JP2016071120A - ND filter - Google Patents

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JP2016071120A
JP2016071120A JP2014199889A JP2014199889A JP2016071120A JP 2016071120 A JP2016071120 A JP 2016071120A JP 2014199889 A JP2014199889 A JP 2014199889A JP 2014199889 A JP2014199889 A JP 2014199889A JP 2016071120 A JP2016071120 A JP 2016071120A
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filter
transmittance
wavelength
material layer
light
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那由太 嶋田
Nayuta Shimada
那由太 嶋田
健児 矢沢
Kenji Yazawa
健児 矢沢
貴壽 山田
Takatoshi Yamada
貴壽 山田
貴志 八木
Takashi Yagi
貴志 八木
めぐみ 阿子島
Megumi Akoshima
めぐみ 阿子島
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National Institute of Advanced Industrial Science and Technology AIST
Oike and Co Ltd
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National Institute of Advanced Industrial Science and Technology AIST
Oike and Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide an ND filter having a constant, wavelength-independent light absorption property in an infrared region with a wavelength of no less than 1500 nm.SOLUTION: An ND filter comprises a base material 11 that exhibits transmittance variation of no greater than 10% in a wavelength range of 1500-2500 nm, inclusive, and a light absorptive material layer 13 provided on a surface of the base material 11, where the light absorptive layer 13 comprises a plurality of laminated graphene films, and features a transmittance of 1-90%, inclusive, at a wavelength of 550 nm, and a difference T(range) between a minimum transmittance T(min)(1500-4000) and a maximum transmittance T(max)(1500-4000) of no greater than 8.0% in a wavelength range of 1500-4000 nm, inclusive.SELECTED DRAWING: Figure 1

Description

本発明は、ＮＤ（ニュートラルデンシティ）フィルタに関する。特に、赤外線領域で波長に依存せず一定の光吸収特性を有するＮＤフィルタに関する。 The present invention relates to an ND (neutral density) filter. In particular, the present invention relates to an ND filter having a constant light absorption characteristic independent of wavelength in the infrared region.

ＮＤ（ニュートラルデンシティ）フィルタは、各種の光学機器における透過光量の制御に用いられている。例えば、カメラやビデオカメラなどのレンズ光学系や、テレビやパソコンのディスプレーの光量調節、バスや飛行機の照明の光量や射出方向の制御等、幅広い分野で利用されている。 An ND (neutral density) filter is used to control the amount of transmitted light in various optical devices. For example, it is used in a wide range of fields, such as lens optical systems such as cameras and video cameras, adjustment of the light amount of television and personal computer displays, and control of the light amount and emission direction of bus and airplane lighting.

従来のＮＤフィルタは、樹脂に有機色素または顔料を混合したり、プラスチック等の透明基材に光学特性を有する膜を蒸着により形成したりして、所定の形状に加工することにより製造されている。このような従来のＮＤフィルタは、可視光領域の光を均一に吸収（減光）するように構成されているものの、赤外線領域の光については、透過するか、不均一な吸収をするものしか知られていない。 Conventional ND filters are manufactured by mixing organic dyes or pigments into a resin, or forming a film having optical properties on a transparent substrate such as plastic by vapor deposition, and processing it into a predetermined shape. . Such a conventional ND filter is configured to uniformly absorb (reduce) light in the visible light region, but only transmits light in the infrared region or absorbs unevenly. unknown.

赤外線領域の光を吸収するＮＤフィルタとして、例えば、特許文献１には、不織布層を少なくとも一層有し、繊維間を抵抗無く透過する光と、繊維によって反射・吸収される光が区別され、繊維の太さ、不織布の目付け重量、厚さ等で透過率を任意に調節することができ、可視光線（４００〜７００ｎｍ）から近赤外線（７００〜２０００ｎｍ）の広範囲の波長の光を吸収（減光）して、透過率を０〜８０％の範囲で調光を可能なＮＤフィルタが記載されている。しかし、特許文献１のＮＤフィルタは、可視光線の範囲の波長の光は均一に吸収するものの、１０００ｎｍ以上の波長の光では、透過率が不均一となる。 As an ND filter that absorbs light in the infrared region, for example, Patent Document 1 has at least one non-woven fabric layer, and distinguishes between light that is transmitted between fibers without resistance and light that is reflected and absorbed by the fibers. The transmittance can be adjusted arbitrarily according to the thickness of the fiber, the weight of the nonwoven fabric, the thickness, etc., and absorbs light in a wide range of wavelengths from visible light (400 to 700 nm) to near infrared (700 to 2000 nm). ND filter capable of dimming in a transmittance range of 0 to 80%. However, although the ND filter of Patent Document 1 uniformly absorbs light having a wavelength in the visible light range, the transmittance is not uniform for light having a wavelength of 1000 nm or more.

また、特許文献２には、半導体基板と、当該半導体基板の一表面側に形成された広帯域遮断フィルタ部と、当該半導体基板の他表面側に形成された狭帯域透過フィルタ部とを備え、８００ｎｍ〜２００００ｎｍの波長域の赤外線を制御する赤外線光学フィルタが記載されている。特許文献２では、広帯域遮断フィルタ部が、屈折率が異なる複数種類の薄膜が積層された多層膜からなり、当該複数種類の薄膜のうち１種類の薄膜が遠赤外線を吸収する遠赤外線吸収材料（例えば、Ａｌ２Ｏ３など）により形成され、残りの１種類の薄膜が上記遠赤外線吸収材料よりも屈折率の高い高屈折率材料（例えば、Ｇｅなど）により形成されていることが記載されている。しかし、特許文献２の赤外線光学フィルタにおいても、１０００ｎｍ以上の波長の光を吸収するものの、広範な赤外線領域の光に対して透過率が均一にはならない。 Patent Document 2 includes a semiconductor substrate, a broadband cutoff filter portion formed on one surface side of the semiconductor substrate, and a narrow band transmission filter portion formed on the other surface side of the semiconductor substrate, and has a wavelength of 800 nm. An infrared optical filter for controlling infrared rays in a wavelength range of ˜20,000 nm is described. In Patent Document 2, the broadband cutoff filter portion is formed of a multilayer film in which a plurality of types of thin films having different refractive indexes are stacked, and one type of thin film among the plurality of types of thin films absorbs far infrared rays ( for example, is formed of Al etc. 2 O 3), the remaining one type of a thin film having a high refractive index than the far-infrared-absorbing material a high refractive index material (e.g., is described to be formed by Ge, etc.) Yes. However, the infrared optical filter of Patent Document 2 also absorbs light having a wavelength of 1000 nm or more, but the transmittance is not uniform for light in a wide infrared region.

特開２００６−０１７８３２号公報JP 2006-017832 A 特開２０１０−１８６１４５号公報JP 2010-186145 A

本発明は、上述の問題を解決するものであって、波長が１５００ｎｍ以上の赤外線領域で波長に依存せず一定の光吸収特性を有するＮＤフィルタを提供することを目的とする。 The present invention solves the above-described problems, and an object of the present invention is to provide an ND filter having a constant light absorption characteristic regardless of the wavelength in an infrared region having a wavelength of 1500 nm or more.

本発明の一実施形態によると、波長１５００ｎｍ以上２５００ｎｍ以下における透過率の変化が１０％以内の基材と、前記基材表面に配置された光吸収材料層と、を備え、前記光吸収材料層は複数のグラフェン膜が積層した構造を有し、波長５５０ｎｍの透過率が１％以上９０％以下であり、且つ、波長１５００ｎｍ以上４０００ｎｍ以下における透過率の最小値Ｔ（ｍｉｎ）（１５００−４０００）と最大値Ｔ（ｍａｘ）（１５００−４０００）との差Ｔ（ｒａｎｇｅ）が８．０％以下を満たすＮＤフィルタが提供される。 According to an embodiment of the present invention, the light absorption material layer includes: a base material whose transmittance change within a wavelength of 1500 nm to 2500 nm is 10% or less; and a light absorption material layer disposed on the surface of the base material. Has a structure in which a plurality of graphene films are laminated, the transmittance at a wavelength of 550 nm is 1% or more and 90% or less, and the minimum value T (min) of the transmittance at a wavelength of 1500 nm or more and 4000 nm or less (1500-4000) And a maximum value T (max) (1500-4000) is provided with an ND filter that satisfies a T (range) of 8.0% or less.

前記ＮＤフィルタにおいて、前記光吸収材料層は、共鳴ラマン散乱測定法により測定された１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．５以下であってもよい。 In the ND filter, the light-absorbing material layer, the minimum intensity value in the range of 1480 cm -1 or 1560 cm -1 or less as determined by resonance Raman scattering measurement method G 1, 1560 cm -1 or 1600 cm -1 or less When the maximum intensity value within the range is G 2 , the G 1 / G 2 ratio may be 0.5 or less.

前記ＮＤフィルタにおいて、前記光吸収材料層は、共鳴ラマン散乱測定法により測定された２５５０ｃｍ−１以上２８００ｃｍ−１以下の範囲内での最大の強度値を２Ｄｍａｘ、最小の強度値を２Ｄｍｉｎとしたときに、２Ｄｍａｘ／２Ｄｍｉｎ比が１．５以上であってもよい。 In the ND filter, the light absorbing material layer comprises a 2D min maximum intensity values 2D max, the minimum intensity value in the range of 2550 cm -1 or 2800 cm -1 or less as determined by resonance Raman scattering measurement method The 2D max / 2D min ratio may be 1.5 or more.

前記ＮＤフィルタにおいて、前記光吸収材料層は、マイクロ波表面波プラズマ化学気相成長法により形成されたグラフェン膜が積層した構造体であってもよい。 In the ND filter, the light absorbing material layer may be a structure in which graphene films formed by a microwave surface wave plasma chemical vapor deposition method are stacked.

前記ＮＤフィルタにおいて、前記基材と、前記光吸収材料層は、接着層を介さずに密着してもよい。 In the ND filter, the base material and the light absorbing material layer may be in close contact without an adhesive layer.

前記ＮＤフィルタにおいて、波長１５００ｎｍ以上２５００ｎｍ以下における前記基材の透過率が９０％以上であってもよい。 In the ND filter, the transmittance of the base material at a wavelength of 1500 nm to 2500 nm may be 90% or more.

本発明によると、波長が１５００ｎｍ以上の赤外線領域で波長に依存せず一定の光吸収特性を有するＮＤフィルタが提供される。 According to the present invention, there is provided an ND filter having a constant light absorption characteristic regardless of the wavelength in an infrared region having a wavelength of 1500 nm or more.

本発明の一実施形態に係るＮＤフィルタ１０を示す模式図である。It is a mimetic diagram showing ND filter 10 concerning one embodiment of the present invention. 本発明の一実施形態に係るＮＤフィルタ２０を示す模式図である。It is a mimetic diagram showing ND filter 20 concerning one embodiment of the present invention. 本発明の一実施例に係るＮＤフィルタの波長１５００〜２５００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in wavelength 1500-2500nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 3000-4000 nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを示す図である。It is a figure which shows the Raman spectrum measured using the laser of 532 nm wavelength of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長１５００〜２５００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in wavelength 1500-2500nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 3000-4000 nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを示す図である。It is a figure which shows the Raman spectrum measured using the laser of 532 nm wavelength of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長１５００〜２５００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in wavelength 1500-2500nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 3000-4000 nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを示す図である。It is a figure which shows the Raman spectrum measured using the laser of 532 nm wavelength of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長１５００〜２５００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in wavelength 1500-2500nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 3000-4000 nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを示す図である。It is a figure which shows the Raman spectrum measured using the laser of 532 nm wavelength of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長１５００〜２５００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in wavelength 1500-2500nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 3000-4000 nm of the ND filter which concerns on one Example of this invention. 本発明の一実施例に係るＮＤフィルタの５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを示す図である。It is a figure which shows the Raman spectrum measured using the laser of 532 nm wavelength of the ND filter which concerns on one Example of this invention. 比較例のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 1500-2500 nm of the ND filter of a comparative example. 比較例のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 3000-4000 nm of the ND filter of a comparative example. 比較例のＮＤフィルタの５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを示す図である。It is a figure which shows the Raman spectrum measured using the 532 nm wavelength laser of the ND filter of a comparative example. 比較例のＮＤフィルタの波長１５００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in wavelength 1500-4000nm of the ND filter of a comparative example. 比較例のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す図である。It is a figure which shows the transmittance | permeability in the wavelength of 3000-4000 nm of the ND filter of a comparative example. 比較例のＮＤフィルタの５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを示す図である。It is a figure which shows the Raman spectrum measured using the 532 nm wavelength laser of the ND filter of a comparative example.

上述したように、赤外線を吸収する不織布層や金属材料を用いると、１０００ｎｍ以上の波長の光では、透過率が不均一となることから、１０００ｎｍ以上、特に１５００ｎｍ以上の波長の光に対して透過率が均一となる材料の探索を行った。その結果、グラフェンは２６０ｎｍの光の吸収ピークを有するものの、１５００ｎｍ以上の赤外線領域には光の吸収ピークを有しないことを見出し、本発明を完成させた。 As described above, when a non-woven fabric layer or a metal material that absorbs infrared rays is used, the transmittance of light with a wavelength of 1000 nm or more becomes non-uniform, so that it transmits light with a wavelength of 1000 nm or more, particularly 1500 nm or more. We searched for materials with uniform rates. As a result, it was found that graphene has a light absorption peak of 260 nm, but does not have a light absorption peak in the infrared region of 1500 nm or more, and completed the present invention.

以下、図面を参照して本発明に係るＮＤフィルタについて説明する。但し、本発明のＮＤフィルタは、以下に示す実施の形態及び実施例の記載内容に限定して解釈されるものではない。なお、本実施の形態及び実施例で参照する図面において、同一部分又は同様な機能を有する部分には同一の符号を付し、その繰り返しの説明は省略する。 The ND filter according to the present invention will be described below with reference to the drawings. However, the ND filter of the present invention is not construed as being limited to the description of the embodiments and examples described below. Note that in the drawings referred to in this embodiment mode and examples, the same portions or portions having similar functions are denoted by the same reference numerals, and repetitive description thereof is omitted.

（実施形態１）
図１は、本発明の一実施形態に係るＮＤフィルタ１０を示す模式図である。ＮＤフィルタ１０は、基材１１と、基材１１の少なくとも１つの面に配置された光吸収材料層１３と、を備える。基材１１は、波長１５００ｎｍ以上２５００ｎｍ以下における透過率の変化１０％以内の基材であって、例えば、ガラス基板、Ｓｉ基板、Ｇｅ基板やＺｎＳ基板、フッ化カルシウムなどのフッ化物基板、サファイア等の酸化物基板、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ＰＣ（ポリカーボネート）、アクリル等の樹脂基板等を用いることができる。２５００ｎｍ以下のＮＤフィルタとして用いる際には、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ＰＣ（ポリカーボネート）、アクリル等の樹脂基板が好適である。また、図１において、基材１１を平板構造として示したが、本発明に係るＮＤフィルタは、これに限定されるものではなく、球体、レンズ型構造等の曲面を有する構造体、粗面を有する構造体、所定のパターン形状を有する構造体等であってもよい。 (Embodiment 1)
FIG. 1 is a schematic diagram showing an ND filter 10 according to an embodiment of the present invention. The ND filter 10 includes a base material 11 and a light absorbing material layer 13 disposed on at least one surface of the base material 11. The base material 11 is a base material having a transmittance change within 10% at a wavelength of 1500 nm to 2500 nm. For example, a glass substrate, a Si substrate, a Ge substrate, a ZnS substrate, a fluoride substrate such as calcium fluoride, sapphire, etc. An oxide substrate, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), an acrylic resin substrate, or the like can be used. When used as an ND filter of 2500 nm or less, resin substrates such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), and acrylic are suitable. Moreover, although the base material 11 was shown in FIG. 1 as a flat plate structure, the ND filter according to the present invention is not limited to this, and a structure having a curved surface, such as a sphere or a lens structure, or a rough surface It may be a structure having a predetermined pattern shape or the like.

光吸収材料層１３は、複数のグラフェン膜１が積層した構造を有する。グラフェン膜はＳＰ２結合した炭素原子による平面状の結晶性炭素膜であり、波長１５００ｎｍ以上４０００ｎｍ以下の広範な赤外線領域の光に対して特異的な吸収ピークを有さず、均一な透過率を有する。本実施形態において、光吸収材料層１３を構成するグラフェン膜１の層数は、所望の透過率を得られるように適宜変更可能であり、特に限定されない。 The light absorbing material layer 13 has a structure in which a plurality of graphene films 1 are stacked. The graphene film is a planar crystalline carbon film with SP 2 bonded carbon atoms, has no specific absorption peak for light in a wide infrared region with a wavelength of 1500 nm to 4000 nm, and has a uniform transmittance. Have. In the present embodiment, the number of graphene films 1 constituting the light absorption material layer 13 can be appropriately changed so as to obtain a desired transmittance, and is not particularly limited.

一実施形態において、ＮＤフィルタ１０の面内での透過率の均一性を確保するためには、光吸収材料層１３を構成するグラフェン膜１の結晶性が高く、且つ欠陥が少ないことが好ましい。低品質のグラフェン膜では、部分的に積層されたグラフェン膜の層数が異なり、光吸収材料層１３全体として均一な透過率を得ることができない。結晶性が高く、且つ欠陥が少ないグラフェン膜は、例えば、国際公開第２０１１／１１５１９７号に記載されたマイクロ波表面波プラズマ化学気相成長法（マイクロ波表面波プラズマＣＶＤ）により形成することができる。 In one embodiment, in order to ensure the uniformity of the transmittance within the surface of the ND filter 10, it is preferable that the graphene film 1 constituting the light absorbing material layer 13 has high crystallinity and few defects. In the low-quality graphene film, the number of partially laminated graphene films is different, and the light absorption material layer 13 as a whole cannot obtain a uniform transmittance. A graphene film having high crystallinity and few defects can be formed by, for example, a microwave surface wave plasma chemical vapor deposition method (microwave surface wave plasma CVD) described in International Publication No. 2011/115197. .

このため、本実施形態において、光吸収材料層１３は、共鳴ラマン散乱測定法により測定された１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．５以下となる。より好ましくは、Ｇ１／Ｇ２比が０．４以下、さらに好ましくは、０．３５以下である。共鳴ラマン散乱測定法により測定された１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値Ｇ１は、ＳＰ２結合の不規則性や欠陥、アモルファスカーボンの存在量に応じて大きくなる。一方、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２は、グラフェンのＳＰ２結合に起因するピークである。したがって、Ｇ１／Ｇ２比が小さいほど、光吸収材料層１３の結晶性が高いことを示す。このようなＧ１／Ｇ２比を有する光吸収材料層１３は、波長１５００ｎｍ以上４０００ｎｍ以下の範囲の光に対して均一な透過率を有するため好ましい。 Therefore, in the present embodiment, the light absorbing material layer 13, a minimum intensity value within been 1480 cm -1 or 1560 cm -1 or less in a range determined by resonance Raman scattering measurement method G 1, 1560 cm -1 or 1600cm When the maximum intensity value within the range of −1 or less is G 2 , the G 1 / G 2 ratio is 0.5 or less. More preferably, the G 1 / G 2 ratio is 0.4 or less, and more preferably 0.35 or less. Resonance minimum intensity value G 1 in a measured 1480 cm -1 or 1560 cm -1 or less range by Raman scattering measurement method, irregularities and defects SP 2 bond, increases according to the amount of the amorphous carbon . On the other hand, G 2 a maximum intensity value in the range of 1560 cm -1 or 1600 cm -1 or less is a peak due to SP 2 bond graphene. Therefore, the smaller the G 1 / G 2 ratio is, the higher the crystallinity of the light absorbing material layer 13 is. The light absorbing material layer 13 having such a G 1 / G 2 ratio is preferable because it has a uniform transmittance with respect to light in a wavelength range of 1500 nm to 4000 nm.

また、本実施形態において、光吸収材料層１３は、共鳴ラマン散乱測定法により測定された２５５０ｃｍ−１以上２８００ｃｍ−１以下の範囲内での最大の強度値を２Ｄｍａｘ、最小の強度値を２Ｄｍｉｎとしたときに、２Ｄｍａｘ／２Ｄｍｉｎ比が１．５以上である。より好ましくは、２Ｄｍａｘ／２Ｄｍｉｎ比が２以上である。２Ｄｍａｘ／２Ｄｍｉｎ比は、光吸収材料層１３が単一の物質、即ちグラフェン膜１１が形成されていることを示す指標である。したがって、２Ｄｍａｘ／２Ｄｍｉｎ比が大きいほど、光吸収材料層１３の純度が高いことを示す。このような２Ｄｍａｘ／２Ｄｍｉｎ比を有する光吸収材料層１３は、波長１５００ｎｍ以上４０００ｎｍ以下の範囲の光に対して均一な透過率を有するため好ましい。 Furthermore, 2D in this embodiment, the light absorbing material layer 13, the maximum intensity values 2D max within the range have been 2550 cm -1 or 2800 cm -1 or less measured by resonance Raman scattering measurement, the minimum intensity value When it is set to min , 2Dmax / 2Dmin ratio is 1.5 or more. More preferably, the 2D max / 2D min ratio is 2 or more. The 2D max / 2D min ratio is an index indicating that the light absorbing material layer 13 is a single substance, that is, the graphene film 11 is formed. Therefore, it shows that the purity of the light absorption material layer 13 is so high that 2Dmax / 2Dmin ratio is large. The light absorbing material layer 13 having such a 2D max / 2D min ratio is preferable because it has a uniform transmittance with respect to light in the wavelength range of 1500 nm to 4000 nm.

本実施形態において、基材１１と、光吸収材料層１３とは、接着層を介さずに密着した構造を有する。従来のＮＤフィルタにおいては、基材と、光吸収材料層とを積層する場合、材質の違いから接着層が必要であった。しかし、接着層は、一般に有機材料により形成されるため、波長２５００ｎｍ以上４０００ｎｍ以下の範囲に特異的な吸収ピークを有するものがほとんどである。したがって、本発明によって２５００ｎｍ以上４０００ｎｍ以下のＮＤフィルタを作製する場合は、基材１１と、光吸収材料層１３との間に有機材料を含む接着層を介在させるのは好ましくない。本発明においては、光吸収材料層１３を構成するグラフェン膜１がガラス基板等の基材１１と静電力により結合するため、接着層を配置することなく、密着させることができる。２５００ｎｍ以下であれば有機材料の特異なピークが観測されない場合もあり、接着層を用いてもよい。 In the present embodiment, the base material 11 and the light absorbing material layer 13 have a structure in which they are in close contact with each other without an adhesive layer. In the conventional ND filter, when a base material and a light absorption material layer are laminated, an adhesive layer is necessary due to the difference in material. However, since the adhesive layer is generally formed of an organic material, most adhesive layers have specific absorption peaks in the wavelength range of 2500 nm to 4000 nm. Therefore, when an ND filter having a wavelength of 2500 nm or more and 4000 nm or less is manufactured according to the present invention, it is not preferable to interpose an adhesive layer containing an organic material between the base material 11 and the light absorbing material layer 13. In the present invention, the graphene film 1 constituting the light-absorbing material layer 13 is bonded to the base material 11 such as a glass substrate by an electrostatic force, and thus can be adhered without arranging an adhesive layer. If it is 2500 nm or less, a specific peak of the organic material may not be observed, and an adhesive layer may be used.

このような構成を有する本実施形態に係るＮＤフィルタ１０は、波長５５０ｎｍの透過率が１％以上９０％以下であり、且つ、光吸収材料層の波長１５００ｎｍ以上４０００ｎｍ以下における透過率の最小値Ｔ（ｍｉｎ）（１５００−４０００）と最大値Ｔ（ｍａｘ）（１５００−４０００）との差Ｔ（ｒａｎｇｅ）が８．０以下を満たす。 The ND filter 10 according to the present embodiment having such a configuration has a transmittance at a wavelength of 550 nm of 1% to 90%, and a minimum value T of the transmittance at a wavelength of 1500 nm to 4000 nm of the light absorbing material layer. The difference T (range) between (min) (1500-4000) and the maximum value T (max) (1500-4000) satisfies 8.0 or less.

したがって、本発明に係るＮＤフィルタは、波長１５００ｎｍ以上４０００ｎｍ以下の範囲の光に対して、均一の透過率を示す光吸収材料層が形成された従来にないＮＤフィルタである。 Therefore, the ND filter according to the present invention is an unconventional ND filter in which a light-absorbing material layer showing a uniform transmittance is formed with respect to light having a wavelength in the range of 1500 nm to 4000 nm.

（実施形態２）
実施形態１においては、基材１１の光の透過面に対して一方の面に光吸収材料層１３を配置した例を示した。実施形態に２においては、基材１１の光の透過面の両面（上面及び下面）に光吸収材料層２３及び光吸収材料層２５をそれぞれ配置する例について説明する。図２は、本発明の一実施形態に係るＮＤフィルタ２０を示す模式図である。ＮＤフィルタ２０は、基材１１と、基材１１の光が透過する対向する２つの面に配置された光吸収材料層２３及び光吸収材料層２５と、を備える。基材１１の構成は、実施形態１で説明したため、詳細な説明は省略する。 (Embodiment 2)
In Embodiment 1, the example which has arrange | positioned the light absorption material layer 13 in one surface with respect to the light permeable surface of the base material 11 was shown. In the second embodiment, an example in which the light absorbing material layer 23 and the light absorbing material layer 25 are respectively disposed on both surfaces (upper surface and lower surface) of the light transmission surface of the substrate 11 will be described. FIG. 2 is a schematic diagram showing an ND filter 20 according to an embodiment of the present invention. The ND filter 20 includes a base material 11 and a light absorption material layer 23 and a light absorption material layer 25 disposed on two opposing surfaces through which light of the base material 11 is transmitted. Since the structure of the base material 11 was demonstrated in Embodiment 1, detailed description is abbreviate | omitted.

光吸収材料層２３及び光吸収材料層２５は、複数のグラフェン膜１が積層した構造を有し、上述した光吸収材料層１３と同様の構成を有する。ここで、光吸収材料層２３と光吸収材料層２５とは、所望の透過率を得られるようにグラフェン膜１の層数を適宜変更可能であり、特に限定されない。また、光吸収材料層２３を構成するグラフェン膜１の層数と光吸収材料層２５を構成するグラフェン膜１の層数とは、等しくてもよく、異なっていてもよい。 The light absorbing material layer 23 and the light absorbing material layer 25 have a structure in which a plurality of graphene films 1 are stacked, and have the same configuration as the light absorbing material layer 13 described above. Here, the number of layers of the graphene film 1 can be appropriately changed between the light absorbing material layer 23 and the light absorbing material layer 25 so as to obtain a desired transmittance, and is not particularly limited. Further, the number of graphene films 1 constituting the light absorbing material layer 23 and the number of graphene films 1 constituting the light absorbing material layer 25 may be equal or different.

その他のＮＤフィルタ２０の構成は、実施形態１のＮＤフィルタ１０と同様であるため、詳細な説明は省略する。本発明に係るＮＤフィルタは、波長１５００ｎｍ以上４０００ｎｍ以下の範囲の光に対して、均一の透過率を示す光吸収材料層が形成された、従来にないＮＤフィルタである。 Since the configuration of the other ND filter 20 is the same as that of the ND filter 10 of the first embodiment, detailed description thereof is omitted. The ND filter according to the present invention is an unconventional ND filter in which a light-absorbing material layer showing a uniform transmittance is formed with respect to light in the wavelength range of 1500 nm to 4000 nm.

（ＮＤフィルタの製造方法）
ＮＤフィルタの製造方法について説明する。所定形状の基材１１を準備する。基材１１は、実施形態１で説明した材質及び形状の基材を任意に選択可能である。また、グラフェン膜１を準備する。グラフェン膜１は、上述したように、結晶性が高く、且つ欠陥が少ないことが好ましい。結晶性が高く、且つ欠陥が少ないグラフェン膜は、例えば、国際公開第２０１１／１１５１９７号、に記載されたマイクロ波表面波プラズマ化学気相成長法（マイクロ波表面波プラズマＣＶＤ）や熱ＣＶＤ法（S. Bae, H. Kim, Y. Lee, X. Xu, J. S. Park, Y. Zheng, J. Balakrishan, T. Lei, H. R. Kim, Y. I. Somg, Y. J. Kim, K. S. Kim, B. Ozyilmaz, J. H. Ahn, B, H. Hong and S. Iijima, Nature Nanotechnol. 5, 574 (2011).）により形成することができる。若しくは、数ナノメートルサイズのグラフェン片の集合体であってもよい。なお、グラフェン膜１は、グラフェンが１層の膜であってもよく、複数層が積層した膜であってもよい。グラフェン膜１の取扱い上、複数層から形成されたグラフェン膜であることが好ましい。 (ND filter manufacturing method)
A method for manufacturing the ND filter will be described. A base material 11 having a predetermined shape is prepared. The base material 11 can arbitrarily select the base material having the material and shape described in the first embodiment. In addition, the graphene film 1 is prepared. As described above, the graphene film 1 preferably has high crystallinity and few defects. A graphene film having high crystallinity and few defects can be obtained by, for example, a microwave surface wave plasma chemical vapor deposition method (microwave surface wave plasma CVD) or a thermal CVD method (described in International Publication No. 2011/115197). S. Bae, H. Kim, Y. Lee, X. Xu, JS Park, Y. Zheng, J. Balakrishan, T. Lei, HR Kim, YI Somg, YJ Kim, KS Kim, B. Ozyilmaz, JH Ahn, B, H. Hong and S. Iijima, Nature Nanotechnol. 5, 574 (2011).). Alternatively, it may be an aggregate of graphene pieces having a size of several nanometers. The graphene film 1 may be a single-layer film of graphene or a film in which a plurality of layers are stacked. In view of handling the graphene film 1, a graphene film formed from a plurality of layers is preferable.

基材１１の光透過面にグラフェン膜を配置することにより、光吸収材料層１３を形成する。ここで、所望の透過率を得るため、必要な層数のグラフェン膜を配置して光吸収材料層１３を形成する。グラフェン膜を配置する場合、所望の透過率を得られる層数のグラフェン膜を準備して、基材１１に配置してもよく、複数層のグラフェン膜を何枚か用意して積層してもよい。上述したように、本実施形態において、基材１１と、光吸収材料層１３との間に有機材料を含む接着層を介在させるのは好ましくない。本発明においては、光吸収材料層１３を構成するグラフェン膜１がガラス基板等の基材１１と静電力により結合するため、接着層を配置することなく、密着させることができる。 The light absorbing material layer 13 is formed by disposing a graphene film on the light transmission surface of the substrate 11. Here, in order to obtain a desired transmittance, the light-absorbing material layer 13 is formed by disposing a required number of graphene films. When a graphene film is arranged, a graphene film having a number of layers that can obtain a desired transmittance may be prepared and arranged on the substrate 11, or a plurality of graphene films may be prepared and laminated. Good. As described above, in the present embodiment, it is not preferable to interpose an adhesive layer containing an organic material between the base material 11 and the light absorbing material layer 13. In the present invention, the graphene film 1 constituting the light-absorbing material layer 13 is bonded to the base material 11 such as a glass substrate by an electrostatic force, and thus can be adhered without arranging an adhesive layer.

なお、実施形態２のＮＤフィルタ２０を形成する場合、光吸収材料層２３と光吸収材料層２５とは、所望の透過率を得られるようにグラフェン膜１の層数を適宜変更可能であり、光吸収材料層２３を構成するグラフェン膜１の層数と光吸収材料層２５を構成するグラフェン膜１の層数とは、等しくてもよく、異なっていてもよい。 In addition, when forming the ND filter 20 of Embodiment 2, the number of layers of the graphene film 1 can be changed as appropriate so that the light absorption material layer 23 and the light absorption material layer 25 can obtain a desired transmittance. The number of graphene films 1 constituting the light absorbing material layer 23 and the number of graphene films 1 constituting the light absorbing material layer 25 may be the same or different.

上述した本発明に係るＮＤフィルタについて、実施例を示してさらに説明する。 The ND filter according to the present invention described above will be further described with reference to examples.

（実施例１）
圧延銅箔（３３μｍ、福田金属箔粉工業）を石英ガラスチューブ内に設置し、メタンガス１０ｓｃｃｍとアルゴンガス５０ｓｃｃｍを流しながら圧力バルブで１．０Ｐａに圧力調整した。ガラスチューブにヒーターを巻きつけて銅箔を約１０００℃で３０分間加熱し、銅箔上にグラフェン膜を形成した。グラフェン膜を形成した銅箔を塩化第二鉄１０％水溶液に入れて銅箔を溶解し、イオン交換水で洗浄した。銅箔を除去したグラフェン膜を基材として石英ガラス（ＵＳＤ−３００、大興製作所）に４枚積層して、実施例１のＮＤフィルタを作製した。 Example 1
Rolled copper foil (33 μm, Fukuda Metal Foil Powder Industry) was placed in a quartz glass tube, and the pressure was adjusted to 1.0 Pa with a pressure valve while flowing 10 sccm of methane gas and 50 sccm of argon gas. A heater was wound around the glass tube, and the copper foil was heated at about 1000 ° C. for 30 minutes to form a graphene film on the copper foil. The copper foil on which the graphene film was formed was put into a 10% ferric chloride aqueous solution to dissolve the copper foil, and washed with ion-exchanged water. Four sheets of the graphene film from which the copper foil was removed were laminated on quartz glass (USD-300, Daiko Seisakusho) to produce the ND filter of Example 1.

（ＮＤフィルタの近赤外領域及び赤外領域の透過率測定）
実施例１のＮＤフィルタの近赤外吸収について紫外可視分光光度計（SolidSpec-3700DUV、島津製作所）を用いて１５００ｎｍ〜２５００ｎｍまでの透過スペクトル（透過率）を測定した。また、３０００ｎｍ〜４０００ｎｍまでの赤外領域はフーリエ変換赤外分光光度計（ＦＴ−ＩＲ）（Spectrum100、PerkinElmer）を用いて測定した。なお、波長２５００ｎｍ〜３０００ｎｍの領域には、大気中に含まれる水の吸収が現れる。測定装置の熱等の影響により測定試料を配置する測定部の水分量（湿度）が変化するため、波長２５００ｎｍ〜３０００ｎｍの領域の透過率を規格化することができない。このため、本明細書においては、波長２５００ｎｍ〜３０００ｎｍの領域の透過率を示さないが、以下に示す波長１５００〜２５００ｎｍ及び３０００〜４０００ｎｍの領域における透過率の測定結果から、波長２５００ｎｍ〜３０００ｎｍの領域の透過率も均一となることが理解できるであろう。 (Measurement of transmittance in the near infrared region and infrared region of the ND filter)
About the near-infrared absorption of the ND filter of Example 1, the transmission spectrum (transmittance) from 1500 nm to 2500 nm was measured using an ultraviolet-visible spectrophotometer (SolidSpec-3700DUV, Shimadzu Corporation). The infrared region from 3000 nm to 4000 nm was measured using a Fourier transform infrared spectrophotometer (FT-IR) (Spectrum 100, PerkinElmer). The absorption of water contained in the atmosphere appears in the wavelength range of 2500 nm to 3000 nm. Since the amount of moisture (humidity) of the measurement unit in which the measurement sample is arranged changes due to the influence of heat or the like of the measurement device, it is not possible to normalize the transmittance in the wavelength range of 2500 nm to 3000 nm. For this reason, in this specification, although the transmittance | permeability of the area | region of wavelength 2500nm-3000nm is not shown, the area | region of wavelength 2500nm-3000nm from the measurement result of the transmittance | permeability in the area | region of the wavelength 1500-2500nm and 3000-4000nm shown below. It will be understood that the transmittance is uniform.

図３に実施例１のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率、図４に実施例１のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す。図３、４の結果から、実施例１のＮＤフィルタは、１５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域において、最小透過率９２．９％、最大透過率９７．２％であり、最大透過率と最小透過率の差は４．３％であった。 FIG. 3 shows the transmittance of the ND filter of Example 1 at a wavelength of 1500 to 2500 nm, and FIG. 4 shows the transmittance of the ND filter of Example 1 at a wavelength of 3000 to 4000 nm. From the results of FIGS. 3 and 4, the ND filter of Example 1 has a minimum transmittance of 92.9% and a maximum transmittance of 97.2% in the 1500 to 2500 nm and 3000 to 4000 nm regions. The difference in minimum transmittance was 4.3%.

（ＮＤフィルタの共鳴ラマン散乱測定）
実施例１のＮＤフィルタについて、共鳴ラマン散乱測定を行った。ＲＥＮＩＳＹＯＵラマン装置により、５３２ｎｍ波長のレーザーを用いて測定したラマンスペクトルを図５に示す。１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．１２であった。また、２５５０〜２８００ｃｍ−１の領域にピークがあり、最大強度（２Ｄｍａｘ）と最小強度（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎは２０．６８であった。 (Resonance Raman scattering measurement of ND filter)
Resonance Raman scattering measurement was performed on the ND filter of Example 1. FIG. 5 shows a Raman spectrum measured using a 532 nm wavelength laser with a RENISYO Raman apparatus. The minimum intensity values at 1480 cm -1 or 1560 cm -1 in the range of maximum intensity value in the range of G 1, 1560 cm -1 or 1600 cm -1 or less is taken as G 2, G 1 / G The 2 ratio was 0.12. Moreover, there was a peak in the region of 2550 to 2800 cm −1 , and the ratio 2D max / 2D min between the maximum intensity (2D max ) and the minimum intensity (2D min ) was 20.68.

（実施例２）
圧延銅箔（３３μｍ、福田金属箔粉工業）をプラズマＣＶＤ装置に配置し、真空ポンプによりプラズマＣＶＤ装置内を１．０−５Ｐａとした。アルゴンガス １０ｓｃｃｍ、メタンガス ３０ｓｃｃｍ、水素ガス ２０ｓｃｃｍをプラズマＣＶＤ装置へ導入し、圧力調整バルブで成膜時の圧力を１０Ｐａに調整した。グラフェン膜の成膜には、出力１．５ｋＷに設定した高周波電源からマイクロ波を、導波管を用いてプラズマＣＶＤ装置内に導入し、プラズマを発生させることで銅箔上にグラフェン膜を成膜した。プラズマ照射時間は６０ｓｅｃとした。グラフェン膜を形成した銅箔を塩化第二鉄１０％水溶液に入れて銅箔を溶解し、イオン交換水で洗浄した。銅箔を除去したグラフェン膜を石英ガラス（ＵＳＤ−３００大興製作所）へ４枚積層して、実施例２のＮＤフィルタを作製した。 (Example 2)
Rolled copper foil (33 μm, Fukuda Metal Foil Powder Industry) was placed in a plasma CVD apparatus, and the inside of the plasma CVD apparatus was set to 1.0 −5 Pa by a vacuum pump. Argon gas 10 sccm, methane gas 30 sccm, and hydrogen gas 20 sccm were introduced into the plasma CVD apparatus, and the pressure during film formation was adjusted to 10 Pa with a pressure adjusting valve. In forming the graphene film, a microwave is introduced into a plasma CVD apparatus using a waveguide from a high-frequency power source set to an output of 1.5 kW, and plasma is generated to form the graphene film on the copper foil. Filmed. The plasma irradiation time was 60 sec. The copper foil on which the graphene film was formed was put into a 10% ferric chloride aqueous solution to dissolve the copper foil, and washed with ion-exchanged water. Four graphene films from which the copper foil was removed were laminated on quartz glass (USD-300 Daiko Seisakusho) to produce an ND filter of Example 2.

（ＮＤフィルタの近赤外領域及び赤外領域の透過率測定）
実施例２のＮＤフィルタの近赤外及び赤外領域の透過率を、実施例１に記載の方法で測定した。図６に実施例２のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率、図７に実施例２のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す。図６、７の結果から、実施例２のＮＤフィルタは、１５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域において、最小透過率７２．９％、最大透過率７９．６％であり、最大透過率と最小透過率の差は６．７％であった。 (Measurement of transmittance in the near infrared region and infrared region of the ND filter)
The transmittance in the near infrared and infrared regions of the ND filter of Example 2 was measured by the method described in Example 1. FIG. 6 shows the transmittance of the ND filter of Example 2 at a wavelength of 1500 to 2500 nm, and FIG. 7 shows the transmittance of the ND filter of Example 2 at a wavelength of 3000 to 4000 nm. From the results of FIGS. 6 and 7, the ND filter of Example 2 has a minimum transmittance of 72.9% and a maximum transmittance of 79.6% in the 1500 to 2500 nm and 3000 to 4000 nm regions. The difference in minimum transmittance was 6.7%.

（ＮＤフィルタの共鳴ラマン散乱測定）
また、実施例２のＮＤフィルタのラマンスペクトルを、実施例１と同様に測定した。図８にＮＤフィルタのラマンスペクトルを示す。１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．３５であった。また、実施例１と同様に２５５０〜２８００ｃｍ−１の領域にピークがあり、最大の強度値（２Ｄｍａｘ）と最小の強度値（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎは２．０３であった。 (Resonance Raman scattering measurement of ND filter)
Further, the Raman spectrum of the ND filter of Example 2 was measured in the same manner as in Example 1. FIG. 8 shows the Raman spectrum of the ND filter. The minimum intensity values at 1480 cm -1 or 1560 cm -1 in the range of maximum intensity value in the range of G 1, 1560 cm -1 or 1600 cm -1 or less is taken as G 2, G 1 / G The 2 ratio was 0.35. Further, as in Example 1, there is a peak in the region of 2550 to 2800 cm −1 , and the ratio of the maximum intensity value (2D max ) to the minimum intensity value (2D min ) 2D max / 2D min is 2.03. It was.

（実施例３）
実施例２の銅箔を除去したグラフェン膜を石英ガラスへ乗せる回数を５回繰り返し、グラフェン膜を５枚積層したこと以外は、実施例２と同様の方法でＮＤフィルタを作製した。 (Example 3)
An ND filter was produced in the same manner as in Example 2 except that the number of times the graphene film from which the copper foil of Example 2 was removed was placed on quartz glass was repeated 5 times and five graphene films were laminated.

（ＮＤフィルタの近赤外領域及び赤外領域の透過率測定）
実施例３のＮＤフィルタの近赤外及び赤外領域の透過率を、実施例１に記載の方法で測定した。図９に実施例３のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率、図１０に実施例３のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す。図９、１０の結果から、実施例３のＮＤフィルタは、１５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域において、最小透過率５２．３％、最大透過率５９．０％であり、最大透過率と最小透過率の差は６．７％であった。 (Measurement of transmittance in the near infrared region and infrared region of the ND filter)
The transmittance in the near infrared and infrared regions of the ND filter of Example 3 was measured by the method described in Example 1. FIG. 9 shows the transmittance of the ND filter of Example 3 at a wavelength of 1500 to 2500 nm, and FIG. 10 shows the transmittance of the ND filter of Example 3 at a wavelength of 3000 to 4000 nm. From the results of FIGS. 9 and 10, the ND filter of Example 3 has a minimum transmittance of 52.3% and a maximum transmittance of 59.0% in the 1500 to 2500 nm and 3000 to 4000 nm regions. The difference in minimum transmittance was 6.7%.

（ＮＤフィルタの共鳴ラマン散乱測定）
実施例３のＮＤフィルタのラマンスペクトルを、ラマンスペクトルを実施例１と同様に測定した。図１１に実施例３のＮＤフィルタのラマンスペクトルを示す。１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．２８であった。また、実施例１と同様に２５５０〜２８００ｃｍ−１の領域にピークがあり、最大の強度値（２Ｄｍａｘ）と最小の強度値（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎは２．６６であった。 (Resonance Raman scattering measurement of ND filter)
The Raman spectrum of the ND filter of Example 3 was measured in the same manner as in Example 1. FIG. 11 shows the Raman spectrum of the ND filter of Example 3. The minimum intensity values at 1480 cm -1 or 1560 cm -1 in the range of maximum intensity value in the range of G 1, 1560 cm -1 or 1600 cm -1 or less is taken as G 2, G 1 / G The 2 ratio was 0.28. Further, as in Example 1, there is a peak in the region of 2550 to 2800 cm −1 , and the ratio 2D max / 2D min between the maximum intensity value (2D max ) and the minimum intensity value (2D min ) is 2.66. It was.

（実施例４）
実施例２のプラズマ照射時間を６００ｓｅｃに変更し、また、銅箔を除去したグラフェン膜を石英ガラスに１枚配置したこと以外は、実施例２と同様の条件で実施例４のＮＤフィルタを作製した。 Example 4
The ND filter of Example 4 was produced under the same conditions as in Example 2 except that the plasma irradiation time of Example 2 was changed to 600 sec and one graphene film from which the copper foil was removed was placed on quartz glass. did.

（ＮＤフィルタの近赤外領域及び赤外領域の透過率測定）
実施例４のＮＤフィルタの近赤外及び赤外領域の透過率を、実施例１に記載の方法で測定した。図１２に実施例４のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率、図１３に実施例４のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す。図１２、１３の結果から、実施例４のＮＤフィルタは、１５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域において、最小透過率４４．１％、最大透過率５１．５％であり、最大透過率と最小透過率の差は７．４％であった。 (Measurement of transmittance in the near infrared region and infrared region of the ND filter)
The transmittance in the near infrared and infrared regions of the ND filter of Example 4 was measured by the method described in Example 1. FIG. 12 shows the transmittance of the ND filter of Example 4 at a wavelength of 1500 to 2500 nm, and FIG. 13 shows the transmittance of the ND filter of Example 4 at a wavelength of 3000 to 4000 nm. From the results of FIGS. 12 and 13, the ND filter of Example 4 has a minimum transmittance of 44.1% and a maximum transmittance of 51.5% in the 1500 to 2500 nm and 3000 to 4000 nm regions. The difference in minimum transmittance was 7.4%.

（ＮＤフィルタの共鳴ラマン散乱測定）
実施例４のＮＤフィルタのラマンスペクトルを、ラマンスペクトルを実施例１と同様に測定した。図１４に実施例４のＮＤフィルタのラマンスペクトルを示す。１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．１４であった。また、実施例１と同様に２５５０〜２８００ｃｍ−１の領域にピークがあり、最大の強度値（２Ｄｍａｘ）と最小の強度値（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎは４．９３であった。 (Resonance Raman scattering measurement of ND filter)
The Raman spectrum of the ND filter of Example 4 was measured in the same manner as in Example 1. FIG. 14 shows the Raman spectrum of the ND filter of Example 4. The minimum intensity values at 1480 cm -1 or 1560 cm -1 in the range of maximum intensity value in the range of G 1, 1560 cm -1 or 1600 cm -1 or less is taken as G 2, G 1 / G The 2 ratio was 0.14. Further, as in Example 1, there is a peak in the region of 2550 to 2800 cm −1 , and the ratio 2D max / 2D min between the maximum intensity value (2D max ) and the minimum intensity value (2D min ) is 4.93. It was.

（実施例５）
ニッケル箔（３０μｍ、ニラコ社）を石英ガラスチューブ内に設置し、メタンガス １０ｓｃｃｍとアルゴンガス ５０ｓｃｃｍを流しながら圧力バルブで１００Ｐａに圧力を調整した。ガラスチューブにヒーターを巻きつけて銅箔を約１０００℃で３０分間加熱し、ニッケル箔上にグラフェン膜を形成した。グラフェン膜付きニッケル箔を塩化第二鉄１０％水溶液に入れて銅箔を溶解し、イオン交換水で洗浄した。ニッケル箔を除去したグラフェン膜を石英ガラス（ＵＳＤ−３００、大興製作所）へ１枚配置し、実施例５のＮＤフィルタを作製した。 (Example 5)
Nickel foil (30 μm, Niraco) was placed in a quartz glass tube, and the pressure was adjusted to 100 Pa with a pressure valve while flowing 10 sccm of methane gas and 50 sccm of argon gas. A heater was wrapped around the glass tube and the copper foil was heated at about 1000 ° C. for 30 minutes to form a graphene film on the nickel foil. The nickel foil with graphene film was placed in a 10% aqueous solution of ferric chloride to dissolve the copper foil, and washed with ion-exchanged water. One graphene film from which the nickel foil was removed was placed on quartz glass (USD-300, Daiko Seisakusho), and an ND filter of Example 5 was produced.

（ＮＤフィルタの近赤外領域及び赤外領域の透過率測定）
実施例５のＮＤフィルタの近赤外及び赤外領域の透過率を、実施例１に記載の方法で測定した。図１５に実施例５のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率、図１６に実施例５のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す。図１５、１６の結果から、実施例５のＮＤフィルタは、１５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域において、最小透過率１７．７％、最大透過率１９．３％であり、最大透過率と最小透過率の差は１．６％であった。 (Measurement of transmittance in the near infrared region and infrared region of the ND filter)
The transmittance in the near infrared and infrared regions of the ND filter of Example 5 was measured by the method described in Example 1. FIG. 15 shows the transmittance of the ND filter of Example 5 at a wavelength of 1500 to 2500 nm, and FIG. 16 shows the transmittance of the ND filter of Example 5 at a wavelength of 3000 to 4000 nm. From the results of FIGS. 15 and 16, the ND filter of Example 5 has a minimum transmittance of 17.7% and a maximum transmittance of 19.3% in the 1500 to 2500 nm and 3000 to 4000 nm regions. The difference in minimum transmittance was 1.6%.

（ＮＤフィルタの共鳴ラマン散乱測定）
実施例５のＮＤフィルタのラマンスペクトルを、ラマンスペクトルを実施例１と同様に測定した。図１７に実施例５のＮＤフィルタのラマンスペクトルを示す。１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．０７であった。また、２５５０〜２８００ｃｍ−１の領域にピークがあり、最大の強度値（２Ｄｍａｘ）と最小の強度値（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎは７．２７であった。 (Resonance Raman scattering measurement of ND filter)
The Raman spectrum of the ND filter of Example 5 was measured in the same manner as in Example 1. FIG. 17 shows the Raman spectrum of the ND filter of Example 5. The minimum intensity values at 1480 cm -1 or 1560 cm -1 in the range of maximum intensity value in the range of G 1, 1560 cm -1 or 1600 cm -1 or less is taken as G 2, G 1 / G The 2 ratio was 0.07. Moreover, there was a peak in the region of 2550 to 2800 cm −1 , and the ratio 2D max / 2D min between the maximum intensity value (2D max ) and the minimum intensity value (2D min ) was 7.27.

（比較例１）
電子銃による黒鉛粉末の蒸発と高周波電源で、Ａｒガスとカーボン粒子の一部イオン化を行い、石英ガラスへ約１５０ｎｍの炭素膜を製膜し、比較例１のＮＤフィルタを作製した。 (Comparative Example 1)
Graphite powder was evaporated with an electron gun and Ar gas and carbon particles were partially ionized with a high frequency power source, and a carbon film of about 150 nm was formed on quartz glass to produce an ND filter of Comparative Example 1.

（ＮＤフィルタの近赤外領域及び赤外領域の透過率測定）
比較例１のＮＤフィルタの近赤外及び赤外領域の透過率を、実施例１に記載の方法で測定した。図１８に比較例１のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率、図１９に比較例１のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す。図１８、１９の結果から、比較例１のＮＤフィルタは、１５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域において、最小透過率８４．２％、最大透過率９４．０％であり、最大透過率と最小透過率の差は９．８％であった。 (Measurement of transmittance in the near infrared region and infrared region of the ND filter)
The transmittance in the near infrared and infrared regions of the ND filter of Comparative Example 1 was measured by the method described in Example 1. FIG. 18 shows the transmittance of the ND filter of Comparative Example 1 at a wavelength of 1500 to 2500 nm, and FIG. 19 shows the transmittance of the ND filter of Comparative Example 1 at a wavelength of 3000 to 4000 nm. From the results of FIGS. 18 and 19, the ND filter of Comparative Example 1 has a minimum transmittance of 84.2% and a maximum transmittance of 94.0% in the 1500 to 2500 nm and 3000 to 4000 nm regions. The difference in minimum transmittance was 9.8%.

（ＮＤフィルタの共鳴ラマン散乱測定）
比較例１のＮＤフィルタのラマンスペクトルを、ラマンスペクトルを実施例１と同様に測定した。図２０に比較例１のＮＤフィルタのラマンスペクトルを示す。１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．８９であった。また、２５５０〜２８００ｃｍ−１の領域にピークがあり、最大の強度値（２Ｄｍａｘ）と最小の強度値（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎは１．２４であった。 (Resonance Raman scattering measurement of ND filter)
The Raman spectrum of the ND filter of Comparative Example 1 was measured in the same manner as in Example 1. FIG. 20 shows the Raman spectrum of the ND filter of Comparative Example 1. The minimum intensity values at 1480 cm -1 or 1560 cm -1 in the range of maximum intensity value in the range of G 1, 1560 cm -1 or 1600 cm -1 or less is taken as G 2, G 1 / G The 2 ratio was 0.89. Moreover, there was a peak in the region of 2550 to 2800 cm −1 , and the ratio 2D max / 2D min between the maximum intensity value (2D max ) and the minimum intensity value (2D min ) was 1.24.

（比較例２）
蝋燭（大創産業）に火をつけ、石英ガラスをその火に近づけることで炭素膜を石英ガラスに形成し、比較例２のＮＤフィルタを作製した。 (Comparative Example 2)
A ND filter of Comparative Example 2 was fabricated by setting a candle on fire (Taisho Sangyo) and forming a carbon film on the quartz glass by bringing the quartz glass close to the fire.

（ＮＤフィルタの近赤外領域及び赤外領域の透過率測定）
比較例２のＮＤフィルタの近赤外及び赤外領域の透過率を、実施例１に記載の方法で測定した。図２１に比較例２のＮＤフィルタの波長１５００〜２５００ｎｍでの透過率、図２２に比較例２のＮＤフィルタの波長３０００〜４０００ｎｍでの透過率を示す。図２１、２２の結果から、比較例２のＮＤフィルタは、１５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域において、最小透過率５７．３％、最大透過率８６．８％であり、最大透過率と最小透過率の差は２９．５％であった。 (Measurement of transmittance in the near infrared region and infrared region of the ND filter)
The transmittance in the near infrared and infrared regions of the ND filter of Comparative Example 2 was measured by the method described in Example 1. FIG. 21 shows the transmittance of the ND filter of Comparative Example 2 at a wavelength of 1500 to 2500 nm, and FIG. 22 shows the transmittance of the ND filter of Comparative Example 2 at a wavelength of 3000 to 4000 nm. From the results of FIGS. 21 and 22, the ND filter of Comparative Example 2 has a minimum transmittance of 57.3% and a maximum transmittance of 86.8% in the 1500 to 2500 nm and 3000 to 4000 nm regions. The difference in minimum transmittance was 29.5%.

（ＮＤフィルタの共鳴ラマン散乱測定）
比較例２のＮＤフィルタのラマンスペクトルを、ラマンスペクトルを実施例１と同様に測定した。図２３に比較例２のＮＤフィルタのラマンスペクトルを示す。１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．６９であった。また、２５５０〜２８００ｃｍ−１の領域にピークがあり、最大の強度値（２Ｄｍａｘ）と最小の強度値（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎは１．１３であった。 (Resonance Raman scattering measurement of ND filter)
The Raman spectrum of the ND filter of Comparative Example 2 was measured in the same manner as in Example 1. FIG. 23 shows the Raman spectrum of the ND filter of Comparative Example 2. The minimum intensity values at 1480 cm -1 or 1560 cm -1 in the range of maximum intensity value in the range of G 1, 1560 cm -1 or 1600 cm -1 or less is taken as G 2, G 1 / G The 2 ratio was 0.69. Moreover, there was a peak in the region of 2550 to 2800 cm −1 , and the ratio 2D max / 2D min between the maximum intensity value (2D max ) and the minimum intensity value (2D min ) was 1.13.

実施例１、２、３、４、５及び比較例１、２のＮＤフィルタの５００〜２５００ｎｍおよび、３０００〜４０００ｎｍの領域内の最小透過率、最大透過率、そして最大透過率と最小透過率の差を表１にまとめる。また、表２に、実施例１、２、３、４、５及び比較例１、２の１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値（Ｇ１）と１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値（Ｇ２）のＧ１／Ｇ２比、２５５０〜２８００ｃｍ−１領域の最大の強度値（２Ｄｍａｘ）と最小の強度値（２Ｄｍｉｎ）の比率 ２Ｄｍａｘ／２Ｄｍｉｎを示す。 The minimum transmittance, the maximum transmittance, and the maximum transmittance and the minimum transmittance in the region of 500 to 2500 nm and 3000 to 4000 nm of the ND filters of Examples 1, 2, 3, 4, 5 and Comparative Examples 1 and 2. The differences are summarized in Table 1. Further, in Table 2, the minimum intensity value in the range 1480 cm -1 or 1560 cm -1 The following Examples 1, 2, 3, 4 and Comparative Examples 1, 2 (G 1) and 1560 cm -1 or more G 1 / G 2 ratio of maximum intensity value (G 2 ) within a range of 1600 cm −1 or less, maximum intensity value (2D max ) and minimum intensity value (2D min ) of 2550-2800 cm −1 region The ratio 2D max / 2D min is shown.

Figure 2016071120
Figure 2016071120

Figure 2016071120
Figure 2016071120

表１より実施例１〜５は最大透過率と最小透過率の差は８．０以下と小さく、１５００〜４０００ｎｍにおいて波長依存の少ない光吸収材料層が形成されたＮＤフィルタである。一方、比較例１と２のＮＤフィルタは９．８以上と最大透過率と最小透過率の差が大きい。表２のＧ１／Ｇ２比は値がより小さいほど結晶性が良く、２Ｄｍａｘ/２Ｄｍｉｎは値がより大きいほどｓｐ２平面構造の乱れが小さい。実施例１〜５はＧ１／Ｇ２比が０．３５以下、２Ｄｍａｘ/２Ｄｍｉｎは２以上であり、比較例１と２はＧ１／Ｇ２比が０．６９以上、２Ｄｍａｘ/２Ｄｍｉｎは１．２４以下である。比較例１と２に比べて、実施例１〜５がグラファイトやグラフェン等に観られる結晶構造を有し、構造の乱れも少ないことが解った。 From Table 1, Examples 1 to 5 are ND filters in which the difference between the maximum transmittance and the minimum transmittance is as small as 8.0 or less, and a light absorbing material layer having a small wavelength dependence is formed at 1500 to 4000 nm. On the other hand, the ND filters of Comparative Examples 1 and 2 have a large difference between the maximum transmittance and the minimum transmittance of 9.8 or more. The smaller the value of the G 1 / G 2 ratio in Table 2, the better the crystallinity, and the larger the 2D max / 2D min value, the smaller the disorder of the sp2 planar structure. In Examples 1 to 5, the G 1 / G 2 ratio is 0.35 or less, 2D max / 2D min is 2 or more, and in Comparative Examples 1 and 2, the G 1 / G 2 ratio is 0.69 or more and 2D max / 2 2D min is 1.24 or less. Compared to Comparative Examples 1 and 2, it was found that Examples 1 to 5 had a crystal structure observed in graphite, graphene, and the like, and the disorder of the structure was small.

１５００〜４０００ｎｍにおいて波長依存の少ないＮＤフィルタを作製する際には、共鳴ラマン散乱測定法によりＧ１／Ｇ２比が０．５以下、２Ｄｍａｘ/２Ｄｍｉｎが１．５以上となるグラフェン膜を基材へ形成することで、１５００〜４０００ｎｍにおいて波長依存の少ない光吸収材料層を有するＮＤフィルタを提供できることが明らかとなった。 When producing an ND filter with less wavelength dependence at 1500 to 4000 nm, a graphene film having a G 1 / G 2 ratio of 0.5 or less and a 2D max / 2D min of 1.5 or more by a resonance Raman scattering measurement method is used. It became clear that the ND filter having a light-absorbing material layer with little wavelength dependence at 1500 to 4000 nm can be provided by forming on the substrate.

１：グラフェン膜、１０：ＮＤフィルタ、１１：基材、１３：光吸収材料層、２０：ＮＤフィルタ、２３：光吸収材料層、２５：光吸収材料層 1: graphene film, 10: ND filter, 11: base material, 13: light absorbing material layer, 20: ND filter, 23: light absorbing material layer, 25: light absorbing material layer

Claims (6)

波長１５００ｎｍ以上２５００ｎｍ以下における透過率の変化が１０％以内の基材と、
前記基材表面に配置された光吸収材料層と、を備え、
前記光吸収材料層は複数のグラフェン膜が積層した構造を有し、波長５５０ｎｍの透過率が１％以上９０％以下であり、且つ、波長１５００ｎｍ以上４０００ｎｍ以下における透過率の最小値Ｔ（ｍｉｎ）（１５００−４０００）と最大値Ｔ（ｍａｘ）（１５００−４０００）との差Ｔ（ｒａｎｇｅ）が８．０％以下を満たすことを特徴とするＮＤフィルタ。 A base material having a change in transmittance within a wavelength of 1500 nm or more and 2500 nm or less within 10%;
A light-absorbing material layer disposed on the substrate surface,
The light absorbing material layer has a structure in which a plurality of graphene films are laminated, the transmittance at a wavelength of 550 nm is 1% to 90%, and the minimum transmittance T (min) at a wavelength of 1500 nm to 4000 nm. An ND filter characterized in that a difference T (range) between (1500-4000) and a maximum value T (max) (1500-4000) satisfies 8.0% or less. 前記光吸収材料層は、共鳴ラマン散乱測定法により測定された１４８０ｃｍ−１以上１５６０ｃｍ−１以下の範囲内での最小の強度値をＧ１、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大の強度値をＧ２としたときに、Ｇ１／Ｇ２比が０．５で以下あることを特徴とする請求項１に記載のＮＤフィルタ。 The light-absorbing material layer, the minimum intensity value within been 1480 cm -1 or 1560 cm -1 or less in a range determined by resonance Raman scattering measurement method G 1, at 1560 cm -1 or 1600 cm -1 in the range maximum intensity value is taken as G 2, ND filter according to claim 1, G 1 / G 2 ratio, characterized in that below 0.5. 前記光吸収材料層は、共鳴ラマン散乱測定法により測定された２５５０ｃｍ−１以上２８００ｃｍ−１以下の範囲内での最大の強度値を２Ｄｍａｘ、最小の強度値を２Ｄｍｉｎとしたときに、２Ｄｍａｘ／２Ｄｍｉｎ比が１．５以上であることを特徴とする請求項１又は２に記載のＮＤフィルタ。 The light-absorbing material layer, when the maximum intensity value within been 2550 cm -1 or 2800 cm -1 or less in a range determined by resonance Raman scattering measurement method was 2D max, the minimum intensity value and 2D min, 2D The ND filter according to claim 1 or 2, wherein a max / 2D min ratio is 1.5 or more. 前記光吸収材料層は、マイクロ波表面波プラズマ化学気相成長法により形成されたグラフェン膜が積層した構造体であることを特徴とする請求項１乃至３の何れか一に記載のＮＤフィルタ。 The ND filter according to claim 1, wherein the light absorbing material layer is a structure in which graphene films formed by a microwave surface wave plasma chemical vapor deposition method are stacked. 前記基材と、前記光吸収材料層は、接着層を介さずに密着することを特徴とする請求項１乃至４の何れか一に記載のＮＤフィルタ。 The ND filter according to claim 1, wherein the base material and the light absorption material layer are in close contact with each other without an adhesive layer. 波長１５００ｎｍ以上２５００ｎｍ以下における前記基材の透過率が９０％以上であることを特徴とする請求項１乃至５の何れか一に記載のＮＤフィルタ。 The ND filter according to any one of claims 1 to 5, wherein a transmittance of the substrate at a wavelength of 1500 nm to 2500 nm is 90% or more.
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