JP6677174B2 - 反射防止膜の製造方法 - Google Patents
反射防止膜の製造方法 Download PDFInfo
- Publication number
- JP6677174B2 JP6677174B2 JP2016572950A JP2016572950A JP6677174B2 JP 6677174 B2 JP6677174 B2 JP 6677174B2 JP 2016572950 A JP2016572950 A JP 2016572950A JP 2016572950 A JP2016572950 A JP 2016572950A JP 6677174 B2 JP6677174 B2 JP 6677174B2
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- JP
- Japan
- Prior art keywords
- material layer
- etching
- antireflection film
- manufacturing
- etching mask
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004519 manufacturing process Methods 0.000 title claims description 49
- 238000005530 etching Methods 0.000 claims description 118
- 229910010272 inorganic material Inorganic materials 0.000 claims description 56
- 239000011147 inorganic material Substances 0.000 claims description 56
- 239000007769 metal material Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 46
- 239000012780 transparent material Substances 0.000 claims description 45
- 238000003486 chemical etching Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 238000001020 plasma etching Methods 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 description 29
- 230000003287 optical effect Effects 0.000 description 25
- 238000005516 engineering process Methods 0.000 description 24
- 238000010586 diagram Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000005566 electron beam evaporation Methods 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000007274 generation of a signal involved in cell-cell signaling Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007794 visualization technique Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/36—Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
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Description
上記反射防止膜は、上記基材に積層され、可視光領域で透明な無機材料からなり、幅が可視光波長以下である凸部と凹部によって構成された微細凹凸構造を有し、上記凹部のアスペクト比が1.5以上である。
上記光学部材は、上記レーザー光源の光学系に配置された光学部材であって、基材と、上記基材に積層し、可視光領域で透明な無機材料からなり、幅が可視光波長以下である凸部と凹部によって構成された微細凹凸構造を有し、上記凹部のアスペクト比が1.5以上である反射防止膜とを備える。
基材上に、可視光領域で透明な無機材料からなる透明材料層を積層し、
上記透明材料層上に、金属材料からなる金属材料層を積層し、
上記金属材料層上に、遷移金属の不完全酸化物からなる無機材料層を積層し、
上記無機材料層にレーザーを照射して前記無機材料を部分的に加工し、
上記無機材料層を現像して加工した部分を除去することで第1のエッチングマスクを形成し、
上記第1のエッチングマスクを用いて前記金属材料層にエッチングを施して第2のエッチングマスクを形成し、
上記第2のエッチングマスクを用いて前記透明材料層にエッチングを施して微細凹凸構造を形成する。
図1及び図2は、本技術の実施形態に係る反射防止構造体10の模式図であり、図1は断面図、図2は平面図である。以下の図においてX方向、Y方向及びZ方向は相互に直交する3方向である。
本実施形態に係る反射防止膜30の製造方法について説明する。なお、以下に示す製造方法は一例であり、反射防止膜30は、以下に示す方法とは異なる方法によって製造することも可能である。図5〜図7は、反射防止膜30の製造プロセスを示す模式図である。
第2のエッチングマスク51は、化学的エッチング又は物理的エッチングにより形成される。化学的エッチングの場合は、金属材料層50と反応しやすく、第1のエッチングマスク61とは反応しづらいガス種を用いたRIE(Reactive Ion Etching)とすることができる。例えば、金属材料層50をAl、第1のエッチングマスク61をW材料(Wの不完全酸化物)からなるものとした場合、ガス種に塩素ガス(Cl2)を用いることによって行うことができる。これにより、金属材料層50に対するエッチング選択比が向上するので、より深く金属材料層50をエッチングすることができる。
透明材料層40のエッチング加工は、透明材料層40と反応し、第2のエッチングマスク51とは反応しづらい化学的エッチングによって行うことができる。具体的には、エッチングガスにCF4、C4F8、CHF3等のフッ素系のガスを用いたRIEとすることができる。これにより、第2のエッチングマスク51に対する透明材料層40の選択比を向上させることができる。
図8は、本実施形態に係るレーザー露光機80の模式図である。本実施形態の被加工体70は、例えば、図8に示すレーザー露光機80によって加工される。同図に示すように、レーザー露光機80は、レーザー露光部D1、信号発生部D2、制御部D3、スライド部D4及び回転部D5を備える。
本実施形態の反射防止構造体10は、顕微鏡、カメラ、望遠鏡等の各種光学機器に搭載することができる。特に、反射防止構造体10は、レーザー光に対する耐性が高いため、レーザー光源を備えた光学機器に好適に利用することができる。なお、反射防止構造体10が搭載可能な光学機器は、上記のものに限定されるものではない。
本実施形態の反射防止膜30は、基材20が透明材料層40との密着性が低い場合は、基材20と透明材料層40との間に密着層を有することもできる。この場合、密着層の厚みは100nm以下が好適である。密着層の材質としては、例えば、Al2O3、Y2O3、Ti2O3、TiO又はTiO2等がある。また、反射防止膜30は、個々に独立した複数の凹部の間に凸部を有する構成であるが、これに限定されず、個々に独立した複数の凸部の間に凹部を有する構成であってもよい。
本技術の技術的思想に基づいて種々の変更が可能である。
可視光領域で透明な無機材料からなり、幅が可視光波長以下である凸部と凹部によって構成された微細凹凸構造を有し、上記凹部のアスペクト比が1.5以上である
反射防止膜。
上記(1)に記載の反射防止膜であって、
可視光及び近赤外線に対する反射率が0.5%未満である
反射防止膜。
上記(1)又は(2)に記載の反射防止膜であって、
上記凹部は、上記凸部を介して配列する細孔であり、
上記アスペクト比は、上記細孔の開口径に対する深さの比である
反射防止膜。
上記(1)から(3)のうちいずれか一つに記載の反射防止膜であって、
上記透明な無機材料は、ドライエッチング可能な材料から選択される
反射防止膜。
上記(1)から(4)のうちいずれか一つに記載の反射防止膜であって、
上記透明な無機材料はSiO2、HfO2、Al2O3、ITO、MgF2、TiO2及びCaF2の中から選択される
反射防止膜。
基材と、
上記基材に積層され、可視光領域で透明な無機材料からなり、幅が可視光波長以下である凸部と凹部によって構成された微細凹凸構造を有し、上記凹部のアスペクト比が1.5以上である反射防止膜と
を具備する光学部材。
レーザー光源と、
上記レーザー光源の光学系に配置された光学部材であって、基材と、上記基材に積層され、可視光領域で透明な無機材料からなり、幅が可視光波長以下である凸部と凹部によって構成された微細凹凸構造を有し、上記凹部のアスペクト比が1.5以上である反射防止膜とを備える光学部材と
を具備する光学機器。
基材上に、可視光領域で透明な無機材料からなる透明材料層を積層し、
上記透明材料層上に、金属材料からなる金属材料層を積層し、
上記金属材料層上に、遷移金属の不完全酸化物からなる無機材料層を積層し、
上記無機材料層にレーザーを照射して上記無機材料を部分的に加工し、
上記無機材料層を現像して加工した部分を除去することで第1のエッチングマスクを形成し、
上記第1のエッチングマスクを用いて上記金属材料層にエッチングを施して第2のエッチングマスクを形成し、
上記第2のエッチングマスクを用いて上記透明材料層にエッチングを施して微細凹凸構造を形成する
反射防止膜の製造方法。
上記(8)に記載の反射防止膜の製造方法であって
上記第2のエッチングマスクを形成する工程では、上記第1のエッチングマスクに対する上記金属材料層のエッチング選択比が0.3以上となるエッチング条件でエッチングを行う
反射防止膜の製造方法。
上記(8)又は(9)に記載の反射防止膜の製造方法であって、
上記第2のエッチングマスクを形成する工程では、上記金属材料に選択的に反応するエッチングガスを用いる化学的エッチングを行う
反射防止膜の製造方法。
上記(8)から(10)のうちいずれか一つに記載の反射防止膜の製造方法であって、
上記第2のエッチングマスクを形成する工程では、上記無機材料より原子量が小さくなるよう上記金属材料を選び、物理的エッチングを行う
反射防止膜の製造方法
上記(8)から(11)のうちいずれか一つに記載の反射防止膜の製造方法であって、
上記微細凹凸構造を形成する工程では、上記第2のエッチングマスクに対する上記透明材料層のエッチング選択比が15以上となるエッチング条件でエッチングを行う
反射防止膜の製造方法。
上記(8)から(12)のうちいずれか一つに記載の反射防止膜の製造方法であって、
上記第2のエッチングマスクを形成する工程では、物理的エッチングを行い、
上記微細凹凸構造を形成する工程では、化学的エッチングを行う
反射防止膜の製造方法。
上記(8)から(13)のうちいずれか一つに記載の反射防止膜の製造方法であって、
上記第2のエッチングマスクを形成する工程では、リアクティブイオンエッチングを行う
反射防止膜の製造方法。
上記(8)から(14)のうちいずれか一つに記載の反射防止膜の製造方法であって、
上記無機材料は、遷移金属の不完全酸化物からなる遷移金属系熱感応性レジストである
反射防止膜の製造方法。
20・・・基材
30・・・反射防止膜
31・・・凹部
32・・・凸部
40・・・透明材料層
50・・・金属材料層
51・・・第2のエッチングマスク
60・・・無機材料層
61・・・第1のエッチングマスク
Claims (8)
- 基材上に、可視光領域で透明な無機材料からなる透明材料層を積層し、
前記透明材料層上に、金属材料からなる金属材料層を積層し、
前記金属材料層上に、遷移金属の不完全酸化物からなる無機材料層を積層し、
前記無機材料層にレーザーを照射して前記無機材料を部分的に加工し、
前記無機材料層を現像して加工した部分を除去することで第1のエッチングマスクを形成し、
前記第1のエッチングマスクを用いて前記金属材料層にエッチングを施して第2のエッチングマスクを形成し、
前記第2のエッチングマスクを用いて前記透明材料層にエッチングを施して微細凹凸構造を形成する
反射防止膜の製造方法。 - 請求項1に記載の反射防止膜の製造方法であって、
前記第2のエッチングマスクを形成する工程では、前記第1のエッチングマスクに対する前記金属材料層のエッチング選択比が0.3以上となるエッチング条件でエッチングを行う
反射防止膜の製造方法。 - 請求項1に記載の反射防止膜の製造方法であって、
前記第2のエッチングマスクを形成する工程では、前記金属材料に選択的に反応するエッチングガスを用いる化学的エッチングを行う
反射防止膜の製造方法。 - 請求項1に記載の反射防止膜の製造方法であって、
前記第2のエッチングマスクを形成する工程では、前記無機材料より原子量が小さくなるよう前記金属材料を選び、物理的エッチングを行う
反射防止膜の製造方法。 - 請求項1に記載の反射防止膜の製造方法であって、
前記微細凹凸構造を形成する工程では、前記第2のエッチングマスクに対する前記透明材料層のエッチング選択比が15以上となるエッチング条件でエッチングを行う
反射防止膜の製造方法。 - 請求項1に記載の反射防止膜の製造方法であって、
前記第2のエッチングマスクを形成する工程では、物理的エッチングを行い、
前記微細凹凸構造を形成する工程では、化学的エッチングを行う
反射防止膜の製造方法。 - 請求項1に記載の反射防止膜の製造方法であって、
前記第2のエッチングマスクを形成する工程では、リアクティブイオンエッチングを行う
反射防止膜の製造方法。 - 請求項1に記載の反射防止膜の製造方法であって、
前記無機材料は、遷移金属の不完全酸化物からなる遷移金属系熱感応性レジストである
反射防止膜の製造方法。
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