JP2011171366A - Uv-led light source for nanoimprint - Google Patents
Uv-led light source for nanoimprint Download PDFInfo
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本発明は、ナノインプリント法により微細凹凸構造を作製する際のＵＶ−ＬＥＤ光源及び当該ＵＶ−ＬＥＤ光源を用いた構造体の製造方法に関する。 The present invention relates to a UV-LED light source for producing a fine concavo-convex structure by a nanoimprint method and a method for producing a structure using the UV-LED light source.
ナノインプリント技術は、生産性が低い電子ビームリソグラフィや高価な光学リソグラフィに代わる技術として注目されている。特に、ＵＶ光を利用するＵＶナノインプリント技術はその生産性の高さから近年注目を浴びている（特許文献１）。 Nanoimprint technology has attracted attention as a technology that replaces electron beam lithography and expensive optical lithography, which have low productivity. In particular, the UV nanoimprint technology using UV light has recently attracted attention due to its high productivity (Patent Document 1).
上記ナノインプリント技術の特徴は、電子ビームリソグラフィ等の生産性問題を克服しようとすることであり、ナノスケールの構造を有する金型を製作して、前記製作された金型を基材上のＵＶ硬化性樹脂膜に押し付けた後に、当該ＵＶ硬化性樹脂膜を硬化させることでナノスケールの構造を転写する。前記操作を複数回繰り返すことで、一つの基材上に金型が有する微細凹凸構造とは反対の微細凹凸構造を容易に作製することが可能である（例えば、特許文献２）。特に、ＵＶナノインプリント法を使用することで、数十ナノメートルから数百ナノメートルの微細構造を容易に形成することができる。例えば、１０Ｇｂｉｔ／ｃｍ２に相当する５０ｎｍハーフピッチで３４×３４マスの網目構造（例えば、非特許文献１）や、４５６ｎｍの直径を有し深さが３５０ｎｍの円筒状の溝が周期７４８ｎｍで並んだ構造（例えば、非特許文献２）等が挙げられる。 The feature of the nanoimprint technology is to overcome productivity problems such as electron beam lithography. A mold having a nanoscale structure is manufactured, and the manufactured mold is UV-cured on a substrate. After pressing against the curable resin film, the nano-scale structure is transferred by curing the UV curable resin film. By repeating the above operation a plurality of times, it is possible to easily produce a fine concavo-convex structure opposite to the fine concavo-convex structure of the mold on one substrate (for example, Patent Document 2). In particular, by using the UV nanoimprint method, a fine structure of several tens of nanometers to several hundreds of nanometers can be easily formed. For example, a 34 × 34 mesh network structure (for example, Non-Patent Document 1) with a 50 nm half pitch corresponding to 10 Gbit / cm 2 and a cylindrical groove having a diameter of 456 nm and a depth of 350 nm are arranged at a period of 748 nm. The structure (for example, nonpatent literature 2) etc. are mentioned.
ＵＶナノインプリント法では、金型にＵＶ硬化性樹脂を充填した状態でＵＶ光を照射しＵＶ硬化性樹脂を硬化させる必要があるため、微細凹凸構造の転写にはＵＶ光を照射するＵＶ光源が重要となる。ナノインプリント法に使用されるＵＶ光源としては、発光管内に水銀の他に金属ハロゲン化物を封入したメタルハライドランプや石英ガラス性の発光管内に高純度の水銀と少量の希ガスを封入した高圧水銀灯、直進性の高いＵＶ光を発する発光ダイオードであるＵＶ−ＬＥＤ等が用いられている。特に、ＵＶ−ＬＥＤ光源は長寿命であり省エネ効果が見込めるため注目されている。 In the UV nanoimprint method, it is necessary to cure the UV curable resin by irradiating the mold with the UV curable resin, so that the UV light source that irradiates the UV light is important for the transfer of the fine uneven structure. It becomes. The UV light source used in the nanoimprint method includes a metal halide lamp in which metal halide is sealed in addition to mercury in the arc tube, a high-pressure mercury lamp in which high purity mercury and a small amount of rare gas are sealed in a quartz glass arc tube, and straight ahead UV-LED etc. which are the light emitting diodes which emit highly efficient UV light are used. In particular, the UV-LED light source has been attracting attention because it has a long life and an energy saving effect is expected.
このように、環境負荷と生産の観点から、ナノインプリント法の光源としてＵＶ−ＬＥＤ光源を使用することが望ましい。しかし、ナノインプリント法の光源としてＵＶ−ＬＥＤ光源を用いた場合、ＵＶ光の直進性の高さから、露光対象に近接して照射する場合ＵＶ−ＬＥＤ光源を構成するＬＥＤのほぼ直下の部分しか露光されず、また露光対象から遠ざけて露光した場合、ＵＶ光強度が著しく低下する為、ナノスケールの微細凹凸構造をナノインプリント法で転写できないという問題がある。特に、微細凹凸の凸部の大きさが、使用するＵＶ−ＬＥＤ光源の照射波長よりも小さくなると、ナノインプリント法による微細凹凸の転写に不良が生じるという問題を発明者は見出してきた。 Thus, it is desirable to use a UV-LED light source as the light source of the nanoimprint method from the viewpoint of environmental load and production. However, when a UV-LED light source is used as the light source for the nanoimprint method, only the portion immediately below the LED constituting the UV-LED light source is exposed due to the high linearity of the UV light. In addition, when the exposure is performed away from the object to be exposed, the intensity of the UV light is remarkably lowered, so that there is a problem that the nanoscale fine uneven structure cannot be transferred by the nanoimprint method. In particular, the inventors have found a problem that if the size of the convex portion of the fine unevenness is smaller than the irradiation wavelength of the UV-LED light source to be used, a defect occurs in the transfer of the fine unevenness by the nanoimprint method.
本発明は、かかる点に鑑みてなされたものであり、ナノインプリント法の光源としてＵＶ−ＬＥＤ光源を用いて微細凹凸構造を作製する際に、金型からの微細凹凸構造の転写が良好になるようなＵＶ−ＬＥＤ光源を提供することを目的とする。 The present invention has been made in view of such a point, and when a fine concavo-convex structure is produced using a UV-LED light source as a light source of the nanoimprint method, the transfer of the fine concavo-convex structure from a mold is improved. An object is to provide a UV-LED light source.
本発明者は上記課題を鋭意検討した結果、ＵＶ−ＬＥＤ光源が、露光対象物との間に特定の構造を有する散乱板を有することで、顕著な効果を奏することを見出し、本発明を完成させた。 As a result of earnestly examining the above problems, the present inventors have found that the UV-LED light source has a remarkable effect by having a scattering plate having a specific structure between the exposure object and the present invention is completed. I let you.
本発明のナノインプリント用ＵＶ−ＬＥＤ光源の一態様は、ＬＥＤを有するＵＶ光照射部と、ＵＶ光照射部から射出されたＵＶ光を透過して散乱するＵＶ散乱板とを具備し、ＵＶ散乱板がＵＶ光照射部と露光対象との間に配置されることを特徴としている。 One aspect of the UV-LED light source for nanoimprinting of the present invention comprises a UV light irradiation part having an LED, and a UV scattering plate that transmits and scatters UV light emitted from the UV light irradiation part. Is arranged between the UV light irradiation unit and the exposure target.
本発明のナノインプリント用ＵＶ−ＬＥＤ光源の一態様において、ＵＶ散乱板は、ＵＶ光照射部から射出されるＵＶ光を透過する基材を有し、且つ、基材の片側表面又は両側表面に、ＵＶ光照射部から射出されるＵＶ光の中心波長の１／１０倍以下の凹凸形状及び／又は中心波長以上の大きさを有する凹凸形状を有することが好ましい。 In one aspect of the UV-LED light source for nanoimprinting of the present invention, the UV scattering plate has a base material that transmits UV light emitted from the UV light irradiation section, and on one or both surfaces of the base material, It is preferable to have a concavo-convex shape not more than 1/10 times the center wavelength of UV light emitted from the UV light irradiation section and / or a concavo-convex shape having a size not less than the center wavelength.
本発明のナノインプリント用ＵＶ−ＬＥＤ光源の一態様において、ＵＶ散乱板は、ＵＶ光照射部から射出されるＵＶ光を透過する基材を有し、且つ、基材中に、ＵＶ光照射部から射出されるＵＶ光の中心波長の１／１０倍以下の分散剤及び／又は中心波長以上の大きさを有する分散剤を有することが好ましい。 In one aspect of the UV-LED light source for nanoimprinting of the present invention, the UV scattering plate has a base material that transmits UV light emitted from the UV light irradiation section, and the UV light irradiation section is provided in the base material from the UV light irradiation section. It is preferable to have a dispersant that is 1/10 times or less of the central wavelength of the emitted UV light and / or a dispersant that has a size that is greater than or equal to the central wavelength.
本発明のナノインプリント用ＵＶ−ＬＥＤ光源の一態様において、ＵＶ光照射部から射出されるＵＶ光の中心波長が、３５５ｎｍ以上３８５ｎｍ以下であることが好ましい。 In one aspect of the UV-LED light source for nanoimprinting of the present invention, the center wavelength of the UV light emitted from the UV light irradiation section is preferably 355 nm or more and 385 nm or less.
本発明の凹凸構造を有する構造体の製造方法は、上記ナノインプリント用ＵＶ−ＬＥＤ光源を用いて、４０ｎｍ以上３８０ｎｍ以下の凹凸ピッチを有する構造体をナノインプリント法で作製することを特徴としている。 The method for producing a structure having a concavo-convex structure according to the present invention is characterized in that a structure having a concavo-convex pitch of 40 nm or more and 380 nm or less is produced by a nanoimprint method using the UV-LED light source for nanoimprint.
本発明によれば、ナノインプリント法の光源としてＵＶ−ＬＥＤ光源を用いて微細凹凸構造を作製する場合であっても、金型からの微細凹凸構造の転写を良好に行うことが可能となる。 According to the present invention, even when a fine concavo-convex structure is produced using a UV-LED light source as a light source for the nanoimprint method, it is possible to transfer the fine concavo-convex structure from a mold satisfactorily.
以下では、本発明の実施の方法について添付図面を参照して説明する。 Hereinafter, a method for carrying out the present invention will be described with reference to the accompanying drawings.
図１は、本実施の形態に係るＵＶ−ＬＥＤ光源と露光対象を基準にした散乱板の設置位置を模式的に示した図である。図２は、本実施の形態に係るＵＶ−ＬＥＤ光源から照射されたＵＶ光の進行方向を模式的に示した図である。図３は、本発明の形態に係るＵＶ−ＬＥＤ光源の散乱板の構造を模式的に示した図である。なお、図１、図２及び図３におけるＵＶ光源や散乱板、散乱板の構造等の各部の数、形状、寸法比等はこれに限定されない。また、図１、図２及び図３は本発明に係るＵＶ−ＬＥＤ光源の一使用態様を示す図である。 FIG. 1 is a diagram schematically showing the installation position of the scattering plate based on the UV-LED light source and the exposure target according to the present embodiment. FIG. 2 is a diagram schematically showing the traveling direction of the UV light emitted from the UV-LED light source according to the present embodiment. FIG. 3 is a diagram schematically showing the structure of the scattering plate of the UV-LED light source according to the embodiment of the present invention. Note that the number, shape, dimensional ratio, and the like of each part of the UV light source, the scattering plate, and the structure of the scattering plate in FIGS. 1, 2, and 3 are not limited thereto. Moreover, FIG.1, FIG2 and FIG.3 is a figure which shows the usage condition of the UV-LED light source which concerns on this invention.
図１に示すように、本発明に係るＵＶ−ＬＥＤ光源１０は、ＬＥＤを有するＵＶ光照射部（ＵＶ−ＬＥＤ１１）と、ＵＶ−ＬＥＤ１１から射出されたＵＶ光を透過して散乱するＵＶ散乱板１５を有している。ＵＶ散乱板１５は、ＵＶ−ＬＥＤ１１のＵＶ照射面１２と露光する対象物（露光対象１４）の露光面１３との間１６に設けられる。 As shown in FIG. 1, a UV-LED light source 10 according to the present invention includes a UV light irradiation unit (UV-LED 11) having an LED and a UV scattering plate that transmits and scatters UV light emitted from the UV-LED 11. 15. The UV scattering plate 15 is provided between the UV irradiation surface 12 of the UV-LED 11 and the exposure surface 13 of the object to be exposed (exposure target 14).
ＵＶ散乱板１５の設置位置は、ＵＶ−ＬＥＤ１１のＵＶ照射面１２と露光対象１４の露光面１３との間１６にあれば特に限定されるものではなく、ＵＶ散乱板１５のＵＶ−ＬＥＤ１１側の面１５ａがＵＶ照射面１２と接している状態（図４（Ａ）参照）や、或いはＵＶ散乱板１５の露光対象１４側の面１５ｂが露光対象１４の露光面１３と接している状態（図４（Ｂ）参照）や、ＵＶ散乱板１５の各面１５ａ及び１５ｂがＵＶ照射面１２と露光対象面１３の双方と接している状態（図４（Ｃ）参照）や、ＵＶ散乱板１５の各面１５ａ及び１５ｂがＵＶ照射面１２と露光対象面１３の双方とも接してない状態であり且つ露光対象面１３とＵＶ照射面１２の間に位置する状態（図１参照）が挙げられる。 The installation position of the UV scattering plate 15 is not particularly limited as long as it is 16 between the UV irradiation surface 12 of the UV-LED 11 and the exposure surface 13 of the exposure target 14, and is not limited to the UV-LED 11 side of the UV scattering plate 15. The surface 15a is in contact with the UV irradiation surface 12 (see FIG. 4A), or the surface 15b on the exposure target 14 side of the UV scattering plate 15 is in contact with the exposure surface 13 of the exposure target 14 (FIG. 4 (B)), the state in which the surfaces 15a and 15b of the UV scattering plate 15 are in contact with both the UV irradiation surface 12 and the exposure target surface 13 (see FIG. 4C), and the UV scattering plate 15 Examples include a state in which each of the surfaces 15a and 15b is not in contact with both the UV irradiation surface 12 and the exposure target surface 13 and is positioned between the exposure target surface 13 and the UV irradiation surface 12 (see FIG. 1).
効率的にＵＶ光を利用し、効果的にナノインプリント法により微細凹凸構造を転写する観点からは、ＵＶ散乱板１５のＵＶ−ＬＥＤ１１側の面１５ａとＵＶ照射面１２との距離が１０ｃｍ以下であると既存のＵＶ−ＬＥＤ光源に容易に設置できる為好ましく、０ｃｍ（図４（Ａ）参照）であると照射されるＵＶ光を効果的に利用できる為好ましい。また、ＵＶ−ＬＥＤ１１と露光対象１４との距離は特に限定されるものではないが、効率的にＵＶ光を利用し、効果的にナノインプリント法により微細凹凸構造を転写する観点からは３０ｃｍ以下であることが好ましく、２０ｃｍ以下であると照射されるＵＶ光を効率的に利用できるためより好ましい。 From the viewpoint of efficiently using UV light and effectively transferring the fine uneven structure by the nanoimprint method, the distance between the UV-LED 11 side surface 15a of the UV scattering plate 15 and the UV irradiation surface 12 is 10 cm or less. It is preferable because it can be easily installed in an existing UV-LED light source, and is preferably 0 cm (see FIG. 4A), since the irradiated UV light can be effectively used. Further, the distance between the UV-LED 11 and the exposure target 14 is not particularly limited, but is 30 cm or less from the viewpoint of efficiently using UV light and effectively transferring the fine concavo-convex structure by the nanoimprint method. It is more preferable that it is 20 cm or less because the irradiated UV light can be used efficiently.
次に、ＵＶ散乱板１５の有無によるＵＶ−ＬＥＤからの照射光について、図２を参照して説明する。ＵＶ散乱板がない場合（図２（Ａ）参照）は、ＵＶ−ＬＥＤ２１から照射されたＵＶ光２３は露光対象２２へと直進性高く進行するが、ＵＶ散乱板２５を設置した場合（図２（Ｂ）参照）は、ＵＶ−ＬＥＤ２１から照射されたＵＶ光２４はＵＶ散乱板２５に入射するまでは直進性を保つが、ＵＶ散乱板２５を透過した後は散乱により照射方向に対してランダムな方向性を有するＵＶ光２６となる。すなわち、露光対象２２からみれば、ＵＶ散乱板２５がない場合はほぼ一定の入射角を有するＵＶ光２３が入射するのに対し、ＵＶ散乱板２５を設置した場合は、様々な入射角を有するＵＶ光２６が入射することになる。 Next, irradiation light from the UV-LED with or without the UV scattering plate 15 will be described with reference to FIG. When there is no UV scattering plate (see FIG. 2 (A)), the UV light 23 irradiated from the UV-LED 21 travels straight toward the exposure target 22, but when the UV scattering plate 25 is installed (FIG. 2). (See (B)), the UV light 24 irradiated from the UV-LED 21 maintains straightness until it enters the UV scattering plate 25, but after passing through the UV scattering plate 25, it is random in the irradiation direction by scattering. It becomes the UV light 26 having a good directionality. That is, when viewed from the exposure target 22, UV light 23 having a substantially constant incident angle is incident when there is no UV scattering plate 25, whereas when the UV scattering plate 25 is installed, it has various incident angles. The UV light 26 is incident.
このように、ＵＶ−ＬＥＤからの射出光を、ＵＶ散乱板を介して露光対象へ照射することにより、露光対象に照射光を均一に照射することができる。したがって、本実施の形態で示したＵＶ−ＬＥＤ光源を用いることにより、露光対象が照射光の波長より小さいナノスケールの微細凹凸構造を有する場合であっても、ナノインプリントを良好に行うことができる。 Thus, the irradiation light can be uniformly irradiated to the exposure target by irradiating the exposure target with the light emitted from the UV-LED via the UV scattering plate. Therefore, by using the UV-LED light source shown in this embodiment mode, nanoimprinting can be satisfactorily performed even when the exposure target has a nanoscale fine uneven structure smaller than the wavelength of irradiation light.
なお、本発明におけるＵＶ−ＬＥＤ光源においてＵＶを露光対象に照射する角度は特に限定されるものではないが、効果的にナノインプリント法により微細凹凸構造を転写する為に、入射角が４５°以下であることが好ましい。より好ましくは、照射されるＵＶ光を効率的に利用する為に入射角が０°であることが好ましい。ここで入射角とは、露光対象面の法線に対して作られる角度であり、露光対象に垂直にＵＶ光を照射する場合が入射角０°を意味し、水平に入射する場合が入射角９０°を意味する。 In the UV-LED light source according to the present invention, the angle at which UV is irradiated onto the object to be exposed is not particularly limited. However, in order to effectively transfer the fine concavo-convex structure by the nanoimprint method, the incident angle is 45 ° or less. Preferably there is. More preferably, the incident angle is preferably 0 ° in order to efficiently use the irradiated UV light. Here, the incident angle is an angle formed with respect to the normal of the exposure target surface. When the UV light is irradiated perpendicularly to the exposure target, the incident angle is 0 °, and when the incident light is horizontal, the incident angle. It means 90 °.
本発明におけるＵＶ−ＬＥＤ光源から照射されるＵＶ光の中心波長の範囲はナノインプリント法により微細凹凸構造を転写する際に使用するＵＶ硬化性樹脂の種類によって変わるが、ＵＶ硬化性樹脂を硬化させるための開始剤の吸収波長から概ね３５５ｎｍ〜３８５ｎｍであることが好ましい。特に、ＵＶ硬化性樹脂の硬化速度が良好になる為、３５５ｎｍ〜３８０ｎｍであることがより好ましい。 The range of the central wavelength of the UV light emitted from the UV-LED light source in the present invention varies depending on the type of the UV curable resin used when transferring the fine concavo-convex structure by the nanoimprint method, but in order to cure the UV curable resin. From the absorption wavelength of the initiator, it is preferably about 355 nm to 385 nm. In particular, since the curing rate of the UV curable resin becomes good, it is more preferably 355 nm to 380 nm.
次に本発明におけるＵＶ−ＬＥＤ光源において使用されるＵＶ散乱板について説明する。 Next, the UV scattering plate used in the UV-LED light source according to the present invention will be described.
図３に示すように、本発明に係るＵＶ−ＬＥＤ光源として設置されるＵＶ散乱板は、基材３１ｃの片側表面３１ａにＵＶ−ＬＥＤの中心波長の１／１０倍以下の凹凸形状、又は、中心波長以上、好ましくは２倍以上の大きさの凹凸形状が形成された散乱板３１とすることができる（図３（Ａ）参照）。あるいは、基材３１ｃの片側表面３１ａにＵＶ−ＬＥＤ光源の中心波長の１／１０以下の凹凸形状と、中心波長以上、好ましくは中心波長の２倍以上の凹凸形状が混合した凹凸が形成された散乱板３１とすることができる。更には、上記のいずれかの凹凸形状が基材３２ｃの両側表面３２ａ、３２ｂに形成された散乱板３２であっても構わない（図３（Ｂ）参照）。尚、散乱板の凹凸形状が形成された面は、ＵＶ−ＬＥＤの照射面側にしてもよく、或いは該表面を露光対象側に向けてもよい。なお、凹凸形状の大きさとは、凸部の大きさをいう。 As shown in FIG. 3, the UV scattering plate installed as the UV-LED light source according to the present invention has an uneven shape that is 1/10 times or less the center wavelength of the UV-LED on one side surface 31a of the substrate 31c, or The scattering plate 31 can be formed with a concavo-convex shape with a center wavelength or more, preferably twice or more (see FIG. 3A). Or the unevenness | corrugation in which the uneven | corrugated shape below 1/10 of the center wavelength of UV-LED light source and the uneven | corrugated shape more than a center wavelength, Preferably twice or more of a center wavelength was formed in the one side surface 31a of the base material 31c. The scattering plate 31 can be obtained. Furthermore, the scattering plate 32 in which any one of the above-described uneven shapes is formed on both side surfaces 32a and 32b of the base material 32c may be used (see FIG. 3B). The surface on which the uneven shape of the scattering plate is formed may be on the irradiation surface side of the UV-LED, or the surface may be directed to the exposure target side. The size of the concavo-convex shape means the size of the convex portion.
また、ＵＶ散乱板を構成する母材（基材３３ｂ）中にＵＶ−ＬＥＤ光源の中心波長の１／１０倍以下、又は、中心波長以上、好ましくは２倍以上の大きさを有する分散材３３ａが形成されたＵＶ散乱板３３を用いることができる（図３（Ｃ）参照）。或いは、ＵＶ散乱板を構成する母材（基材３３ｂ）中にＵＶ−ＬＥＤ光源の中心波長の１／１０倍以下の大きさの分散材と、中心波長以上、好ましくは２倍以上の大きさを有する分散材との双方が混合分散されたＵＶ散乱板であっても構わない。また、分散剤としては、屈折率が母材と０．１以上異なる構造とすることが好ましい。 Further, a dispersion material 33a having a size of 1/10 times or less of the center wavelength of the UV-LED light source in the base material (base material 33b) constituting the UV scattering plate, or more than the center wavelength, preferably 2 times or more. Can be used (see FIG. 3C). Alternatively, in the base material (base material 33b) constituting the UV scattering plate, a dispersion material having a size not more than 1/10 times the center wavelength of the UV-LED light source and a size not less than the center wavelength, preferably not less than 2 times. It is also possible to use a UV scattering plate in which both of the dispersion material and the dispersion material are mixed and dispersed. Further, the dispersant preferably has a structure having a refractive index different from that of the base material by 0.1 or more.
更には、上記図３（Ａ）〜（Ｃ）の構成を組み合わせて、基材３４ｂの表面（３４ｃ、３４ｄ）に凹凸形状を有し且つ基材３４ｂ中に分散材（３４ａ）を分散させたＵＶ散乱板３４（図３（Ｄ）参照）としてもよい。 Further, by combining the configurations shown in FIGS. 3A to 3C, the surface (34c, 34d) of the base material 34b has an uneven shape, and the dispersion material (34a) is dispersed in the base material 34b. A UV scattering plate 34 (see FIG. 3D) may be used.
尚、ＵＶ散乱板自体の外形は特に限定されるものではなく、板状や湾曲状や筒状等が挙げられる。効率的にＵＶ光を利用する為に、ＵＶ光照射面が平らな場合は平板状のＵＶ散乱板を用いることが好ましく、ＵＶ光照射面が湾曲している場合は、照射面と同様の曲率を有するＵＶ散乱板を用いることが好ましい。 The outer shape of the UV scattering plate itself is not particularly limited, and examples thereof include a plate shape, a curved shape, and a cylindrical shape. In order to use UV light efficiently, it is preferable to use a flat UV scattering plate when the UV light irradiation surface is flat, and when the UV light irradiation surface is curved, the curvature is the same as that of the irradiation surface. It is preferable to use a UV scattering plate having
以下、表面に凹凸を持つＵＶ散乱板について説明し、続いて内部に屈折率の異なる構造を持つＵＶ散乱板について説明する。 Hereinafter, a UV scattering plate having irregularities on the surface will be described, and subsequently, a UV scattering plate having a structure with a different refractive index inside will be described.
ＵＶ散乱板表面に形成される凹凸形状は、ＵＶ散乱板全てに渡り形成されても良いし、ＵＶ光が透過する部分のみに形成されてもよい。該凹凸形状は、ＵＶ光を効果的に散乱させ且つナノインプリント法により微細凹凸構造を効果的に転写する為に、ＵＶ−ＬＥＤから照射されるＵＶ光の中心波長の１／１０倍以下及び／又は１〜２倍以上の大きさであることが好ましい。波長の１／１０倍以下の微細凹凸構造に対しては主にレイリー散乱による散乱が生じ、波長の１〜２倍以上の微細凹凸構造に対しては主にミー散乱による散乱が生じる。 The concavo-convex shape formed on the surface of the UV scattering plate may be formed over the entire UV scattering plate, or may be formed only in a portion through which the UV light is transmitted. The concavo-convex shape is less than 1/10 times the center wavelength of the UV light emitted from the UV-LED and / or in order to effectively scatter UV light and effectively transfer the fine concavo-convex structure by the nanoimprint method. The size is preferably 1 to 2 times or more. Scattering mainly due to Rayleigh scattering occurs for a fine uneven structure having a wavelength of 1/10 or less of the wavelength, and scattering mainly due to Mie scattering occurs for a fine uneven structure having a wavelength of 1 to 2 times or more of the wavelength.
ＵＶ散乱板表面に形成される凹凸形状の分布や規則性は特に限定されるものでなく、例えば単一の大きさを有する凹凸が不規則に形成されている状態や単一の大きさを有する凹凸が規則的に形成されている状態や、或いは複数の大きさの凹凸が規則的に形成されている状態や複数の大きさの凹凸が不規則に形成されている状態等が挙げられる。より好ましくは、ＵＶ−ＬＥＤから照射されるＵＶ光は波長に分布を有する為、照射されるＵＶ光を効果的に散乱させる為に、複数の大きさの凹凸形状がＵＶ散乱板表面に形成されていることが好ましい。 The distribution and regularity of the uneven shape formed on the surface of the UV scattering plate is not particularly limited. For example, the unevenness having a single size is irregularly formed or has a single size. Examples include a state where irregularities are regularly formed, a state where irregularities with a plurality of sizes are regularly formed, and a state where irregularities with a plurality of sizes are irregularly formed. More preferably, since the UV light emitted from the UV-LED has a distribution in wavelength, a plurality of uneven shapes are formed on the surface of the UV scattering plate in order to effectively scatter the irradiated UV light. It is preferable.
ＵＶ散乱板表面に形成される凹凸形状の形成方法は特に限定されるものではないが、例えば、微細凹凸構造を有する鑢等でＵＶ散乱板となる基材表面を擦る方法や、切削等により凹凸を形成する方法や、インプリント法により散乱板となる基材表面に凹凸を転写する方法や、溶剤により散乱板となる基材表面を溶解させ凹凸を形成する方法や、化学溶液析出法やｓｏｌ−ｇｅｌ法等で散乱板となる基材表面に凹凸を形成する方法や、スパッタや蒸着等で散乱板となる基材表面に凹凸を形成する方法や、ガラスやポリスチレンスルホン酸、フッ化ビニリデン、ポリカーボネート、アクリル樹脂、メタアクリル樹脂等の微粒子を散乱板となる基材表面にスピンコーティング法やグラビアメッシュによる塗布やディップ法やスプレー法や交互積層法等を利用し添着する方法や、エレクトロスピニング法等によりファイバーを基材表面に添着し散乱板となる基材表面に凹凸を形成する方法や、プラズマやコロナ放電等で散乱板となる基材表面に凹凸を形成する方法や、押し出し成型時に散乱板となる基材表面に凹凸を形成する方法等が挙げられる。 The method for forming the uneven shape formed on the surface of the UV scattering plate is not particularly limited. For example, the method for rubbing the surface of the substrate serving as the UV scattering plate with a wrinkle or the like having a fine uneven structure, or unevenness by cutting or the like. , A method of transferring irregularities on the surface of the base material to be a scattering plate by an imprint method, a method of forming irregularities by dissolving the base material surface to be a scattering plate with a solvent, a chemical solution deposition method and a sol A method of forming irregularities on the surface of the base material that becomes the scattering plate by the -gel method, a method of forming irregularities on the surface of the base material that becomes the scattering plate by sputtering or vapor deposition, glass, polystyrene sulfonic acid, vinylidene fluoride, Applying fine particles such as polycarbonate, acrylic resin, methacrylic resin, etc. to the surface of the base material that serves as a scattering plate by spin coating, gravure mesh, dipping, spraying, or alternating lamination A method of attaching using fibers, a method of attaching fibers to the surface of a substrate by electrospinning or the like, and forming irregularities on the surface of the substrate that becomes a scattering plate, or a surface of a substrate that becomes a scattering plate by plasma or corona discharge Examples thereof include a method for forming irregularities and a method for forming irregularities on the surface of a base material that becomes a scattering plate during extrusion molding.
ＵＶ散乱板を構成する基材の材質としては、ＵＶ−ＬＥＤから射出されるＵＶ光を透過すれば特に限定されるものではなく、例えば、ポリエチレンテレフタレート、ポリカーボネート、アクリル樹脂、メタアクリル樹脂、石英、ガラス等が挙げられる。 The material of the base material constituting the UV scattering plate is not particularly limited as long as it transmits UV light emitted from the UV-LED. For example, polyethylene terephthalate, polycarbonate, acrylic resin, methacrylic resin, quartz, Glass etc. are mentioned.
ＵＶ散乱板を構成する基材の内部に形成される屈折率が母材とは０．１以上異なる構造（分散剤）は、基材内部全てに渡り形成されても良いし、ＵＶ光が透過する部分のみに形成されてもよい。該構造は、ＵＶ光を効果的に散乱させ且つナノインプリント法により微細凹凸構造を効果的に転写する為に、ＵＶ−ＬＥＤ光源から照射されるＵＶ光の散乱板の母材中での光学的中心波長の１／１０倍以下及び／又は１〜２倍以上の大きさであることが好ましい。波長の１／１０倍以下の微細凹凸構造に対しては主にレイリー散乱による散乱が、波長の１〜２倍以上の微細凹凸構造に対しては主にミー散乱による散乱が生じる。 A structure (dispersant) having a refractive index different from that of the base material by 0.1 or more formed in the base material constituting the UV scattering plate may be formed over the entire base material, or transmits UV light. You may form only in the part to do. The structure has an optical center in a base material of a UV light scattering plate irradiated from a UV-LED light source in order to effectively scatter UV light and effectively transfer a fine uneven structure by a nanoimprint method. The size is preferably 1/10 or less and / or 1 to 2 or more times the wavelength. Scattering mainly due to Rayleigh scattering occurs for fine uneven structures having a wavelength of 1/10 or less of the wavelength, and scattering mainly due to Mie scattering occurs for fine uneven structures having a wavelength of 1 to 2 times or more of the wavelength.
これらの屈折率が母材とは０．１以上異なる構造（分散剤）の分布や規則性は特に限定されるものではないが、例えば単一の大きさを有する分散剤が不規則に形成されている状態や、単一の大きさを有する分散剤が規則的に形成されている状態や、或いは複数の大きさの分散剤が規則的に形成されている状態や、複数の大きさの分散剤が不規則に形成されている状態等が挙げられる。より好ましくは、ＵＶ−ＬＥＤ光源から照射されるＵＶ光は波長が分布を有す為、効果的に照射されるＵＶ光を散乱させる為に、複数の大きさの分散剤が散乱板内部に形成されることが好ましい。 The distribution and regularity of the structure (dispersant) whose refractive index is 0.1 or more different from that of the base material is not particularly limited, but for example, a dispersant having a single size is irregularly formed. A state in which a dispersant having a single size is regularly formed, a state in which a dispersant having a plurality of sizes is regularly formed, and a dispersion having a plurality of sizes. The state etc. in which the agent is irregularly formed are mentioned. More preferably, since the UV light emitted from the UV-LED light source has a wavelength distribution, a plurality of sizes of dispersing agents are formed inside the scattering plate in order to effectively scatter the irradiated UV light. It is preferred that
分散剤を散乱板内部に形成する方法は特に限定されるものではないが、例えば、散乱板となる基材を製造する際に、２種類以上の樹脂を混合した原料を利用する方法やポリエチレンテレフタレート、ポリカーボネート、アクリル樹脂、メタアクリル樹脂、ポリスチレンスルホン酸、フッ化ビニリデン、石英、ガラス等の微粒子を主成分となる樹脂中に混合した原料を利用する方法や原料となる樹脂の中に気泡や溶剤泡を混入する方法や、２種類以上の樹脂を混合した原料やポリエチレンテレフタレート、ポリカーボネート、アクリル樹脂、メタアクリル樹脂、ポリスチレンスルホン酸、フッ化ビニリデン、石英、ガラス等の微粒子を主成分となる樹脂中に混合した原料を利用し基材を製造した後にこれらの添加物を溶剤や加熱や酸等により溶解させる方法等が挙げられる。なお、分散剤の形状としては、球状、楕円状、迷路状（複数ポリマを混合したときに自発的に形成される構造）等様々な形状とすることができる。 The method for forming the dispersing agent inside the scattering plate is not particularly limited. For example, when producing a base material to be a scattering plate, a method using a raw material in which two or more kinds of resins are mixed, or polyethylene terephthalate , Polycarbonate, acrylic resin, methacrylic resin, polystyrene sulfonic acid, vinylidene fluoride, quartz, glass, etc. In a resin containing mainly fine particles such as foam mixing method, raw materials mixed with two or more kinds of resins, polyethylene terephthalate, polycarbonate, acrylic resin, methacrylic resin, polystyrene sulfonic acid, vinylidene fluoride, quartz, glass, etc. After manufacturing the base material using the raw materials mixed in, these additives are dissolved by solvent, heating, acid, etc. And a method such as to. In addition, as a shape of a dispersing agent, it can be set as various shapes, such as spherical shape, an ellipse shape, and a maze shape (structure formed spontaneously when a several polymer is mixed).
散乱板の材質としては、ＵＶ光を透過すれば特に限定されるものではなく、例えば、ポリエチレンテレフタレート、ポリカーボネート、アクリル樹脂、メタアクリル樹脂、石英、ガラス等が挙げられる。 The material of the scattering plate is not particularly limited as long as it transmits UV light, and examples thereof include polyethylene terephthalate, polycarbonate, acrylic resin, methacrylic resin, quartz, and glass.
ナノインプリント法において、本発明に係るＵＶ−ＬＥＤ光源を適用することにより著しい効果を得ることができる微細凹凸として、凹凸の大きさが４０ｎｍ〜３８０ｎｍであり且つピッチが３８６ｎｍ以下の微細凹凸構造がある。これは、散乱板がない場合、ＵＶ−ＬＥＤ光源から照射されるＵＶ光は直進性高く露光対象へと照射される。該露光対象の微細凹凸構造が、凹凸の大きさが４０ｎｍ〜３８０ｎｍであり且つピッチが３８６ｎｍ以下で形成されている場合は、照射されるＵＶ光は該微細凹凸に対して散乱及び回折を伴わない為、直進性の高いＵＶ光が照射される部分以外のＵＶ硬化性樹脂は硬化せず、それによりナノインプリント法による転写が不完全になると推定される。例えば、波長が３５５ｎｍのＵＶ光に対して、微細凹凸のピッチが３５６ｎｍ以下になると回折光はゼロ次の回折光のみとなり、波長３８５ｎｍのＵＶ光に対して、微細凹凸のピッチが３８６ｎｍ以下になると回折光はゼロ次の回折光のみとなる。一方で、本発明に係るＵＶ−ＬＥＤ光源に散乱板が存在することで、露光対象の微細凹凸による散乱及び回折が生じなくとも、散乱板を透過したＵＶ光は露光対象に対して様々な入射角を持って照射されるため、ナノインプリント法による転写が良好に行われるものと推定される。 In the nanoimprint method, as a fine unevenness that can obtain a remarkable effect by applying the UV-LED light source according to the present invention, there is a fine uneven structure having an unevenness of 40 nm to 380 nm and a pitch of 386 nm or less. This is because, when there is no scattering plate, UV light emitted from the UV-LED light source is irradiated straight onto the exposure target with high straightness. When the fine concavo-convex structure to be exposed is formed with a concavo-convex size of 40 nm to 380 nm and a pitch of 386 nm or less, the irradiated UV light is not scattered and diffracted with respect to the fine concavo-convex structure. Therefore, it is presumed that the UV curable resin other than the portion irradiated with the UV light having high straightness does not cure, and that the transfer by the nanoimprint method is incomplete. For example, when the pitch of fine irregularities is 356 nm or less for UV light with a wavelength of 355 nm, the diffracted light is only zero-order diffracted light, and when the pitch of fine irregularities is 386 nm or less for UV light with a wavelength of 385 nm. Diffracted light is only zero-order diffracted light. On the other hand, the presence of the scattering plate in the UV-LED light source according to the present invention allows the UV light transmitted through the scattering plate to be incident on the exposure target in various ways, even if scattering and diffraction due to fine unevenness of the exposure target do not occur. Since it is irradiated with an angle, it is presumed that transfer by the nanoimprint method is performed well.
次に、本発明の効果を明確にするために行った実施例について説明する。なお、本発明は、以下の実施例によって何ら限定されるものではない。 Next, examples performed for clarifying the effects of the present invention will be described. In addition, this invention is not limited at all by the following examples.
（実施例１）
微細凹凸の大きさが１５０ｎｍ且つピッチが１４０ｎｍの微細凹凸構造を表面に有するニッケル製の金型に株式会社ハーベスのDurasurf 2101Zを用い離型処理を施し、トリメチロールプロパントリアクリレート（東亞合成株式会社 Ｍ３５０）を主成分とするＵＶ硬化性樹脂を前記金型の微細凹凸構造面上に滴下し、１００μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルムを貼り合わせると同時にハンドローラーを用いＵＶ硬化性樹脂を引き延ばし、露光対象を作製した。続いて、鑢により１〜１００μｍ程度の大きさを有する凹凸形状をＰＥＴフィルム表面に形成し、中心波長が３７５±５ｎｍであり且つ出力が２．６ＷのＵＶ−ＬＥＤハンドライトのＵＶ照射面に固定し、ＵＶ散乱板を有するＵＶ−ＬＥＤ光源を作製した。その後、前記露光対象に該ＵＶ−ＬＥＤ光源を用いＵＶ光を３分間照射した。照射後、露光対象の金型とＰＥＴフィルムを剥離した。
Example 1
A nickel mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 140 nm on the surface was subjected to mold release using Durasurf 2101Z from Harves Co., Ltd., and trimethylolpropane triacrylate (Toagosei Co., Ltd. M350 ) As a main component is dripped onto the fine concavo-convex structure surface of the mold, a polyethylene terephthalate (PET) film having a thickness of 100 μm is bonded, and at the same time, the UV curable resin is stretched using a hand roller, and exposed. A subject was created. Subsequently, a concavo-convex shape having a size of about 1 to 100 μm is formed on the PET film surface with a scissors, and fixed to the UV irradiation surface of a UV-LED handlight having a center wavelength of 375 ± 5 nm and an output of 2.6 W. Then, a UV-LED light source having a UV scattering plate was produced. Then, UV light was irradiated to the said exposure object for 3 minutes using this UV-LED light source. After the irradiation, the mold to be exposed and the PET film were peeled off.
得られたＰＥＴフィルムのＵＶ硬化性樹脂と接していた面を、原子間力顕微鏡を用いて評価した。その結果、フィルム全面に渡り微細凹凸構造が形成されていた（図５（Ａ）参照）。 The surface of the obtained PET film that was in contact with the UV curable resin was evaluated using an atomic force microscope. As a result, a fine concavo-convex structure was formed over the entire film surface (see FIG. 5A).
（実施例２）
微細凹凸の大きさが１５０ｎｍ且つピッチが１４０ｎｍの微細凹凸構造を表面に有するニッケル製の金型に株式会社ハーベスのDurasurf 2101Zを用い離型処理を施し、トリメチロールプロパントリアクリレート（東亞合成株式会社 Ｍ３５０）を主成分とするＵＶ硬化性樹脂を前記金型の微細凹凸構造面上に滴下し、１００μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルムを貼り合わせると同時にハンドローラーを用いＵＶ硬化性樹脂を引き延ばし、露光対象を作製した。続いて、平均粒径２μｍのポリメチルメタクリレート微粒子を分散させた１−ヒドロキシシクロヘキシルフェニルケトンを含有するトリメチロールプロパントリアクリレート溶液を、ＰＥＴフィルム上に製膜し、ＵＶ光により硬化させることで散乱板を作製した。続いて該散乱板を中心波長が３７５±５ｎｍであり且つ出力が２．６ＷのＵＶ−ＬＥＤハンドライトのＵＶ照射面に固定し、散乱板を有するＵＶ−ＬＥＤ光源を作製した。その後、前記露光対象に該ＵＶ−ＬＥＤ光源を用いＵＶ光を３分間照射した。照射後、露光対象の金型とＰＥＴフィルムを剥離した。
(Example 2)
A mold made of nickel having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 140 nm on the surface was subjected to mold release treatment using Durasurf 2101Z of Harves Co., Ltd., and trimethylolpropane triacrylate (Toagosei Co., Ltd. M350 ) As a main component is dripped onto the fine concavo-convex structure surface of the mold, a polyethylene terephthalate (PET) film having a thickness of 100 μm is bonded, and at the same time, the UV curable resin is stretched using a hand roller, and exposed. A subject was created. Subsequently, a trimethylolpropane triacrylate solution containing 1-hydroxycyclohexyl phenyl ketone in which polymethyl methacrylate fine particles having an average particle diameter of 2 μm are dispersed is formed on a PET film and cured by UV light, thereby scattering plates. Was made. Subsequently, the scattering plate was fixed to the UV irradiation surface of a UV-LED handlight having a center wavelength of 375 ± 5 nm and an output of 2.6 W, thereby producing a UV-LED light source having a scattering plate. Then, UV light was irradiated to the said exposure object for 3 minutes using this UV-LED light source. After the irradiation, the mold to be exposed and the PET film were peeled off.
得られたＰＥＴフィルムのＵＶ硬化性樹脂と接していた面を、原子間力顕微鏡を用いて評価した。その結果、フィルム全面に渡り微細凹凸構造が形成されていた（図５（Ｂ）参照）。 The surface of the obtained PET film that was in contact with the UV curable resin was evaluated using an atomic force microscope. As a result, a fine concavo-convex structure was formed over the entire film surface (see FIG. 5B).
（比較例１）
微細凹凸の大きさが１５０ｎｍ且つピッチが１４０ｎｍの微細凹凸構造を表面に有するニッケル製の金型に株式会社ハーベスのDurasurf 2101Zを用い離型処理を施し、トリメチロールプロパントリアクリレート（東亞合成株式会社 Ｍ３５０）を主成分とするＵＶ硬化性樹脂を前記金型の微細凹凸構造面上に滴下し、１００μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルムを貼り合わせると同時にハンドローラーを用いＵＶ硬化性樹脂を引き延ばし、露光対象を作製した。続いて、該露光対象に中心波長が３７５±５ｎｍであり且つ出力が２．６ＷのＵＶ−ＬＥＤ光源を用いＵＶ光を３分間照射した。照射後、露光対象の金型とＰＥＴフィルムを剥離した。
(Comparative Example 1)
A nickel mold having a fine concavo-convex structure with a fine concavo-convex size of 150 nm and a pitch of 140 nm on the surface was subjected to mold release using Durasurf 2101Z from Harves Co., Ltd., and trimethylolpropane triacrylate (Toagosei Co., Ltd. M350 ) As a main component is dripped onto the fine concavo-convex structure surface of the mold, a polyethylene terephthalate (PET) film having a thickness of 100 μm is bonded, and at the same time, the UV curable resin is stretched using a hand roller, and exposed. A subject was created. Subsequently, the exposure object was irradiated with UV light for 3 minutes using a UV-LED light source having a center wavelength of 375 ± 5 nm and an output of 2.6 W. After the irradiation, the mold to be exposed and the PET film were peeled off.
得られたＰＥＴフィルムのＵＶ硬化性樹脂と接していた面を、原子間力顕微鏡を用いて評価した。その結果、微細凹凸構造の転写は確認できなかった（図５（Ｃ）参照）。 The surface of the obtained PET film that was in contact with the UV curable resin was evaluated using an atomic force microscope. As a result, transfer of the fine uneven structure could not be confirmed (see FIG. 5C).
本発明のナノインプリント用のＵＶ−ＬＥＤ光源によれば、低寿命且つ高消費電力の高圧水銀等のようなＵＶ光源を使用することなく、高寿命且つ低消費電力のＵＶ−ＬＥＤ光源からナノインプリント法により効果的に微細凹凸構造を転写できる点で有用である。 According to the UV-LED light source for nanoimprinting of the present invention, a UV-LED light source having a long life and a low power consumption can be obtained by a nanoimprint method without using a UV light source such as a high-pressure mercury having a low life and a high power consumption. This is useful in that the fine uneven structure can be effectively transferred.
１０ ＵＶ−ＬＥＤ光源
１１ ＵＶ−ＬＥＤ
１２ ＵＶ−ＬＥＤの照射面
１３ 露光対象の照射面
１４ 露光対象
１５ 散乱板
１６ 露光対象の露光面との間
２１ ＵＶ−ＬＥＤ
２２ 露光対象
２３ 散乱板がない場合のＵＶ光の進行
２４ 散乱板までのＵＶ光の進行
２５ 散乱板
２６ 散乱板通過後のＵＶ光の進行
３１ 片側表面にのみ微細凹凸が形成された散乱板
３２ 両側表面に微細凹凸が形成された散乱板
３３ 屈折率の異なる構造を内部に含む散乱板
３４ 屈折率の異なる構造を内部に含み且つ表面に微細凹凸が形成された散乱板
10 UV-LED light source 11 UV-LED
12 UV-LED irradiation surface 13 Exposure target irradiation surface 14 Exposure target 15 Scattering plate 16 Between exposure target exposure surface 21 UV-LED
22 Exposure object 23 Progression of UV light when there is no scattering plate 24 Progression of UV light to the scattering plate 25 Scattering plate 26 Progression of UV light after passing through the scattering plate 31 Scattering plate with fine irregularities formed only on one side surface 32 Scattering plate with fine irregularities formed on both surface surfaces 33 Scattering plate containing structures with different refractive indices inside 34 Scattering plate containing structures with different refractive indexes inside and fine irregularities formed on the surface
Claims (5)
A structure having a concavo-convex pitch of 40 nm or more and 380 nm or less is produced by the nanoimprint method using the nanoimprint UV-LED light source according to any one of claims 1 to 4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021068890A (en) * | 2019-10-23 | 2021-04-30 | キヤノン株式会社 | System and method for curing imprint film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021068890A (en) * | 2019-10-23 | 2021-04-30 | キヤノン株式会社 | System and method for curing imprint film |
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