and the rotation speed of a board | substrate. It is a figure explaining the irradiation pattern in Example 2. FIG. It is a graph which shows the relationship between the processing line width of the pattern obtained in Example 2, and a dose amount. It is a SEM photograph of the pattern obtained in Example 3 at the rotation speed 2rpm at the time of irradiation. It is a SEM photograph of the pattern obtained in Example 3 at the rotation speed of 1500 rpm at the time of irradiation. It is a graph which shows the relationship between the average line | wire width of the pattern obtained in Example 3, and an electron beam incident angle. It is a figure explaining the irradiation pattern in Example 4. FIG. In Example 4, it is a SEM photograph of the pattern obtained when it irradiated with 100-times multiplication factor and dose amount 250microC / cm < ² >. In Example 4, it is a SEM photograph of the pattern obtained when it irradiated with magnification 300 times and dose amount 250microC / cm < ² >. In Example 4, it is a SEM photograph of the pattern obtained when it irradiated with magnification 600 times and dose amount 250microC / cm < ² >. In Example 4, it is a SEM photograph of the pattern obtained when it irradiated with the magnification of 600 times and the dose amount of 100 μC / cm ² . In Example 4, it is a SEM photograph of the pattern obtained when it irradiated with the magnification of 600 times and the dose amount of 400 μC / cm ² . In Example 5, it is a SEM photograph of the pattern obtained when it irradiated on the conditions 1 of Table 6. FIG. In Example 5, it is the SEM photograph of the pattern obtained when it irradiated on the conditions 2 of Table 6. FIG. In Example 5, it is a SEM photograph of the pattern obtained when it irradiated on condition 3 of Table 6. FIG. It is a figure explaining the irradiation pattern in Example 6. FIG. 10 is a SEM photograph of the L & S pattern obtained in Example 6. 10 is a SEM photograph of the L & S pattern obtained in Example 7. It is a graph which shows the relationship between the processing line width of the pattern obtained in Example 7, and rotation speed. It is a graph which shows the relationship between the process line width of the pattern obtained in Example 7, and the rotation speed in the rotation speed vicinity of 50 rpm at the time of irradiation. The SEM photograph of the L & S pattern in each electron beam incident angle obtained by the dosage amount of 200 micro C / cm < ² > of Example 8 is shown. The SEM photograph of the L & S pattern in each electron beam incident angle obtained by the dosage amount of 200 micro C / cm < ² > of Example 8 is shown. It is a graph which shows the relationship between the process line | wire width of the pattern obtained by the dosage amount of 200 micro C / cm < ² > of Example 8, and an electron beam incident angle. 10 is a SEM photograph of an L & S pattern obtained at an electron beam incident angle obtained at a dose of 100 μC / cm ² in Example 8. FIG. 6 is an SEM photograph of an L & S pattern obtained at an electron beam incident angle obtained at a dose of 150 μC / cm ² in Example 8. FIG. 10 is a graph showing a relationship between an electron beam incident angle and a processing line width when a dose amount of Example 8 is 150 μC / cm ² . It is a graph showing the relationship between an electron beam incident angle and a processing line width in each dose amount of Example 9. It is a figure explaining the irradiation pattern in Example 10. FIG. It is a figure explaining the irradiation pattern in Example 10. FIG. 4 is an SEM photograph of an L & S pattern obtained in Example 10 with a dose amount of 200 μC / cm ² . In Example 11, it is a graph which shows the relationship between the process line width of the pattern obtained by each dose amount, and the electron beam incident angle in the design dimension of the line of 0.5 micrometer and the space of 1.0 micrometer. It is a SEM photograph of the pattern obtained by the design dimension of dose amount 200 micro C / cm < ² >, line 0.3 micrometer, and space 0.6 micrometer when changing the electron beam incident angle in Example 11. FIG. It is a graph which shows the relationship between the process line width of the pattern in each dose amount obtained by the design dimension of 0.3 micrometer of line in Example 11, and the space of 0.6 micrometer, and an electron beam incident angle. It is a graph which shows the relationship between the processing line width of the pattern obtained by each dose amount, and an electron beam incident angle when the sample is fixed without rotating in Reference Example 1 (0 rpm).

1. Production of endless pattern (endless mold) The first production method of an endless pattern of the present invention includes at least the following steps.
(1A) a step of rotating a substrate that is cured or solubilized by irradiation with an electron beam or an ion beam (hereinafter sometimes referred to as a “sensitive substrate”) in a rotation direction;
(2) a step of irradiating an electron beam or an ion beam;
(3) A step of removing a part of the substrate by the irradiation or by development after the irradiation.

In the second method for producing an endless pattern according to the present invention, the substrate is formed of a material that is not cured and solubilized by irradiation with an electron beam or an ion beam (hereinafter, sometimes referred to as “insensitive substrate”). And (1B) a film that is cured or solubilized by irradiation with an electron beam or ion beam on an insensitive substrate endless in the circumferential direction (hereinafter referred to as “sensitivity”). A step of rotating the substrate in a rotation direction.
That is, the second method for producing an endless pattern of the present invention includes at least the following steps.
(1B) The substrate, which is endless in the circumferential direction and provided with a film that is cured or solubilized by irradiation with an electron beam or an ion beam (hereinafter sometimes referred to as a “sensitive film”), is rotated in the rotational direction. Rotating,
(2) a step of irradiating an electron beam or an ion beam;
(3) A step of removing a part of the film by the irradiation or by development after the irradiation.

  Furthermore, in the first and second manufacturing methods, the substrate rotation step (1A) or (1B) and the irradiation step (3) may be performed as separate steps or simultaneously. In other words, the electron beam or ion beam may be irradiated while rotating the substrate in the rotation direction, or the substrate is not rotated when the electron beam or ion beam is irradiated, and the substrate is rotated when not irradiated. The peripheral surface may be irradiated.

  In the production of the endless mold of the present invention, at least one of a scanning direction and a scanning speed of the electron beam or ion beam, a moving direction and a moving speed of the substrate, and a rotating direction and a rotating speed of the substrate are adjusted. Thus, various patterns can be formed endlessly.

(1) Preparation of substrate In the present invention, the substrate may be either a columnar substrate having a core portion or a cylindrical substrate having no core portion as long as the substrate has an endless shape continuous in the circumferential direction. Good. Further, the cross-sectional shape may be any of a circle, an ellipse, a polygon, and the like, and can be appropriately selected according to the use of the formed pattern-formed product.
Hereinafter, for convenience, the substrate of the present invention may be referred to as a “cylindrical substrate”, and the following “cylindrical substrate” includes “columnar substrate”, “substrate having an elliptical cross section”, and “ It should be read as a substrate having various shapes as appropriate, such as “a substrate having a polygonal cross section”.

The material of the substrate may be any of metal, glass, ceramics, resin and the like.
Since the desired shape cannot be obtained if the surface roughness of the substrate is larger than the size of the shape that can be formed by irradiation with a beam or the like, the surface roughness is preferably sufficiently small. Specifically, the surface roughness (arithmetic average roughness) (Ra) of the substrate is preferably 10 μm or less, more preferably 1 μm or less, and further preferably 0.1 μm or less. Here, the average surface roughness (arithmetic average roughness) (Ra) is a portion of the measurement length L in the direction of the center line from the roughness curve measured with a stylus meter, and the center line of the extracted portion Is the X axis, the axis orthogonal thereto is the Y axis, and the roughness curve is represented by Y = f (X), the value given by the following equation is expressed in μm units (determining L and The average roughness is measured according to JIS B 0601).

In order to obtain such a smooth surface, the substrate is preferably made of a material that can be mirror-cut, ground, or polished.
In addition, from the viewpoint of ease of smooth processing, the cross-sectional shape of the endless substrate preferably has a high roundness. Further, even when the obtained endless mold is used for roll transfer, a substrate having a high roundness is suitable for contacting the transfer object without unevenness. Therefore, the substrate in the present invention is preferably cylindrical or columnar.

  As a substrate material satisfying the above conditions, relatively soft metals such as aluminum and brass can be cited. In addition, as the insensitive substrate, stainless steel, simple metals (copper, iron, etc.), carbon steel, alloys and the like can be applied.

  Further, if the substrate itself is a sensitive substrate that is cured or solubilized by irradiation with an electron beam or ion beam, a pattern can be formed by irradiation without providing a sensitive film described later. Examples of such sensitive substrates include resins (acrylic resin, epoxy resin, etc.), glass, etc. When used as a nanoimprint mold as it is, acrylic resin, epoxy resin, Glass is preferred.

(1B) Application of sensitive film on cylindrical substrate When the substrate is an insensitive substrate, a sensitive film is applied on the cylindrical substrate. As the sensitive film, a resist film, a metal deposit film, an oxide layer, a fluoride layer, or the like can be applied. The metal deposit film means a film deposited by vacuum vapor deposition or sputter vapor deposition.
It is desirable that the sensitive film has excellent sensitivity to the beam or has good workability. A resist is suitable as a material having high sensitivity. The resist may be either an organic resist or an inorganic resist, and may be either a positive resist or a negative resist.

Examples of the inorganic resist include SOG (Spin On Glass), SiO ₂ and TiO _2.
An oxide such as Al ₂ O ₃ or a fluoride such as LiF or AlF can be used. When an inorganic resist is used, particularly when SOG is used, it can be used as a mold for nanoimprinting without removing the resist. Thus, in the case of an inorganic resist, the resist peeling operation becomes unnecessary, and the manufacturing operation can be simplified.

  Conventionally known SOG can be applied, for example, silicate (Hydrogen Siloxane), Ladder Hydrogen Silsesquioxane, Hydrogen Silsesqioxane (HSQ). , Hydrogenated alkylsilsesquioxane (HOSP), methylsiloxane known as Accuglass 512B, Ladder Methyl Silsesquioxane, and the like.

  Examples of the organic resist include PMMA (polymethyl methacrylate), ZEP-520 (manufactured by Nippon Zeon Co., Ltd.), and calixarene.

  The application of the sensitive film on the cylindrical substrate can be performed by vacuum deposition, dip (immersion), spray, doctor blade or the like. When a drying step for evaporating the solvent in the resist material is necessary after the application of the sensitive film, it is preferable to add a heating step (first heating step described later: PB). Heating can be performed in a furnace, oven, or the like.

The sensitive film may be a single layer or a multilayer. In the case of multiple layers, the same kind of resist material may be applied in multiple layers, or different resist materials may be laminated.
The thickness of the sensitive film is preferably 10 nm to 100 μm, more preferably 50 nm to 10 μm, and still more preferably 100 nm to 1 μm.

(2) First heating step (PB)
The formed resist layer is preferably baked or semi-baked (PB: Pre Bake) as described above to remove a certain amount of solvent and stabilize the adhesion, sensitivity, and shape of the resist. The PB heating temperature and heating time are appropriately determined because the preferred range varies depending on the type of resist and solvent. In general, the pattern is formed by changing the heating temperature and the heating time, and the PB conditions for increasing the aspect ratio are determined.
Specifically, the heating temperature of PB is preferably 100 ° C. or higher and 500 ° C. or lower.

(3) Beam irradiation In the present invention, beams used for pattern drawing are an electron beam and an ion beam.
For the ion beam, ions of gallium, argon, helium, silicon, or the like can be used.
The electron beam and the ion beam may be any of a focused beam, a beam processed so that a shower-like beam can be locally irradiated with a limiting aperture, a multi-beam source, and the like.
In particular, the ion beam is preferably a focused ion beam (FIB) obtained by narrowing a beam obtained by accelerating ions with an electric field from the viewpoint of nano-order processing.

  In general, the beam irradiation is often performed in a vacuum. However, since there is an apparatus that can extract an electron beam in the atmosphere, the irradiation may be performed in the atmosphere.

In the present invention, (2A) even a method of irradiating the electron beam or ion beam while rotating the substrate in the rotation direction (hereinafter sometimes referred to as “continuous irradiation method”), or (2B) A method in which the substrate is not rotated when the electron beam or ion beam is irradiated, but the substrate is rotated after the beam irradiation on the specific surface is finished, and another surface is irradiated with a beam so that the pattern is continuous (hereinafter referred to as “joint irradiation method”). May be referred to). The continuous irradiation method (2A) is preferable in order not to cause a pattern seam.
Hereinafter, the irradiation method in the present invention will be described with reference to FIGS. Here, it is described that the cylindrical substrate 100 is irradiated. However, the cylindrical substrate 100 here includes a case of a sensitive substrate and a case where a sensitive film is provided on a non-sensitive substrate. .

FIG. 1 illustrates an electron beam or ion beam irradiation method in the continuous irradiation method (2A). FIG. 1 is a schematic view of a cylindrical substrate observed in perspective.
In the present invention, the X axis is defined as the axial direction of the cylindrical substrate 100, and the Y axis is defined as the radial direction of the cylindrical substrate 100. If the beam B is scanned and irradiated in the X-axis (one axis) direction while rotating the cylindrical substrate 100 in the R direction, drawing can be performed on the entire surface of the cylindrical substrate.

  However, the beam B may be scanned not only in the X-axis direction but also in the Y-axis direction. As shown in FIG. 2A, when the beam B is irradiated toward the center O of the cylindrical substrate 100, the incident angle of the beam B becomes 0 degree. As shown in FIG. 2B, when the irradiation position of the beam B is shifted in parallel with the radial direction (Y-axis direction) from the center O, the incident angle varies in the range of 0 ° to 90 °. The method shown in FIG. 2B can change the incident angle more easily than the method of irradiating the cylindrical substrate 100 with the beam B obliquely (FIG. 3).

  In the electron beam and ion beam, when the incident angle θ is increased, the beam diameter is projected as cos θ and irradiated to the irradiated object, so that secondary electron emission from the sensitive substrate and the sensitive film increases. Since it is presumed that the curing or solubilization of the sensitive substrate and the sensitive film will proceed due to the secondary electrons, the apparent sensitivity can be improved by increasing the incident angle θ of the beam as shown in FIG. 2 or FIG. Is considered possible. The effect of this beam incident angle θ is the same in the “joint irradiation method” described later.

  From the viewpoint of improving the apparent sensitivity, the incident angle θ of the beam is preferably 30 ° to 80 °, more preferably 40 ° to 80 °, and further preferably 45 ° to 70 °. preferable.

Further, as shown in FIG. 2B, when the incident angle of the electron beam or ion beam to the substrate is expressed as plus in the rotation direction of the substrate and minus in the reverse rotation direction, the incident angle of the beam is − It is preferable that the angle is 60 ° to + 40 °.
Further, from the viewpoint of improving the apparent sensitivity using the secondary electrons of the irradiated beam, it is preferable to irradiate at an irradiation angle on the + side. Further, from the viewpoint of improving the apparent sensitivity using backscattering, it is more preferable that the angle is −30 ° or more and less than 0 °, or greater than 0 ° and + 30 ° or less.

Here, backscattering and secondary electrons will be described.
When the acceleration voltage is low, the electrons incident on the resist spread immediately, but when the acceleration voltage is high, the electrons spread after entering deep into the solid. The spread of the electron beam in the incident direction is referred to as forward scattering, and the scattering that spreads laterally or returns to the incident direction as a result of repeated scattering is referred to as backscattering. Backscattering is caused by the reflection of incident electrons, or the incident electrons collide with molecules constituting the resist and ionize to generate secondary electrons, and the secondary electrons are scattered.

  In view of ease of operability, it is also preferable to irradiate the beam at an incident angle of 0 °. Therefore, from the viewpoint of improving the ease of operability and the apparent sensitivity, the beam incident angle θ is preferably 0 ° to 60 °.

  The rotational speed of the cylindrical substrate 100 in the continuous irradiation method is preferably 1 to 10000 rpm, and more preferably 100 to 5000 rpm, more preferably 500 to 2000 rpm in consideration of the influence of vibration of the jig due to rotation. Is more preferable from the viewpoint of microfabrication.

  Further, considering drawing of the entire circumference of the cylindrical substrate 100 after suppressing vibration of the jig due to rotation, it is preferable to set the speed to 50 to 80 rpm from the viewpoint of microfabrication.

  Next, FIG. 4 shows a method of drawing a line and space (L & S) pattern on the cylindrical substrate 100 in the continuous irradiation method. 4A is a bitmap pattern, FIG. 4B is a diagram showing a state of irradiation while rotating, and FIG. 4C is a cross-sectional view of the obtained pattern. As shown in FIG. 4, an L & S pattern is formed by irradiating the beam B while rotating the cylindrical substrate 100 with a bitmap pattern having an irradiated portion and an unirradiated portion in the X-axis direction.

Further, by changing the dose and acceleration voltage of the beam in the X-axis direction so that the bitmap pattern shown in FIG. 5A is obtained, the beam is irradiated, and the substrate is rotated, as shown in FIG. 5B. It is possible to control the depth and height of the pattern. In FIG. 5A, a black region on the X axis indicates a region irradiated with an increased dose or increased acceleration voltage, and a white region on the X axis decreases the dose or increases the acceleration voltage. Shows the area irradiated at low. The Z-axis in FIG. 5B represents the film thickness direction in the sensitive substrate or the sensitive film.
As shown in FIG. 5, three-dimensional processing is also possible with the continuous irradiation method.

  In the continuous irradiation method, a spiral pattern can be produced by synchronizing the rotational speed of the cylindrical substrate 100 and the beam scanning speed as shown in FIG. In this way, by drawing the beam on the cylindrical substrate 100, a geometric shape that cannot be produced on a plane can be produced.

Next, referring to FIG. 7, an electron beam or ion beam irradiation method in the joint irradiation method (2B) will be described. FIG. 7 is a schematic view of the cylindrical substrate 100 observed from the axial direction (X-axis direction).
First, as shown in FIG. 7A, a specific surface is irradiated with a beam without rotating the substrate during irradiation with an electron beam or an ion beam. The specific surface refers to a region on the circumferential surface of the substrate that can be irradiated by beam scanning without rotating the substrate. Next, the irradiation is stopped, and the substrate is rotated so that the unirradiated substrate surface is arranged at the irradiation position (FIG. 7B). Beam irradiation is performed in this state (FIG. 7C). Thereafter, as shown in FIGS. 7D and 7E, the beam irradiation and the rotation of the substrate are repeated to irradiate the entire circumferential surface of the substrate.
In the joint irradiation method, it is desirable that the joint portion of the pattern is overlapped so that the pattern drawn by the irradiation of the specific surface and the pattern drawn by the next irradiation are connected.

(4) Second heating step (PEB)
The resist layer that has undergone the irradiation step may be baked or semi-baked (PEB: Post Exposure Bake). In particular, when an inorganic resist containing a contrast enhancing agent such as a photobase generator, a thermal base generator, a photoacid generator, or a thermal acid generator is used, the contrast of the pattern is enhanced by heat. It is preferable to apply.

  The heating temperature in the second heating step (PEB) is preferably 50 ° C. or higher and 500 ° C. or lower, and more preferably 70 ° C. or higher and 200 ° C. or lower.

(5) Development Part of the irradiated sensitive substrate or sensitive film is removed by the beam irradiation or by the developer. In the negative type sensitive substrate and the sensitive film, the beam irradiated portion remains and the unirradiated portion is removed. In the positive-type sensitive substrate or film, the beam irradiated portion is removed, and the unirradiated portion remains.

Development methods include dipping, spraying, and thermal desorption. Various developers can be used depending on the type of resist. For example, when SOG is used as the resist, a hydrofluoric acid buffer (BHF) or the like can be used as the developer. Examples of the hydrofluoric acid buffer include a mixed solution of hydrofluoric acid and ammonium fluoride. The development time with the hydrofluoric acid buffer is preferably 30 to 300 seconds, more preferably 60 to 120 seconds. When TMMR (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is used as a resist, γ-butyrolactone or the like can be used as a developer. When PMMA is used as a resist, isopropyl alcohol or methyl isobutyl ketone is used as a developer. Further, a mixed solution of these can be used.
Steps such as rinsing and drying can be appropriately performed after the development.

If the sensitive film itself has sufficient hardness, the pattern can be used as it is as a nanoimprint mold. Details of such an endless mold will be described later.
For example, when an inorganic resist is used, since the strength of the inorganic resist is sufficient, a mold that has been subjected to a release treatment with a silane coupling agent such as PTFE (polytetrafluoroethylene) can be used as a mold. . It is also preferable to use diamond-like carbon (DLC) or the like as a resist because it has properties such as releasability and low friction.

  Further, a release agent can be coated on the surface of the sensitive film having the unevenness, or a protective layer for reinforcing the strength can be formed to make an endless mold. Examples of the strength reinforcing protective layer include hard films such as titanium and titanium compounds.

(6) Etching After development, the cylindrical substrate may be etched using the resist as a mask to form an endless mold. Etching methods include wet etching by an immersion method and dry etching such as plasma. Since the shape is endless, dry etching can also be performed while rotating. In some cases, the sensitive film is removed after the etching, and thereafter, a process such as rinsing, drying, mold release treatment, and reinforcing coating is performed.

2. Endless Mold The endless mold produced by the above method can be applied as it is as an element. For example, if a metal film is formed in a spiral pattern by the above method, it can be applied as a coil. An endless mold having an L & S pattern can be used as a diffraction grating, and a three-dimensional endless mold as shown in FIG. 5 can be applied to a curved lens (f-θ lens, lenticular lens) or the like. In addition, endless molds can be applied to Fresnel zone plates, binary optical elements, hologram optical elements, antireflection films, media such as CDs and DVDs, and the like.

The endless mold of the present invention can have a processed part having a line width of 100 nm or less. Such an endless mold can be obtained by the above production method. Naturally, a processed portion wider than a line width of 100 nm can be formed by the above manufacturing method.
The line width can be finely formed to be 100 nm or less, further 80 nm or less, and about 10 nm depending on the adjustment, depending on the type of resist, irradiation conditions, development conditions, and the like.

  The endless mold of the present invention can be used as a mold for molding a resin pattern molded product described later, and can be transferred to a resin or a film.

3. Method for Producing Resin Pattern Molded Product The method for producing a resin pattern molded product of the present invention uses an endless mold obtained by the method for producing an endless pattern as a mold for molding. When pressing the resin on the microfabricated product, set the temperature higher than the glass transition temperature of the resin to soften the resin, press the mold against the resin, cure the resin, and then peel the mold and resin To do.

The production process of the resin pattern molded product is shown in FIG.
The resin 30 is sandwiched between the glass 40 and the endless mold having the resist layer 20 with the unevenness formed on the substrate 10 by the above method (FIG. 8A), and the pressure is kept constant (FIG. 8). 8 (2)), the resin 30 is cured (FIG. 8 (3)). Thereafter, when the mold is pulled apart, a resin pattern molded product of the resin 30 is formed on the glass 40 (FIG. 8 (4)).

  In the method for producing a resin pattern molded product of the present invention, it is desirable that the mold and the resin are peeled off satisfactorily. When the mold is formed of an organic material such as a resin, it is difficult to remove the mold. Therefore, it is preferable to use an endless mold formed using an inorganic resist such as SOG, or an endless mold having a release agent on the surface. Examples of the release agent include silane coupling agents, and it is also preferable to provide a metal sensitive film so that the release agent can be easily removed. However, since the release agent also peels off when imprinted repeatedly, it is preferable that the release agent can be carried out without peeling treatment if possible.

  The endless mold of the present invention can be suitably used for roller nanoimprint. Pattern transfer by roller nanoimprint is a method in which the endless pattern of the present invention is used as a mold, a load is applied to the endless pattern of the present invention while the resin is heated, and the pattern is transferred to the resin. Since the endless pattern of the present invention is formed on a cylindrical substrate or the like, the pattern can be transferred onto the resin continuously and without interruption by repeated rotation of the substrate.

  This method is effective for pattern transfer onto a resin film having a length of several meters or more. In this roller transfer system, the contact between the mold and the resin is not a surface contact as in the case of batch transfer or the step and repeat system, but is a line contact. There is an advantage that it becomes easy to do. Further, since the load is applied to the molded substrate by line contact, the indentation stress (pressure) of the contact portion can be increased even with a small load, and the output of the press mechanism can be decreased. That is, the roller transfer method is a method capable of performing large-area nanoimprinting with a relatively simple apparatus configuration.

The resin for producing the resin pattern molded product may be any one of a thermoplastic resin and a photo-curing resin.
Examples of the thermoplastic resin include acrylic resins such as PMMA, polycarbonate, polyimide and the like, and acrylic resins such as PMMA are preferable.
As the photo-curing resin, a resin that is cured by ultraviolet rays or the like is preferable, and examples thereof include acrylic resins, epoxy resins, urethane resins, and mixtures thereof.

  In addition, when using photocurable resin, a base | substrate or a mold must permeate | transmit light, such as an ultraviolet-ray. On the other hand, when a thermoplastic resin is used, a heating step is required, and the mold is also easily deteriorated by heat. Therefore, it is preferable to apply a heat resistant resin.

4). Resin pattern molded article The resin pattern molded article of the present invention obtained by the above method can have a processed part having a line width of 100 nm or less. It is also possible to have a processed part with a line width of 10 nm or less. Naturally, a processed portion wider than a line width of 100 nm can be formed by the above manufacturing method.
The obtained fine pattern molded product or three-dimensional mold can be used for an optical element because of its shape and material. Examples thereof include a Fresnel zone plate, a diffraction grating, a binary optical element, a hologram optical element, an antireflection film, and a medium such as a CD or a DVD.

  Moreover, the film transferred by the endless mold or the plating foil peeled off after plating or the like on the film can be wound around a larger roll to form a roll mold. This is effective when a seamless uniform pattern is produced. When transferring to a flat surface by nanoimprinting, the problem of seam is reduced, but there are problems such as difficulty in batch transfer to a large surface, so the roll nanoimprinting method is useful when creating large-area molded products. It is beneficial.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.

  In Examples 1 to 5, TMMR-S2000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a resist, and in Examples 6 to 11 and Reference Example 1, PMMA (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used.

[Example 1]
-Production of endless mold by continuous irradiation method-
--Drawing characteristics depending on the number of rotations--
<Preparation of irradiation device>
A scanning electron microscope (SEM, Elionix ESA-2000) was used for electron beam irradiation. The electron microscope was modified to include a jig for attaching the cylindrical substrate and a rotating device having a mechanism for rotating the cylindrical substrate in the rotation direction.

<Deposition of resist film>
As the substrate, cylindrical brass with a mirror finish was used. The diameter of the cylindrical substrate was 3 cm and the length was 3 cm. This substrate was ultrasonically cleaned with acetone and ethanol.

A resist was applied on the substrate. TMMR S2000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a resist, and PM thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a thinning solution to prepare a TMMR diluent having a volume concentration of TMMA of 50%.
The TMMR diluted solution was applied by dipping (dipping method). In the TMMR diluent, a resist was applied to the cylindrical substrate surface at an intrusion speed of 3.0 mm / second, an immersion time of 5.0 seconds, and a coating pull-up speed of 0.1 mm / second (one layer application).

  Then, in order to dry a resist, it baked at 200 degreeC for 30 minutes. When the film thickness of the formed TMMR resist was measured by an optical interference method, it was 2.5 to 3.0 μm over the entire surface. Since the TMMR resist is a negative resist, an electron beam irradiated portion remains and forms a pattern.

<Electron beam irradiation>
A cylindrical substrate provided with a resist was mounted in an SEM, and an electron beam was irradiated while rotating the substrate. The conditions for rotation and irradiation are as follows.
・ Acceleration voltage: 30 kV
-Beam current: 4.0 nA
・ Beam diameter: 150nm (measured by knife edge method)
-Dose amount: 424.4 μC / cm ²
・ Rotation speed: 10, 100, 500, 1000, 2000, 3000 rpm
Pattern: Line & Space (L & S) Pattern: Pattern design value: 0.1 μm line (electron beam irradiated part) and 19.9 μm space (electron beam non-irradiated part)
・ Electron beam scanning method: raster scan

<PEB, development>
After the electron beam irradiation, firing (PEB) was performed at 90 ° C. for 2 minutes using a high temperature furnace.
It developed with the developing solution after PEB. The developer used was SV-gamma-butyrolactone (room temperature: about 23 ° C.) and was immersed for 2 minutes. Then, it dried with nitrogen gas.

<Result>
SEM photographs of the obtained L & S pattern are shown in FIGS. FIG. 9A shows a rotation speed of 10 rpm, (b) a rotation speed of 100 rpm, (c) a rotation speed of 500 rpm, (d) a rotation speed of 1000 rpm, (e) a rotation speed of 2000 rpm, and (f) a rotation speed of 3000 rpm. It is the SEM photograph of the pattern obtained by irradiating while rotating by.

As shown in the SEM photograph of FIG. 9, the L & S pattern was formed over the entire circumference at any rotational speed. Further, the pattern width after development was larger than the designed line width. This is probably because the beam diameter is as large as 150 nm due to the characteristics of the TMMR resist. Further, since the film thickness is as thick as 3 μm, it is presumed that the proximity effect has a great influence and the line width is widened.
Therefore, it is considered that fine processing of 100 nm or less is possible by irradiating with a nano-order electron beam and reducing the resist film thickness to about 100 nm.

  FIG. 10 shows the line width of the pattern of FIG. The line width in FIG. 10 is an average value when a total of 25 points are measured at five locations with different measurement positions for one line.

  As can be seen from FIG. 10, the change in the line width due to the rotational speed is small, and it can be confirmed that a fine L & S can be produced at the rotational speed of 500 to 2000 rpm. In addition, the fluctuation | variation of the processing line width in the rotation speed of 500 rpm or less is estimated to be the fluctuation | variation by the natural frequency of a jig.

[Example 2]
-Production of endless mold by continuous irradiation method-
--Drawing characteristics depending on dose amount--
TMMR resist was applied under the following conditions.
<Deposition of resist film>
Substrate: cylindrical sample (aluminum, diameter 10 mm)
Resist: TMMR diluent (volume concentration 50%)
TMMR: S2000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
Thin liquid for TMMR: PM thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
<Application conditions>
Coating penetration speed 3.0mm / sec
Immersion time: 5.0 sec
Application lifting speed 0.5mm / sec
Under the above conditions, TMMR resist was applied.

<PB>
After coating, firing (PB) was performed at 200 ° C. for 30 minutes using a high-temperature furnace.

<Electron beam irradiation>
The columnar substrate after PB was mounted in the SEM, and the electron beam was irradiated while rotating the substrate. The conditions for rotation and irradiation are as follows.

Experimental apparatus: Scanning electron microscope (SEM: ESA-2000)
Roller coating and engraving equipment (Mitsui Electric Seiki Co., Ltd.)
Beam current: 0.85nA
Acceleration voltage: 30 kV
Beam diameter: 222nm
Number of rotations during irradiation: 1500 rpm
Average resist film thickness: 2.41 μm
Dose amount: 50, 100, 150, 200 μC / cm ²
Drawing pattern: L & S pattern shown in FIG.
The SEM was produced at a magnification of 300 times (a square having a drawing range of 300 μm on one side).

<PEB, development>
After the electron beam irradiation, firing (PEB) was performed at 90 ° C. for 2 minutes using a high temperature furnace.
It developed with the developing solution after PEB. The developer used was SV-gamma-butyrolactone (room temperature: about 23 ° C.) and was immersed for 2 minutes. Then, it dried with nitrogen gas.

<Result>
FIG. 12 shows the relationship between the dose and the processing line width measured from the SEM photograph of the obtained L & S pattern.
As shown in the graph of FIG. 12, it has been found that the processing line width increases as the dose increases.

[Example 3]
-Production of endless molds by continuous irradiation method and fixed irradiation method-
--- Drawing characteristics due to difference in rotation speed and electron beam incident angle--
In the same manner as in Example 2, a resist film was formed and PB was performed to prepare a columnar sample provided with a resist film.

A cylindrical sample was mounted in the SEM, and electron beam rotation irradiation was performed under the following conditions.
At this time, the incident angle of the electron beam is changed to −60 °, −50 °, −40 °, −30 ° −20 °, −10 °, 0 °, + 10 °, + 20 °, + 30 °. The line width of the L & S pattern was measured.
In addition, in order to compare the line width according to the difference in the rotation direction of the sample, the electron beam incident angle is changed, and the L & S pattern line width at the rotation speed of 2 rpm and 1500 rpm is measured. The line width broadening with the change of electron beam incident angle was compared. Further, the comparison of the line width broadening in the change of the electron beam incident angle when the sample was irradiated without rotating at the time of irradiation (in the case of fixed irradiation) was compared.

<Irradiation conditions>
Experimental apparatus: As in Example 2, beam current: 0.85 nA
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Number of rotations during irradiation: 0, 2, 1500 rpm
Average resist film thickness: 2.02 μm
Dose amount: 100 μC / cm ²
Drawing pattern: same as Example 2

The method for obtaining the electron beam incident angle will be described below.
In FIG. 2B, the angle (θ) was changed by changing the irradiation position (± Y) of the electron beam. The relationship between the electron beam incident angle and the moving distance is obtained by the following equation, and the relationship is shown in Table 1 below.
Formula Y [mm] = 5.0 × sin θ

  With respect to the movement distance Y, the center line of the circle is set to 0 ° as a reference, and the case of shifting in the same direction as the rotation direction of the sample is plus, and the case of shifting in the direction opposite to the rotation direction is minus.

<Result>
An electron micrograph of the L & S pattern at the rotation speed of 2 rpm during irradiation is shown in FIG. 13, and an electron micrograph of the L & S pattern at the rotation speed of 1500 rpm at irradiation is shown in FIG.
From the SEM photographs of FIGS. 13 and 14, it was found that the line width was wider when the rotation speed was 2 rpm than when the rotation speed was 1500 rpm. This is because the resist TMMR has high sensitivity, and thus it is considered that the line width is widened by reducing the number of rotations.

  The relationship between the electron beam incident angle shown in FIGS. 13 and 14 and the average line width of the L & S pattern is shown in Table 2 below and shown as a graph in FIG.

  From the graph of FIG. 15, the line width increases as the electron beam incident angle is increased from 0 ° to 30 ° with reference to the line width at 0 °, but the line width spread becomes maximum at 30 °. When it is larger than 30 °, the spread of the line width gradually decreases. Further, when the angle is increased to 60 °, the line width becomes unstable. This is because the line width broadens from 0 ° to 30 ° due to the effect of backscattering, but the angle becomes larger at 30 ° or more, making it less susceptible to the effect of backscattering and the line width gradually becoming wider. It is done. In addition, it is considered that the influence on the line width due to the change in the incident angle of the electron beam is suppressed by the effect of PEB applied when TMMR is used as the resist.

  Moreover, there was no difference in the line width expansion in the change in the incident angle of the electron beam between the negative side and the positive side at the rotation speeds of 2 rpm and 1500 rpm. Further, the line width when the sample was irradiated without rotation during irradiation (in the case of fixed irradiation) was 1.6 μm, and was not changed by the change in the electron beam incident angle. Therefore, it was found that the processing line width in the case of fixed irradiation becomes finer than that of rotational irradiation. This is considered that the vibration of the sample caused by the rotation affects the irradiation.

[Example 4]
-Production of endless mold by splicing irradiation method-
As in Example 1, however, an endless mold was produced by the joint irradiation method under the following conditions. In addition, the minimum rotation angle of the engraving operation of the irradiation apparatus is 0.5 °.
・ Acceleration voltage: 10 kV
-Beam current: 4.0 nA
・ Beam diameter: 400nm (measured by knife edge method)
・ Dose amount: 250 μC / cm ²
・ Pattern: Line & space (L & S) pattern shown in FIG. 16 ・ Magnification: 100 times, 300 times, 600 times

In the joint irradiation method, irradiation is performed with overlapping at the joint so that the pattern drawn before the rotation and the pattern after the rotation are connected. A method of calculating the rotation angle for forming such a seam will be described.
Since the radius r of the used cylindrical sample is 15 mm, the moving distance x of the observation surface when the sample is rotated by 0.5 ° is 0.135 mm from the following formula.

  Since the irradiable area of the used irradiation apparatus is 12 cm × 9 cm, the irradiable areas at the respective magnifications of 100 times, 300 times, and 600 times are 1200 μm × 900 μm, 400 μm × 300 μm, and 200 μm × 150 μm, respectively. Therefore, in consideration of a short side of the irradiation region, the region width that can be irradiated at each magnification is 900 μm, 300 μm, and 150 μm, respectively. From the above, the rotation angle for overlapping irradiation at the joint portion is as shown in Table 3.

  SEM photographs of the obtained L & S pattern are shown in FIGS. FIG. 17 is an SEM photograph when irradiated at a magnification of 100 times, FIG. 18 at a magnification of 300 times, and FIG. 19 at a magnification of 600 times.

As shown in the SEM photographs of FIGS. 17 to 19, the L & S pattern was formed over the entire circumference at any magnification.
Table 4 shows the results of measuring the widths of the lines and spaces of the portion irradiated once and not the joint, and the twice irradiated portion of the joint from the SEM photographs of FIGS.

From Table 4, it can be seen that the portion irradiated once is the value closest to the theoretical value when the magnification is 600 times. Further, in the case of 100 times, the value was nearly twice the theoretical value.
The portion irradiated twice was also the value closest to the theoretical value (1.5 times) when the magnification was 600 times, and was nearly three times the theoretical value when the magnification was 300 times.
At any magnification, the line width was thicker at the portion irradiated twice than at the portion irradiated once. In addition to the reason that the amount of electron beam irradiation has increased due to two irradiations, it is presumed that the irradiation position has shifted due to rotation in the overlapping irradiation portion. For this reason, the larger the magnification, the easier it is for the line width to be widened. Therefore, it is desirable that the magnification is not set too high. However, from the results of this example, the magnification of 600 times is the most accurate. Turned out to be high.

In a further magnification 600 times, 100 .mu.C ^/ cm 2 the dose, it was also prepared samples were irradiated with 400μC / cm ^2. SEM photographs of the obtained L & S pattern are shown in FIGS.

  From the SEM photographs of FIGS. 19 to 21, the widths of the lines and spaces of the once irradiated portion and the twice irradiated portion at each dose when the magnification is 600 times are measured, and the results are shown in Table 5.

From Table 5, it was found that the portion irradiated once and the portion irradiated twice are approximate values regardless of the dose. In addition, it can be seen that the pattern can be clearly observed at any dose amount. From this, it is considered that the irradiation accuracy is not affected when the dose amount is in the range of 100 to 400 μC / cm ² .

In addition, in the irradiation conditions of Example 4, there were many states in which the L & S pattern was peeled off or shifted as a whole. However, as shown in FIGS. 19 and 20, since the pattern can be confirmed even though the pattern is twisted and overlapped, the irradiation was performed accurately, but such peeling and misalignment occurred during development. It is thought that.
In order to prevent this phenomenon, it seems to be effective to further increase the dose amount and irradiate deeply into the resist film. By curing to the deep part of the resist, it seems possible to suppress the phenomenon that the lower part of the pattern flows during development.

[Example 5]
-Production of endless mold by splicing irradiation method-
As in Example 4, however, an endless mold was produced by the joint irradiation method under the following conditions.
・ Acceleration voltage: 10 kV
-Beam current: 4.0 nA
・ Beam diameter: 400nm (measured by knife edge method)
・ Dose amount: 400 μC / cm ²
・ Magnification: 300 times ・ Rotation angle: 1 °
・ Pattern: Line & space (L & S) pattern shown in Table 6 below

  SEM photographs of the obtained L & S pattern are shown in FIGS. FIG. 22 is an SEM photograph when irradiation is performed under condition 1 in Table 6, FIG. 23 is irradiation under condition 2, and FIG.

  The widths of the lines and spaces of the once irradiated portion and the twice irradiated portion were measured from the SEM photographs of FIGS.

From Table 7, the line width was 1.1 times the theoretical value when the line pattern was 100 dots, but more than twice when the line pattern was 30 dots. This is considered due to the spot diameter of the electron beam of the SEM.
Further, as apparent from FIGS. 22 to 24, the thinner the line pattern is, the more noticeable the deviation of the joint portion irradiated twice. From this, it is considered that the alignment needs to be performed more accurately in order to produce a finer pattern.

<Summary of Examples 1-5>
When TMMR is used as the resist, the line width increases as the electron beam incident angle is increased from 0 ° to 30 ° under the same dose conditions. When it was larger than °, the spread of the line width gradually decreased. On the other hand, when the angle was increased to 60 °, the line width became unstable. From the above, it has been found that when the electron beam incident angle is 0 ° to 30 °, by increasing the electron beam incident angle, a pattern having the same line width can be produced with a lower dose.
As for the number of rotations at the time of irradiation, when comparing the line widths produced at 2 rpm and 1500 rpm, the line width at 2 rpm was wider than that at 1500 rpm. Further, regarding the change in the incident angle of the electron beam on the − side and the + side, there was no difference in the line width. In TMMR, it is considered that the influence on the line width due to the change in the electron beam incident angle is suppressed by the effect of PEB.

[Example 6]
-Production of endless mold by continuous irradiation method-
--Drawing characteristics depending on dose amount--
<Deposition of resist film>
Substrate: cylindrical sample (aluminum, diameter 10 mm)
Resist: PMMA diluent (volume concentration 50%)
PMMA: OEBR-1000 (Tokyo Ohka Kogyo Co., Ltd.)
Thin solution for PMMA: LB thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.)

<Application conditions>
Coating penetration speed 3.0mm / sec
Immersion time: 5.0 sec
Coating lifting speed 0.1mm / sec
Under the above conditions, a PMMA resist was applied.

<PB>
After coating, firing (PB) was performed at 180 ° C. for 20 minutes using a high-temperature furnace.

<Electron beam irradiation>
The columnar substrate after PB was mounted in the SEM, and the electron beam was irradiated while changing the dose amount to 100, 200, and 500 μC / cm ² while rotating the substrate. The conditions for rotation and irradiation are as follows.

Experimental apparatus: apparatus similar to Example 2 Beam current: 4.0 nA
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Beam incident angle: 0 °
Number of rotations during irradiation: 1500 rpm
Average resist film thickness: 523 nm
Dose amount: 100, 200, 500 μC / cm ²
Drawing pattern: L & S pattern shown in FIG.
The SEM was produced at a magnification of 300 times (a square having a drawing range of 300 μm on one side).

<Development>
After irradiation, the film was developed with a developer. As the developer, a developer for OEBR-1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) (room temperature: about 23 ° C.) was used, and the developer was immersed for 2 minutes. Then, it dried with nitrogen gas.

<Result>
An SEM photograph of the obtained L & S pattern is shown in FIG.
Figures 26, when the dose of 100 .mu.C / cm ² shallow depth of the pattern, considered since when the 500μC / cm ² have clung pattern each other, the optimal dose is 200μC / cm ² It is done.

[Example 7]
-Production of endless mold by continuous irradiation method-
--Drawing characteristics depending on the number of rotations--
In the same manner as in Example 6, a resist film was formed and PB was performed to prepare a columnar sample provided with the resist film.

  A cylindrical sample was mounted in the SEM, and the rotation speed of the sample was changed to 2, 10, 50, 100, 200, 500, 100, 1500 rpm, and electron beam rotation irradiation was performed under the following conditions. Moreover, it changed every 10 rpm between 10-100 rpm, and performed electron beam rotation irradiation.

<Irradiation conditions>
Experimental apparatus: As in Example 2, beam current: 4.0 nA
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Beam incident angle: 0 °
Average resist film thickness: 523 nm
Dose amount: 200 μC / cm ²
Drawing pattern: same as in Example 6

<Development>
After the irradiation, development was performed in the same manner as in Example 6.

<Result>
FIG. 27 shows an SEM photograph of the obtained L & S pattern, and FIG. 28 is a graph showing the relationship between the rotational speed and the processing line width. From FIG. 28, under this condition, it is considered that the finest processing line width can be obtained around the rotation speed of 50 rpm at the time of irradiation.
FIG. 29 is a graph showing the relationship between the rotational speed and the processing line width around the rotational speed of 50 rpm during irradiation. From FIG. 29, under this condition, the finest processing line width is obtained when the rotation speed during irradiation is 40 rpm, but when the rotation speed during irradiation is 40 rpm or less, the L & S pattern is formed in the circumferential direction of the roll. There was a part that was not done. In the production of the roll-shaped nanoimprint mold, a pattern needs to be formed on the entire surface in the circumferential direction of the roll. Therefore, it is considered that the rotation speed at the time of irradiation at which the finest line width is obtained is 50 rpm.

[Example 8]
-Production of endless mold by continuous irradiation method-
-Drawing characteristics due to differences in electron beam incident angle-
In the same manner as in Example 6, a resist film was formed and PB was performed to prepare a columnar sample provided with the resist film.

A cylindrical sample is mounted in the SEM, and the incident angle of the beam is changed to −60 °, −50 °, −40 °, −20 °, −10 °, 0 °, + 10 °, + 20 °, + 30 °, Electron beam rotation irradiation was performed under the following conditions. Note that a dose of ^{100μC / cm 2, 150μC / cm} 2
In this case, irradiation was not performed at an incident beam incident angle of −10 °, 0 °, and + 10 °.

<Irradiation conditions>
Experimental apparatus: Similar to Example 2, beam current: 4.0 nA, 2.5 nA (only at 150 μC / cm ² )
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Number of rotations during irradiation: 50 rpm
Resist average film thickness: 505 nm, 430 nm (only at 150 μC / cm ² )
Dose amount: 100, 150, 200 μC / cm ²
Drawing pattern: same as in Example 6

<Development>
After the irradiation, development was performed in the same manner as in Example 6.

<Result>
30 and 31 show SEM photographs of the L & S pattern at each electron beam incident angle when the dose is 200 μC / cm ² . FIG. 32 shows the relationship between the electron beam incident angle and the processing line width when the dose is 200 μC / cm ² .
From FIG. 32, the processing line width increases as the electron beam incident angle increases. This is presumably because the influence of secondary electrons increases as the electron beam incident angle increases. Comparing the + and-sides of the electron beam incident angle, up to ± 20 °, the-side is considered to have a larger processing line width and is more susceptible to secondary electrons. The processed line width is large, and it is thought that it is easily affected by secondary electrons. Therefore, it is considered that the dose amount can be reduced by using the + side as the electron beam incident angle.

FIG. 33 shows an SEM photograph of the L & S pattern at each electron beam incident angle when the dose is 100 μC / cm ² .
From FIG. 33, it is considered that it is difficult to use the L & S pattern except for the case where the electron beam incident angle is −60 °, because the L & S pattern is not prepared for one roll. At the electron beam incident angles of + 20 ° and + 30 °, no L & S pattern was present.
As a result, from FIG. 33, it is considered that the dose amount is insufficient when the dose amount is 100 μC / cm ² .

Next, FIG. 34 shows the L & S pattern at each electron beam incident angle when the dose is 150 μC / cm ² . FIG. 35 shows the relationship between the electron beam incident angle and the processing line width when the dose is 150 μC / cm ² .
From FIG. 35, the processing line width increases as the electron beam incident angle increases. This is presumably because the influence of secondary electrons increases as the electron beam incident angle increases. When the + side and − side of the electron beam incident angle are compared, it is considered that the + side has a larger processing line width and is easily influenced by secondary electrons. Therefore, it is considered that the dose amount can be reduced by using the + side as the electron beam incident angle.

[Example 9]
-Production of endless mold by continuous irradiation method-
-Drawing characteristics due to differences in electron beam incident angle at each dose-
In the same manner as in Example 6, a resist film was formed and PB was performed to prepare a columnar sample provided with the resist film.

  A cylindrical sample is mounted in the SEM, and the incident angle of the beam is changed to −60 °, −50 °, −40 °, −20 °, −10 °, 0 °, + 10 °, + 20 °, + 30 °, Electron beam rotation irradiation was performed under the following conditions.

<Irradiation conditions>
Experimental apparatus: as in Example 2, beam current: 1.5 nA
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Number of rotations during irradiation: 50 rpm
Average resist film thickness: 391 nm
Dose amount: 100, 125, 150, ²⁰⁰ μC / cm ²
Drawing pattern: same as in Example 6

<Development>
After the irradiation, development was performed in the same manner as in Example 6.

<Result>
FIG. 36 shows the relationship between the electron beam incident angle and the processing line width at each dose.
From FIG. 36, when comparing the + side and the − side of the electron beam incident angle, it is considered that the + side has a larger processing line width and is easily influenced by secondary electrons. Therefore, it is considered that the dose amount can be reduced by using the + side as the electron beam incident angle.
Further, the processing line width when the electron beam incident angle is 0 ° and the dose amount is 200 μC / cm ² is almost equal to the processing line width when the electron beam incident angle is + 30 ° and the dose amount is 125 μC / cm ^2. ing. Accordingly, it is contemplated that the dose by the electron beam incident angle + 30 ° can be suppressed from 200μC / cm ² to 125μC / cm ^2.

[Example 10]
-Production of endless mold by continuous irradiation method-
--- Micro processing--
In the same manner as in Example 6, a resist film was formed and PB was performed to prepare a columnar sample provided with the resist film.

  A cylindrical sample was mounted in the SEM, and the electron beam rotation irradiation was performed under the following conditions while changing the design value of the L & S pattern in order to produce a fine L & S pattern.

<Irradiation conditions>
Experimental apparatus: As in Example 2, beam current: 4.0 nA
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Beam incident angle: 0 °
Number of rotations during irradiation: 50 rpm
Average resist film thickness: 430 nm
Dose amount: 200 μC / cm ²
Drawing pattern: pattern shown in FIGS. 37 and 38

<Development>
After the irradiation, development was performed in the same manner as in Example 6.

<Result>
FIG. 39 shows an SEM photograph of each L & S pattern when the dose is 200 μC / cm ² .
From FIG. 39, in the case of a line of 0.3 μm and a space of 0.6 μm, there are portions where the patterns are bonded to each other, and a pattern for one round of the roll is not formed. Therefore, under this condition, it is considered that the finest line width when the electron beam incident angle is 0 ° is a line of 0.5 μm and a space of 1.0 μm.

[Example 11]
-Production of endless mold by continuous irradiation method-
-Drawing characteristics due to difference in electron beam incident angle at each dose in fine L & S pattern-
In the same manner as in Example 6, a resist film was formed and PB was performed to prepare a columnar sample provided with the resist film.

  A cylindrical sample is mounted in the SEM, and the incident angle of the beam is changed to −60 °, −50 °, −40 °, −20 °, −10 °, 0 °, + 10 °, + 20 °, + 30 °, Electron beam rotation irradiation was performed under the following conditions.

<Irradiation conditions>
Experimental apparatus: as in Example 2, beam current: 1.5 nA
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Number of rotations during irradiation: 50 rpm
Average resist film thickness: 308 nm (in the case of the pattern shown in FIG. 37)
439 (in the case of the pattern shown in FIG. 38)
Dose amount: 100, 125, 150, ²⁰⁰ μC / cm ²
Drawing pattern: pattern shown in FIGS. 37 and 38

<Development>
After the irradiation, development was performed in the same manner as in Example 6.

<Result>
FIG. 40 is a graph showing the relationship between the electron beam incident angle and the processing line width at each dose amount of 0.5 μm line and 1.0 μm space. FIG. 41 shows an SEM photograph of a pattern with a line of 0.3 μm and a space of 0.6 μm when the dose is 200 μC / cm ² when the electron beam incident angle is changed. FIG. 42 is a graph showing the relationship between the electron beam incident angle and the processing line width at each dose amount of 0.3 μm line and 0.6 μm space.
From FIG. 41, when the electron beam incident angle was 0 °, the pattern was not completely formed, but when the electron beam incident angle was −10 °, the pattern was formed for one circle. The finest pattern when the electron beam incident angle is changed is considered to be a line of 0.3 μm and a space of 0.6 μm.

[Reference Example 1]
-Drawing characteristics due to differences in electron beam incident angle at each dose when irradiated without rotation--
In the same manner as in Example 6, a resist film was formed and PB was performed to prepare a columnar sample provided with the resist film.

  A cylindrical sample is mounted in the SEM, and the incident angle of the beam is changed to −60 °, −50 °, −40 °, −20 °, −10 °, 0 °, + 10 °, + 20 °, + 30 °, Electron beam irradiation was performed under the following conditions without rotating the sample.

<Irradiation conditions>
Experimental apparatus: As in Example 2, beam current: 0.65 nA
Acceleration voltage: 30 kV
Beam diameter: 150 nm
Number of rotations during irradiation: 0 rpm
Average resist film thickness: 455 nm
Dose amount: 100, 125, 150, ²⁰⁰ μC / cm ²
Drawing pattern: The same as in Example 6.

<Development>
After the irradiation, development was performed in the same manner as in Example 6.

<Result>
FIG. 43 shows a graph of the relationship between the electron beam incident angle and the processing line width at each dose when the sample is fixed without rotating (0 rpm). The L & S of the pattern at this time is a line of 1.0 μm and a space of 2.0 μm.
From FIG. 43, the processed line width is smaller when the sample is irradiated without being rotated than when the sample is irradiated while being rotated. Therefore, it is considered that vibration due to rotation has an influence on irradiation.

In the present invention, the method of irradiating the sample while rotating provides an extremely excellent effect that a seamless endless pattern can be obtained. Further, based on the result of Reference Example 1, vibration due to rotation is suppressed. As a result, a finer pattern may be obtained.
Further, based on the result of Reference Example 1, as in Examples 4 and 5, after the sample was fixed and irradiated without rotation, the sample was rotated and the sample was fixed and irradiated again. The influence of vibration due to can be suppressed. However, it is necessary to accurately position the irradiation at the joint.

<Summary of Examples 6 to 11 and Reference Example 1>
When PMMA was used as the resist, the rotation speed during irradiation was optimally 50 rpm, and the line width increased as the electron beam incident angle was increased from 0 ° to 60 °. In addition, the larger the dose, the more easily affected by changes in the incident angle of the electron beam and the line width increased. Accordingly, it has been found that the dose amount can be suppressed lower as the electron beam incident angle is increased.
Comparing the + side and − side of the electron beam incident angle, it was found that the dose amount can be reduced by using the + side. When the dose amount was 200 μC / cm ² and the electron beam incident angle was −10 °, an L & S pattern having a line of 0.3 μm and a space of 0.6 μm was obtained, and the finest line width was obtained.

10 Substrate 20 Resist layer 30 Resin 40 Glass 100 Cylindrical substrate

Claims (8)

Rotating a substrate that is endless in the circumferential direction and hardened or solubilized by irradiation with an electron beam or an ion beam in a rotation direction;
Irradiating an electron beam or an ion beam at a predetermined angle when the incident angle when irradiating toward the rotation axis of the substrate is 0 °;
Removing a part of the substrate by the irradiation or by development after the irradiation;
A method for producing an endless pattern having Rotating the substrate endless in the circumferential direction and provided with a film to be cured or solubilized by irradiation with an electron beam or an ion beam in a rotation direction;
Irradiating an electron beam or an ion beam at a predetermined angle to the film when an incident angle when irradiating toward the rotation axis of the substrate is 0 °;
Removing a part of the film by the irradiation or by development after the irradiation;
A method for producing an endless pattern having   3. The method for producing an endless pattern according to claim 1, wherein the electron beam or the ion beam is irradiated while rotating the substrate in a rotation direction.   The pattern is drawn by adjusting at least one of a scanning direction and a scanning speed of the electron beam or ion beam, a moving direction and a moving speed of the substrate, and a rotating direction and a rotating speed of the substrate. The method for producing an endless pattern according to claim 3.   3. The method for producing an endless pattern according to claim 1, wherein the substrate is not rotated during irradiation with the electron beam or ion beam.   6. The method for producing an endless pattern according to claim 1, wherein an incident angle of the electron beam or ion beam with respect to the substrate is 30 ° or more and 80 ° or less.   The method for producing an endless pattern according to claim 6, wherein an incident angle of the electron beam or ion beam to the substrate is 40 ° or more and 80 ° or less.   When the incident angle of the electron beam or ion beam with respect to the substrate is plus in the rotation direction of the substrate and minus in the reverse rotation direction, the incident angle is not less than −30 ° and less than 0 °, or greater than 0 ° and + 30 °. The method for producing an endless pattern according to any one of claims 1 to 5, wherein: