WO2015147294A1 - Surface roughening method - Google Patents
Surface roughening method Download PDFInfo
- Publication number
- WO2015147294A1 WO2015147294A1 PCT/JP2015/059755 JP2015059755W WO2015147294A1 WO 2015147294 A1 WO2015147294 A1 WO 2015147294A1 JP 2015059755 W JP2015059755 W JP 2015059755W WO 2015147294 A1 WO2015147294 A1 WO 2015147294A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic resin
- layer
- substrate
- surface roughening
- etching
- Prior art date
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- 238000007788 roughening Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 165
- 239000011347 resin Substances 0.000 claims abstract description 165
- 239000000758 substrate Substances 0.000 claims abstract description 105
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 238000005530 etching Methods 0.000 claims abstract description 65
- 239000010954 inorganic particle Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
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- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
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- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 238000001039 wet etching Methods 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 9
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- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
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- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
- H10D86/01—Manufacture or treatment
- H10D86/021—Manufacture or treatment of multiple TFTs
- H10D86/0212—Manufacture or treatment of multiple TFTs comprising manufacture, treatment or coating of substrates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/875—Arrangements for extracting light from the devices
- H10K59/877—Arrangements for extracting light from the devices comprising scattering means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- An object of the present invention is to provide a method for roughening the surface of a substrate.
- the present invention utilizes a layer in which an inorganic substance and an organic substance are mixed on the substrate, and utilizes a difference in etching rate between the inorganic and organic oxygen gas to etch the surface of the substrate where oxygen gas is etched and the surface roughness not etched.
- the surface of the substrate can be roughened by etching with oxygen gas or fluorine-based gas using the surface roughened layer as a mask, for example, fine irregularities can be formed on the substrate,
- the organic resin layer (A) has a thickness of 0.001 to 10 ⁇ m, or 0.005 to 3.0 ⁇ m
- the organic resin layer (B) has a thickness of 0.001 to 10 ⁇ m, or 0.005. It has a film thickness of ⁇ 3.0 ⁇ m.
- the solution was added to 0.38 g, tetramethoxymethyl glycoluril 0.13 g, and propylene glycol monomethyl ether 28.8 g. Thereafter, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.2 ⁇ m to prepare a solution of the composition (a3-4).
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
本発明は基板上の表面粗化方法に係わり、この方法は特にＬＥＤ等の光取り出し層に適用することができる。 The present invention relates to a surface roughening method on a substrate, and this method can be applied particularly to a light extraction layer such as an LED.
近年、ＬＥＤ技術が利用されている。そして、その発光効率の向上のための技術として光取り出し層の研究が行われている。
ＬＥＤ等の光取り出し層としては有機ＥＬ素子内部の発光層と基板の間に、光散乱層を設ける手法が提案されている（特許文献１参照）。光散乱層としては、透明な樹脂に、該樹脂とは屈折率の異なる微粒子が分散されたものが用いられる。発光部で発光した光は、光散乱層により散乱されて、様々な方向に進行方向を変える。多重散乱の結果、空気との界面において全反射角内の角度域に入射した光が取り出されうる。光散乱層においては、光の進行方向がランダムに変化するため、微粒子のサイズ分布は広く、微粒子の配列はランダムであり、また微粒子の体積分率は大きいことが好ましい。ここで微粒子のサイズ分布が狭いと、或いは微粒子の体積分率が小さいと、光散乱層の散乱能が低くなってしまう。しかし、微粒子のサイズ分布が広いと樹脂中で微粒子を理想的に配列させることが困難となり、また微粒子のサイズ分布が広い場合に体積分率を大きくしようとすると、光散乱層の平坦性が著しく低下し、それにより薄膜構造である発光部の平坦性が損なわれて、発光素子の信頼性が大きく低下する。
In recent years, LED technology has been utilized. Research on the light extraction layer has been conducted as a technique for improving the luminous efficiency.
As a light extraction layer for an LED or the like, a method of providing a light scattering layer between a light emitting layer inside an organic EL element and a substrate has been proposed (see Patent Document 1). As the light scattering layer, a transparent resin in which fine particles having a refractive index different from that of the resin are dispersed is used. The light emitted from the light emitting unit is scattered by the light scattering layer and changes the traveling direction in various directions. As a result of multiple scattering, light incident on an angle region within the total reflection angle at the interface with air can be extracted. In the light scattering layer, the traveling direction of light randomly changes, so that the size distribution of the fine particles is wide, the arrangement of the fine particles is random, and the volume fraction of the fine particles is preferably large. Here, when the size distribution of the fine particles is narrow or the volume fraction of the fine particles is small, the scattering ability of the light scattering layer is lowered. However, if the size distribution of the fine particles is wide, it becomes difficult to ideally arrange the fine particles in the resin, and if the volume fraction is wide when the size distribution of the fine particles is wide, the flatness of the light scattering layer is remarkably high. As a result, the flatness of the light emitting part having a thin film structure is impaired, and the reliability of the light emitting element is greatly reduced.
また、反射層と、前記反射層上に形成された、変動係数が１０％以下の微粒子および前記微粒子と屈折率の異なるマトリックスを含む３次元回折層とを備え、前記微粒子の３次元回折層の体積に対する体積分率が５０％以上であり、前記微粒子が配列して短距離周期性を有する第一の領域を形成し、さらにその第一の領域がランダムな向きで隣接して集合した第二の領域を形成していることを特徴とする、光取り出し層が開示されている（特許文献２参照）。 A reflective layer; and a three-dimensional diffraction layer formed on the reflective layer and including a fine particle having a coefficient of variation of 10% or less and a matrix having a refractive index different from that of the fine particle. The volume fraction with respect to the volume is 50% or more, the fine particles are arranged to form a first region having a short-range periodicity, and the first region is gathered adjacently in a random direction. A light extraction layer is disclosed (see Patent Document 2).
本発明は基板の表面を粗化する方法を提供することを課題とする。特に、本発明は基板上に無機物と有機物が混在する層を利用して、無機物と有機物の酸素ガスのエッチング速度差を利用して基板の表面に酸素ガスがエッチングされる部分とエッチングされない表面粗化層とを形成することができる方法、そして更にその表面粗化層をマスクとして酸素ガス又はフッ素系ガスのエッチングにより基板表面を粗化、例えば基板上に微細な凹凸を形成することができ、また、ガスエッチングに変えて酸性水溶液を用いる湿式エッチングによっても同様に表面を粗化することができる方法を提供することを課題とする。 An object of the present invention is to provide a method for roughening the surface of a substrate. In particular, the present invention utilizes a layer in which an inorganic substance and an organic substance are mixed on the substrate, and utilizes a difference in etching rate between the inorganic and organic oxygen gas to etch the surface of the substrate where oxygen gas is etched and the surface roughness not etched. The surface of the substrate can be roughened by etching with oxygen gas or fluorine-based gas using the surface roughened layer as a mask, for example, fine irregularities can be formed on the substrate, It is another object of the present invention to provide a method that can similarly roughen the surface by wet etching using an acidic aqueous solution instead of gas etching.
本発明は第１観点として、基板上に又は基板より上方の層上に無機粒子（ａ１）と有機樹脂（ａ２）を含む組成物（ａ３）を塗布し乾燥と硬化を行って有機樹脂層（Ａ）を形成する第１工程と、該基板の上方からエッチングを行って同基板の表面を粗化する第２工程とを含む表面粗化方法、
第２観点として、前記エッチングは少なくとも１回なされ、そのうち少なくとも１回のエッチングは酸素系ガスによるガスエッチングである第１観点に記載の表面粗化方法、
第３観点として、前記エッチングは酸性水溶液による湿式エッチングである第１観点に記載の表面粗化方法、
第４観点として、前記無機粒子（ａ１）は平均粒子径５～１０００ｎｍの金属酸化物粒子である第１観点乃至第３観点のうちいずれか一つに記載の表面粗化方法、
第５観点として、前記組成物（ａ３）は、無機粒子（ａ１）としてシリカが有機溶剤に分散したシリカゾルと、有機樹脂（ａ２）の溶液とを含むものである第１観点に記載の表面粗化方法、
第６観点として、前記有機樹脂層（Ａ）は、有機樹脂（ａ２）１００質量部に対して無機粒子（ａ１）を５～５０質量部の割合で含有するものである第１観点乃至第５観点のうちいずれか一つに記載の表面粗化方法、
第７観点として、前記有機樹脂（ａ２）は、ヒドロキシ基、カルボキシル基、アミノ基、又はそれらの組み合わせからなる官能基を含む繰り返し単位構造を有してなるものである第１観点乃至第６観点のうちいずれか一つに記載の表面粗化方法、
第８観点として、エッチングが基板上に形成された（高さ）／（直径）で示される孔のアスペクト比で０．１～２０の範囲に形成するまで行われる第１観点乃至第７観点のうちいずれか一つに記載の表面粗化方法、
第９観点として、前記有機樹脂層（Ａ）は０．００１～１０μｍの膜厚を有する層である第１観点乃至第８観点のうちいずれか一つに記載の表面粗化方法、
第１０観点として、第１工程が、基板上に又は基板より上方の層上に有機樹脂（ｂ２）を含む組成物（ｂ３）を塗布し乾燥と硬化を行って有機樹脂層（Ｂ）を形成し、更に有機樹脂層（Ｂ）の上に無機粒子（ａ１）と有機樹脂（ａ２）を含む組成物（ａ３）を塗布し乾燥と硬化を行って有機樹脂層（Ａ）を形成する第１’工程である第２観点乃至第９観点のうちいずれか一つに記載の表面粗化方法、
第１１観点として、前記有機樹脂（ｂ２）として有機樹脂（ａ２）から選択される樹脂を用いる第１０観点に記載の表面粗化方法、
第１２観点として、前記有機樹脂層（Ｂ）は０．００１～１０μｍの膜厚を有する層である第１０観点又は第１１観点に記載の表面粗化方法、
第１３観点として、前記組成物（ａ３）及び／又は組成物（ｂ３）は更に架橋剤及び架橋触媒を含有している第１観点乃至第１２観点のうちいずれか一つに記載の表面粗化方法、並びに
第１４観点として、形成される表面粗化層はＬＥＤの光取り出し層である第１観点乃至第１３観点のうちいずれか一つに記載の表面粗化方法、である。
In the present invention, as a first aspect, a composition (a3) containing inorganic particles (a1) and an organic resin (a2) is applied on a substrate or a layer above the substrate, dried and cured, and then an organic resin layer ( A surface roughening method including a first step of forming A) and a second step of roughening the surface of the substrate by etching from above the substrate,
As a second aspect, the surface roughening method according to the first aspect, wherein the etching is performed at least once, and at least one of the etching is gas etching with an oxygen-based gas,
As a third aspect, the surface roughening method according to the first aspect, wherein the etching is wet etching with an acidic aqueous solution,
As a fourth aspect, the surface roughening method according to any one of the first to third aspects, wherein the inorganic particles (a1) are metal oxide particles having an average particle diameter of 5 to 1000 nm,
As a fifth aspect, the surface roughening method according to the first aspect, wherein the composition (a3) includes silica sol in which silica is dispersed in an organic solvent as inorganic particles (a1) and a solution of the organic resin (a2). ,
As a sixth aspect, the organic resin layer (A) contains the inorganic particles (a1) at a ratio of 5 to 50 parts by mass with respect to 100 parts by mass of the organic resin (a2). The surface roughening method according to any one of the aspects,
As a seventh aspect, the organic resin (a2) has a repeating unit structure including a functional group comprising a hydroxy group, a carboxyl group, an amino group, or a combination thereof. The surface roughening method according to any one of
As an eighth aspect, according to the first aspect to the seventh aspect, the etching is performed until the etching is performed in the range of 0.1 to 20 in the aspect ratio of the hole indicated by (height) / (diameter) formed on the substrate. The surface roughening method according to any one of the above,
As a ninth aspect, the surface roughening method according to any one of the first aspect to the eighth aspect, wherein the organic resin layer (A) is a layer having a thickness of 0.001 to 10 μm.
As a tenth aspect, the first step forms the organic resin layer (B) by applying a composition (b3) containing the organic resin (b2) on the substrate or a layer above the substrate, and drying and curing. Then, a composition (a3) containing inorganic particles (a1) and an organic resin (a2) is applied onto the organic resin layer (B), dried and cured to form an organic resin layer (A). The surface roughening method according to any one of the second aspect to the ninth aspect, which is a process,
As an eleventh aspect, the surface roughening method according to the tenth aspect using a resin selected from the organic resin (a2) as the organic resin (b2),
As a twelfth aspect, the organic resin layer (B) is a layer having a film thickness of 0.001 to 10 μm, the surface roughening method according to the tenth aspect or the eleventh aspect,
As a thirteenth aspect, the composition (a3) and / or the composition (b3) further contains a crosslinking agent and a crosslinking catalyst, and the surface roughening according to any one of the first to twelfth aspects. Method and as a fourteenth aspect, the surface roughening layer to be formed is the surface roughening method according to any one of the first aspect to the thirteenth aspect, which is a light extraction layer of an LED.
本発明により、基板の表面を粗化する新規な方法が提供される。特に、本発明の方法は、基板上に無機物と有機物が混在する層を利用して、無機物と有機物の酸素ガスのエッチング速度差を利用することができるので、基板の表面に酸素ガスがエッチングされる部分とエッチングされない表面粗化層とを形成することができ、そして更にその表面粗化層をマスクとして酸素ガス又はフッ素系ガスのエッチングにより基板表面を粗化、例えば基板上に微細な凹凸を形成することができ、また、本発明の方法に従うと、ガスエッチングに変えて酸性水溶液を用いる湿式エッチングによっても同様に表面を粗化することができる。 The present invention provides a novel method for roughening the surface of a substrate. In particular, the method of the present invention can utilize the difference in the etching rate of the oxygen gas between the inorganic material and the organic material using a layer in which the inorganic material and the organic material are mixed on the substrate, so that the oxygen gas is etched on the surface of the substrate. And a surface roughened layer that is not etched, and the surface roughened layer is used as a mask to roughen the substrate surface by etching with oxygen gas or fluorine-based gas. For example, fine irregularities are formed on the substrate. According to the method of the present invention, the surface can be similarly roughened by wet etching using an acidic aqueous solution instead of gas etching.
有機ＥＬディスプレイでは、ガラスや透明プラスチック等の基板上にＩＴＯ電極、正孔注入層、正孔輸送層、発光層、電子輸送層、電子注入層、電極が形成される。
また、サファイア上にＮ型半導体、発光域、Ｐ型半導体、ＩＴＯ電極、ＳｉＯ２層が形成される。
In an organic EL display, an ITO electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an electrode are formed on a substrate such as glass or transparent plastic.
Further, an N-type semiconductor, a light emitting region, a P-type semiconductor, an ITO electrode, and a SiO 2 layer are formed on sapphire.
本発明ではこれらの光取り出し層として使われるガラスや透明プラスチックやＳｉＯ２層などの表面を粗化、例えば微細な凹凸を形成することで光の反射を低減することが可能であり、それにより発光効率を向上させることができる。 In the present invention, it is possible to reduce the reflection of light by roughening the surface of the glass, transparent plastic, SiO 2 layer, etc. used as the light extraction layer, for example, by forming fine irregularities. Efficiency can be improved.
従来法として光取り出し層に用いられる基板に無機粒子等を付着させる手法があるが密着性が問題となっていた。本発明はそれら手法とは異なり、基板表面を物理的なエッチングにより粗化、例えば凹凸等を形成させるものである。 As a conventional method, there is a method of attaching inorganic particles or the like to a substrate used for a light extraction layer, but adhesion has been a problem. In the present invention, unlike those methods, the substrate surface is roughened by physical etching, for example, irregularities are formed.
本発明は粗化させる基板上に又は基板より上方の層上に無機粒子（ａ１）と有機樹脂（ａ２）を含む組成物（ａ３）を塗布し乾燥と硬化を行って有機樹脂層（Ａ）を形成する第１工程と、それに続く該基板の上方からガスでエッチングを行って同基板の表面を粗化する第２工程とを含んでいる。有機樹脂層（Ａ）に含まれる無機粒子（ａ１）と有機樹脂（ａ２）との酸素ガスのエッチング速度差を利用して、有機樹脂層（Ａ）に凹凸を形成する。有機樹脂層（Ａ）の凹凸はその後、更に続けられる酸素ガスのエッチング、又はその他のガス（フッ素系ガス、塩素系ガス）によって基板表面にエッチングされる部分とエッチングされない部分が生じ凹凸が形成される。
場合によっては形成された凹凸が更にエッチングされて基板の下方に向かってエッチング層が形成される。
乾燥と硬化は同時に行うことも、乾燥をした後に硬化を行うこともできる。
In the present invention, a composition (a3) containing inorganic particles (a1) and an organic resin (a2) is applied on a substrate to be roughened or on a layer above the substrate, dried and cured, and then an organic resin layer (A). And a subsequent second step of roughening the surface of the substrate by etching with gas from above the substrate. Concavities and convexities are formed in the organic resin layer (A) using the etching rate difference of oxygen gas between the inorganic particles (a1) and the organic resin (a2) contained in the organic resin layer (A). Then, the unevenness of the organic resin layer (A) is formed by further continuing etching of oxygen gas, or a portion etched on the substrate surface by another gas (fluorine-based gas, chlorine-based gas) and a portion not etched. The
In some cases, the formed irregularities are further etched to form an etching layer toward the lower side of the substrate.
Drying and curing can be performed simultaneously, or curing can be performed after drying.
上記有機樹脂層（Ａ）は酸素エッチングを行う上でマスクの機能を果たす。基板上に無機粒子を含まない有機樹脂層（Ｂ）を形成し、その上に無機粒子を含む有機樹脂層（Ａ）を形成して、酸素ガスでエッチングすることにより、マスクとしての（Ａ）層と（Ｂ）層の膜厚が厚くなり、その後の酸素系ガス又はその他のガスエッチング（例えばフッ素系ガス）によりエッチング差を生じやすくなるため高いアスペクト比を有する基板の粗化が可能になる。
また、ガスエッチングに変えて酸性水溶液を用いる湿式エッチングによっても上記と同様に粗化が可能になる。
The organic resin layer (A) functions as a mask in performing oxygen etching. An organic resin layer (B) containing no inorganic particles is formed on a substrate, an organic resin layer (A) containing inorganic particles is formed thereon, and etching is performed with oxygen gas, whereby (A) as a mask Layers (B) and (B) become thicker, and subsequent oxygen etching or other gas etching (for example, fluorine-based gas) tends to cause an etching difference, so that a substrate having a high aspect ratio can be roughened. .
In addition, roughening is possible in the same manner as described above by wet etching using an acidic aqueous solution instead of gas etching.
上記粗化とは基板表面をエッチングにより荒らすものであり、基板表面に化学的や物理的な変化を生じさせる。その一例として基板表面に凹凸が形成される。 The above roughening means that the surface of the substrate is roughened by etching, and a chemical or physical change is caused on the surface of the substrate. As an example, irregularities are formed on the substrate surface.
基板の粗化は無機粒子の平均粒子径や、有機樹脂層（Ａ）に含まれる無機粒子の濃度（割合）によって変化し、必要とする基板上の粗化形状（凹凸形状）により決定される。 The roughening of the substrate varies depending on the average particle diameter of the inorganic particles and the concentration (ratio) of the inorganic particles contained in the organic resin layer (A), and is determined by the required roughening shape (uneven shape) on the substrate. .
本発明ではエッチングが少なくとも１回なされ、そのうち少なくとも１回のエッチングは酸素系ガスによるガスエッチングで行われる。酸素系ガスはガス成分として酸素を含むエッチングガスであり、酸素によって有機樹脂層（Ａ）やその下層に存在する有機樹脂層（Ｂ）中の有機樹脂（ａ２）や有機樹脂（ｂ２）が垂直方向にエッチングされ、また有機樹脂層（Ａ）中の無機粒子（ａ１）は酸素ガスに対してエッチング抵抗を示す。そして、有機樹脂層（Ａ）や有機樹脂層（Ｂ）のエッチングが基板面に到達した段階で、引き続き酸素系ガスでエッチングを行う場合や、その他のガス（例えば、フッ素成分を含むガス）によって基板をエッチングすることができる。 In the present invention, etching is performed at least once, and at least one of the etching is performed by gas etching using an oxygen-based gas. The oxygen-based gas is an etching gas containing oxygen as a gas component, and the organic resin (a2) and the organic resin (b2) in the organic resin layer (A) and the organic resin layer (B) existing below the oxygen resin are vertical due to oxygen. Etching is performed in the direction, and the inorganic particles (a1) in the organic resin layer (A) exhibit etching resistance against oxygen gas. When the etching of the organic resin layer (A) or the organic resin layer (B) reaches the substrate surface, the etching is continued with an oxygen-based gas, or other gases (for example, a gas containing a fluorine component). The substrate can be etched.
また、本発明ではエッチングが酸性水溶液による湿式エッチングで行うことができる。酸性水溶液により有機樹脂層（Ａ）やその下層に存在する有機樹脂層（Ｂ）中の有機樹脂（ａ２）や有機樹脂（ｂ２）が垂直方向にエッチングされ、また有機樹脂層（Ａ）中の無機粒子（ａ１）は酸性水溶液に対してエッチング抵抗を示す。そして、有機樹脂層（Ａ）や有機樹脂層（Ｂ）のエッチングが基板面に到達した段階で、引き続き酸性水溶液で基板をエッチングすることができる。 In the present invention, the etching can be performed by wet etching using an acidic aqueous solution. The organic resin (a2) and the organic resin (b2) in the organic resin layer (A) and the organic resin layer (B) existing below the organic resin layer (A) are etched in the vertical direction by the acidic aqueous solution, and the organic resin layer (A) The inorganic particles (a1) exhibit etching resistance against acidic aqueous solutions. Then, when the etching of the organic resin layer (A) or the organic resin layer (B) reaches the substrate surface, the substrate can be continuously etched with an acidic aqueous solution.
湿式エッチングに用いられる酸性水溶液は、酸と水を含んでいて、必要により過酸化水素や水溶性有機溶剤を含有することができる。酸は硫酸、硝酸、塩酸が用いられる。水溶性有機溶剤はアルコール系やエーテル系やケトン系やエステル系である。例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトシキ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル等を用いることができる。これらの有機溶剤は単独で、または２種以上の組合せで使用される。
水と有機溶剤を合わせた全溶剤中での酸の濃度は０．０１～９７質量％であり、全溶剤中での過酸化水素の濃度は０．０１～４０質量％である。
The acidic aqueous solution used for wet etching contains an acid and water, and may contain hydrogen peroxide and a water-soluble organic solvent as necessary. As the acid, sulfuric acid, nitric acid, and hydrochloric acid are used. Water-soluble organic solvents are alcohol-based, ether-based, ketone-based and ester-based. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxypropionic acid Chill, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate and the like can be used. These organic solvents are used alone or in combination of two or more.
The concentration of the acid in the total solvent including water and the organic solvent is 0.01 to 97% by mass, and the concentration of hydrogen peroxide in the total solvent is 0.01 to 40% by mass.
本発明ではガスエッチングと湿式エッチングを両方組み合わせて行っても良い。 In the present invention, both gas etching and wet etching may be combined.
本発明に用いられる無機粒子（ａ１）は金属酸化物が用いられる。例えば酸化珪素（シリカ）、酸化チタン、酸化ジルコニウム、酸化アルミニウム等が挙げられる。特に酸化珪素（シリカ）が好ましい。平均粒子径としては５～１０００ｎｍ、又は５～２００ｎｍ、又は１０～５０ｎｍの範囲で用いることができる。これらの無機粒子はコロイド状態で有機樹脂（ａ２）に添加することが好ましく、上記無機粒子（ａ１）の有機溶剤に分散したゾルを、有機樹脂（ａ２）又は有機樹脂（ａ２）の溶液に添加することで組成物（ａ３）が得られ、この組成物（ａ３）を基材に、又は予め有機樹脂層（Ｂ）が形成された基材に被覆される。
典型的には無機粒子（ａ１）としてシリカが有機溶剤に分散したシリカゾルと、有機樹脂（ａ２）の溶液とを混合して組成物（ａ３）が得られる。
A metal oxide is used for the inorganic particles (a1) used in the present invention. Examples thereof include silicon oxide (silica), titanium oxide, zirconium oxide, and aluminum oxide. In particular, silicon oxide (silica) is preferable. The average particle diameter can be 5 to 1000 nm, 5 to 200 nm, or 10 to 50 nm. These inorganic particles are preferably added to the organic resin (a2) in a colloidal state, and the sol dispersed in the organic solvent of the inorganic particles (a1) is added to the solution of the organic resin (a2) or the organic resin (a2). By doing this, a composition (a3) is obtained, and this composition (a3) is coated on a substrate or a substrate on which the organic resin layer (B) has been formed in advance.
Typically, a silica sol in which silica is dispersed in an organic solvent as inorganic particles (a1) and a solution of the organic resin (a2) are mixed to obtain the composition (a3).
組成物（ａ３）中及び、その組成物（ａ３）を塗布して得られる有機樹脂層（Ａ）中には、有機樹脂（ａ２）１００質量部に対して無機粒子（ａ１）を１～１００質量部の割合で含有して形成される。 In the composition (a3) and in the organic resin layer (A) obtained by applying the composition (a3), 1 to 100 inorganic particles (a1) are added to 100 parts by mass of the organic resin (a2). It is formed by containing at a ratio of part by mass.
有機樹脂（ａ２）としては繰り返し単位にヒドロキシ基、カルボキシル基、アミノ基、又はそれらの組み合わせを有する極性基を官能基として有することが好ましい。これら官能基は無機粒子との相容性や、基板への塗布性の点で好ましい。 The organic resin (a2) preferably has a polar group having a hydroxy group, a carboxyl group, an amino group, or a combination thereof as a functional group in the repeating unit. These functional groups are preferable in terms of compatibility with inorganic particles and coatability on a substrate.
上記官能基を含む樹脂としてはアクリル系樹脂、ノボラック系樹脂等が挙げられる。 Examples of the resin containing the functional group include acrylic resins and novolac resins.
アクリル系樹脂としては、ヒドロキシ基やカルボキシル基やアミノ基を有するモノマーの単独重合体や、それらとその他の樹脂との共重合体が挙げられる。モノマーとしては（メタ）アクリル酸や、（メタ）アクリル酸エステルや、ビニル化合物が挙げられる。 Examples of the acrylic resin include homopolymers of monomers having a hydroxy group, a carboxyl group or an amino group, and copolymers of these with other resins. Examples of the monomer include (meth) acrylic acid, (meth) acrylic acid ester, and vinyl compound.
ヒドロキシル基やカルボキシル基やアミノ基を有するモノマーは、（メタ）アクリル酸、（メタ）アクリルアミド、ヒドロキシアルキル（メタ）アクリレート、カルボキシアルキル（メタ）アクリレート、アミノアルキル（メタ）アクリレート、ヒドロキシスチレン、ヒドロキシビニルナフタレン、安息香酸ビニル等のモノマーの単独重合体や、その他の樹脂との共重合体が挙げられる。その他の樹脂としては上記官能基を含まないモノマーが挙げられ、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート等のアルキル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、スチレン、ｔ－ブチルスチレン、ビニルナフタレン等が挙げられる。 Monomers having hydroxyl group, carboxyl group or amino group are (meth) acrylic acid, (meth) acrylamide, hydroxyalkyl (meth) acrylate, carboxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate, hydroxystyrene, hydroxyvinyl Examples thereof include homopolymers of monomers such as naphthalene and vinyl benzoate, and copolymers with other resins. Examples of other resins include monomers that do not contain the above functional groups. Examples include alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. , T-butylstyrene, vinylnaphthalene and the like.
これらのアクリル系モノマーはラジカル重合やカチオン重合で上記のアクリル系樹脂が得られる。 These acrylic monomers can obtain the above acrylic resins by radical polymerization or cationic polymerization.
ノボラック樹脂としては、フェノール性ヒドロキシ基含有化合物やアミノ基含有芳香族化合物と、アルデヒド化合物との反応で得られるノボラック樹脂や、フェノール性ヒドロキシ基含有化合物やアミノ基含有芳香族化合物と、ヒドロキシ基やカルボキシル基やアミノ基含有アルデヒド化合物との反応で得られるノボラック樹脂が挙げられる。フェノール性ヒドロキシ基を有する化合物としては、フェノール、クレゾール、サリチル酸、ナフトール等の１価フェノール、カテコール、レゾルシノール等の２価フェノール、ピロガロール、フロログリシノール等の３価フェノール、ビフェノール、ビスフェノールＡ、ビスフェノールＳ等の多核フェノールが挙げられる。 As the novolak resin, a novolak resin obtained by reaction of a phenolic hydroxy group-containing compound or amino group-containing aromatic compound and an aldehyde compound, a phenolic hydroxy group-containing compound or amino group-containing aromatic compound, a hydroxy group, A novolak resin obtained by a reaction with a carboxyl group or amino group-containing aldehyde compound may be mentioned. Examples of the compound having a phenolic hydroxy group include monohydric phenols such as phenol, cresol, salicylic acid and naphthol, dihydric phenols such as catechol and resorcinol, trihydric phenols such as pyrogallol and phloroglicinol, biphenol, bisphenol A, and bisphenol S. And polynuclear phenols.
アミノ基含有芳香族化合物としては、ピロール、フェニルナフチルアミン、フェニルインドール、カルバゾール等が挙げられる。 Examples of the amino group-containing aromatic compound include pyrrole, phenylnaphthylamine, phenylindole, and carbazole.
アルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、イソブチルアルデヒド、バレルアルデヒド、カプロンアルデヒド、２－メチルブチルアルデヒド、ヘキシルアルデヒド、ウンデカンアルデヒド、７－メトキシ－３，７－ジメチルオクチルアルデヒド、シクロヘキサンアルデヒド、３－メチル－２－ブチルアルデヒド、グリオキザール、マロンアルデヒド、スクシンアルデヒド、グルタルアルデヒド、アジピンアルデヒド等の飽和脂肪族アルデヒド類、アクロレイン、メタクロレイン等の不飽和脂肪族アルデヒド類、フルフラール、ピリジンアルデヒド等のヘテロ環式アルデヒド類、ベンズアルデヒド、ナフチルアルデヒド、アントリルアルデヒド、フェナントリルアルデヒド、サリチルアルデヒド、フェニルアセトアルデヒド、３－フェニルプロピオンアルデヒド、トリルアルデヒド、（Ｎ，Ｎ－ジメチルアミノ）ベンズアルデヒド、アセトキシベンズアルデヒド等の芳香族アルデヒド類等が挙げられる。中でもヒドロキシ基又はカルボキシル基含有アルデヒド化合物が好ましく、例えばヒドロキシベンズアルデヒド、カルボキシベンズアルデヒド、ヒドロキシナフトアルデヒド、カルボキシナフトアルデヒド、ヒドロキシピレンアルデヒド、カルボキシピレンアルデヒドが挙げられる。 Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, capronaldehyde, 2-methylbutyraldehyde, hexyl aldehyde, undecane aldehyde, 7-methoxy-3,7-dimethyloctyl aldehyde , Cyclohexanealdehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, saturated aliphatic aldehydes such as adipine aldehyde, unsaturated aliphatic aldehydes such as acrolein, methacrolein, furfural, Heterocyclic aldehydes such as pyridine aldehyde, benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenane Lil aldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N, N-dimethylamino) benzaldehyde, and aromatic aldehydes such as acetoxy benzaldehyde and the like. Of these, hydroxy group- or carboxyl group-containing aldehyde compounds are preferred, and examples thereof include hydroxybenzaldehyde, carboxybenzaldehyde, hydroxynaphthaldehyde, carboxynaphthaldehyde, hydroxypyrenealdehyde, and carboxypyrenealdehyde.
フェノール性ヒドロキシ基含有化合物やアミノ基含有芳香族化合物とアルデヒド化合物は、フェニル基１当量に対して、アルデヒド類を０．１～１０当量の割合で用いることができる。上記縮合反応で用いられる酸触媒としては、例えば硫酸、リン酸、過塩素酸等の鉱酸類、ｐ－トルエンスルホン酸、ｐ－トルエンスルホン酸一水和物等の有機スルホン酸類、蟻酸、シュウ酸等のカルボン酸類が使用される。酸触媒の使用量は、使用する酸類の種類によって種々選択される。通常、フェノール性ヒドロキシ基含有化合物やアミノ基含有芳香族化合物とアルデヒド化合物の合計の１００質量部に対して、０．００１～１００００質量部、好ましくは０．０１～１０００質量部、より好ましくは０．１～１００質量部である。 In the phenolic hydroxy group-containing compound, amino group-containing aromatic compound and aldehyde compound, aldehydes can be used at a ratio of 0.1 to 10 equivalents per 1 equivalent of the phenyl group. Examples of the acid catalyst used in the above condensation reaction include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate, formic acid and oxalic acid. Carboxylic acids such as are used. The amount of the acid catalyst used is variously selected depending on the type of acids used. Usually, 0.001 to 10000 parts by mass, preferably 0.01 to 1000 parts by mass, more preferably 0 to 100 parts by mass of the total of the phenolic hydroxy group-containing compound or amino group-containing aromatic compound and aldehyde compound. 1 to 100 parts by mass.
上記の縮合反応は無溶剤でも行われるが、通常溶剤を用いて行われる。溶剤としては反応を阻害しないものであれば全て使用することができる。例えばテトラヒドロフラン、ジオキサン等の環状エーテル類が挙げられる。また、使用する酸触媒が例えば蟻酸のような液状のものであるならば溶剤としての役割を兼ねさせることもできる。 The above condensation reaction is carried out without solvent, but is usually carried out using a solvent. Any solvent that does not inhibit the reaction can be used. Examples thereof include cyclic ethers such as tetrahydrofuran and dioxane. In addition, if the acid catalyst used is a liquid such as formic acid, it can also serve as a solvent.
縮合時の反応温度は通常４０℃～２００℃である。反応時間は反応温度によって種々選択されるが、通常３０分～５０時間程度である。 The reaction temperature during the condensation is usually 40 ° C to 200 ° C. The reaction time is variously selected depending on the reaction temperature, but is usually about 30 minutes to 50 hours.
本発明に用いられる有機樹脂（ａ２）、更に以下に述べられる有機樹脂（ｂ２）は以下に例示することができる。
本発明に用いられる組成物（ａ３）は上記有機樹脂（ａ２）と無機粒子（ａ１）と溶剤を含む。必要に応じて界面活性剤等の添加剤を含むことができる。 The composition (a3) used in the present invention contains the organic resin (a2), inorganic particles (a1), and a solvent. If necessary, an additive such as a surfactant can be contained.
この組成物の固形分は０．１～７０質量％、または０．１～６０質量％である。固形分は組成物（ａ３）から溶剤を除いた全成分の含有割合である。固形分中に有機樹脂（ａ２）を１～９９．９質量％、または２０～９９．９質量％の割合で含有することができる。 The solid content of this composition is 0.1 to 70% by mass, or 0.1 to 60% by mass. Solid content is the content rate of all the components remove | excluding the solvent from the composition (a3). The organic resin (a2) can be contained in the solid content in a proportion of 1 to 99.9% by mass, or 20 to 99.9% by mass.
本発明に用いられる有機樹脂（ａ２）は、重量平均分子量が６００～１００００００、又は６００～２０００００である。 The organic resin (a2) used in the present invention has a weight average molecular weight of 600 to 1000000 or 600 to 200000.
また、本発明の表面粗化方法は、基板上に有機樹脂（ｂ２）を含む組成物（ｂ３）を塗布し乾燥と硬化を行って有機樹脂層（Ｂ）を形成し、更に有機樹脂層（Ｂ）の上に無機粒子（ａ１）と有機樹脂（ａ２）を含む組成物（ａ３）を塗布し乾燥と硬化を行って有機樹脂層（Ａ）を形成する第１工程（この工程を特に第１’工程という）と、基板の上方からエッチング（ガスエッチング又は湿式エッチング）を行って同基板の表面を粗化する第２工程とを含むものでもある。 Moreover, the surface roughening method of this invention apply | coats the composition (b3) containing organic resin (b2) on a board | substrate, performs drying and hardening, forms an organic resin layer (B), and also organic resin layer ( A first step (particularly the first step) in which a composition (a3) containing inorganic particles (a1) and an organic resin (a2) is applied onto B) and dried and cured to form an organic resin layer (A). 1 'step) and a second step of roughening the surface of the substrate by etching (gas etching or wet etching) from above the substrate.
有機樹脂層（Ｂ）の有機樹脂（ｂ２）は、上記有機樹脂層（Ａ）の有機樹脂（ａ２）と同様の範囲の樹脂から選択することができる。更に有機樹脂（ｂ２）と有機樹脂（ａ２）は同じ樹脂を用いることができる。 The organic resin (b2) of the organic resin layer (B) can be selected from resins in the same range as the organic resin (a2) of the organic resin layer (A). Furthermore, the same resin can be used for the organic resin (b2) and the organic resin (a2).
本発明に用いられる組成物（ｂ３）は上記有機樹脂（ｂ２）と溶剤を含む。必要に応じて界面活性剤等の添加剤を含むことができる。この組成物の固形分は０．１～７０質量％、または０．１～６０質量％である。固形分は組成物（ｂ３）から溶剤を除いた全成分の含有割合である。固形分中に有機樹脂（ｂ２）を１～１００質量％、または１～９９．９質量％、または５０～９９．９質量％の割合で含有することができる。 The composition (b3) used in the present invention contains the organic resin (b2) and a solvent. If necessary, an additive such as a surfactant can be contained. The solid content of the composition is 0.1 to 70% by mass, or 0.1 to 60% by mass. Solid content is the content rate of all the components remove | excluding the solvent from the composition (b3). The organic resin (b2) can be contained in the solid content in a proportion of 1 to 100% by mass, or 1 to 99.9% by mass, or 50 to 99.9% by mass.
本発明に用いられる有機樹脂（ｂ２）は、重量平均分子量が６００～１００００００、又は６００～２０００００である。 The organic resin (b2) used in the present invention has a weight average molecular weight of 600 to 1000000 or 600 to 200000.
有機樹脂層（Ｂ）は組成物（ｂ３）を基板上に塗布し乾燥と硬化を行って得られるが、有機樹脂層（Ｂ）の上層に有機樹脂層（Ａ）が上塗りされるため、インターミキシング（層混合）を防ぐために、組成物（ｂ３）は更に架橋剤及び架橋触媒を含有することができる。 The organic resin layer (B) is obtained by applying the composition (b3) on the substrate, drying and curing, and the organic resin layer (A) is overcoated on the organic resin layer (B). In order to prevent mixing (layer mixing), the composition (b3) may further contain a crosslinking agent and a crosslinking catalyst.
また、必要により有機樹脂層（Ａ）も、組成物（ａ３）に架橋剤及び架橋触媒を含有することができる。 If necessary, the organic resin layer (A) can also contain a crosslinking agent and a crosslinking catalyst in the composition (a3).
組成物（ａ３）や組成物（ｂ３）に用いられる架橋剤としては、メラミン系、置換尿素系、またはそれらのポリマー系等が挙げられる。好ましくは、少なくとも２個の架橋形成置換基を有する架橋剤であり、メトキシメチル化グリコールウリル、ブトキシメチル化グリコールウリル、メトキシメチル化メラミン、ブトキシメチル化メラミン、メトキシメチル化ベンゾグワナミン、ブトキシメチル化ベンゾグワナミン、メトキシメチル化尿素、ブトキシメチル化尿素、またはメトキシメチル化チオ尿素等の化合物である。また、これらの化合物の縮合体も使用することができる。架橋剤の添加量は、使用する塗布溶剤、使用する下地基板、要求される溶液粘度、要求される膜形状などにより変動するが、全固形分に対して０．００１～８０質量％、好ましくは０．０１～５０質量％、さらに好ましくは０．０５～４０質量％である。 Examples of the crosslinking agent used for the composition (a3) and the composition (b3) include melamine-based, substituted urea-based, or their polymer-based ones. Preferably, a cross-linking agent having at least two cross-linking substituents, methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, Compounds such as methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. Moreover, the condensate of these compounds can also be used. The addition amount of the crosslinking agent varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80% by mass, preferably based on the total solid content. 0.01 to 50% by mass, more preferably 0.05 to 40% by mass.
本発明では上記架橋反応を促進するための触媒としては、ｐ－トルエンスルホン酸、トリフルオロメタンスルホン酸、ピリジニウムｐ－トルエンスルホン酸、サリチル酸、スルホサリチル酸、クエン酸、安息香酸、ヒドロキシ安息香酸、ナフタレンカルボン酸等の酸性化合物又は／及び２，４，４，６－テトラブロモシクロヘキサジエノン、ベンゾイントシレート、２－ニトロベンジルトシレート、その他有機スルホン酸アルキルエステル等の熱酸発生剤を配合する事が出来る。配合量は全固形分に対して、０．０００１～２０質量％、好ましくは０．０００５～１０質量％、さらに好ましくは０．０１～３質量％である。 In the present invention, the catalyst for promoting the crosslinking reaction includes p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid. Acidic compounds such as acids or / and thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters may be added. I can do it. The blending amount is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total solid content.
本発明で組成物（ａ３）や組成物（ｂ３）に用いられる界面活性剤としては、例えばポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェノールエーテル、ポリオキシエチレンノニルフェノールエーテル等のポリオキシエチレンアルキルアリルエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（（株）トーケムプロダクツ製、商品名）、メガファックＦ１７１、Ｆ１７３、Ｒ４０（大日本インキ（株）製、商品名）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム（株）製、商品名）、アサヒガードＡＧ７１０、サーフロンＳ３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子（株）製、商品名）等のフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）等を挙げることができる。これらの界面活性剤の配合量は、本発明のリソグラフィー用レジスト下層膜材料の全固形分に対して通常２．０質量％以下、好ましくは１．０質量％以下である。これらの界面活性剤は単独で添加してもよいし、また２種以上の組合せで添加することもできる。 Examples of the surfactant used in the composition (a3) or the composition (b3) in the present invention include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like. Polyoxyethylene alkyl allyl ethers such as oxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan mono Sorbitan fatty acid esters such as stearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene Nonionic interfaces such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Activator, Ftop EF301, EF303, EF352 (trade name, manufactured by Tochem Products Co., Ltd.), MegaFuck F171, F173, R40 (trade name, manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (Sumitomo 3M) Fluorine-based surface actives such as Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd., trade name) Agent, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.) and the like. The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film material for lithography of the present invention. These surfactants may be added alone or in combination of two or more.
本発明で組成物（ａ３）や組成物（ｂ３）に用いられる溶剤としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトシキ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル等を用いることができる。これらの有機溶剤は単独で、または２種以上の組合せで使用される。 Examples of the solvent used in the composition (a3) or the composition (b3) in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxypropionic acid Ethyl, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate and the like can be used. These organic solvents are used alone or in combination of two or more.
さらに、プロピレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルアセテート等の高沸点溶剤を混合して使用することができる。これらの溶剤の中でプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、乳酸ブチル、及びシクロヘキサノン等がレベリング性の向上に対して好ましい。 Furthermore, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate can be mixed and used. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone and the like are preferable for improving the leveling property.
次に本発明の表面粗化方法について説明すると、基板や基材の表面にスピナー、コーター等の適当な塗布方法により組成物（ｂ３）や組成物（ａ３）を塗布後、ベークして硬化させ有機樹脂層（Ａ）や有機樹脂層（Ｂ）を作成する。 Next, the surface roughening method of the present invention will be described. After the composition (b3) or the composition (a3) is applied to the surface of the substrate or base material by an appropriate application method such as a spinner or a coater, it is baked and cured. An organic resin layer (A) and an organic resin layer (B) are created.
本発明では有機樹脂層（Ａ）が０．００１～１０μｍ、又は０．００５～３．０μｍの膜厚を有していて、有機樹脂層（Ｂ）が０．００１～１０μｍ、又は０．００５～３．０μｍの膜厚を有する。 In the present invention, the organic resin layer (A) has a thickness of 0.001 to 10 μm, or 0.005 to 3.0 μm, and the organic resin layer (B) has a thickness of 0.001 to 10 μm, or 0.005. It has a film thickness of ˜3.0 μm.
また塗布後ベーキングする条件としては８０～４００℃で０．５～１２０分間である。 The conditions for baking after coating are 80 to 400 ° C. and 0.5 to 120 minutes.
基板上に有機樹脂層（Ｂ）を形成しその上に有機樹脂層（Ａ）を形成するか、又は有機樹脂層（Ｂ）を形成せずに有機樹脂層（Ａ）を形成し、上記条件で硬化させた後、基板の上方からガスでエッチングを行って同基板の表面を粗化する。このエッチングガスは最初に酸素系ガスによるエッチングが行われることが好ましく、これにより無機粒子（ａ１）が存在しない部分が垂直方向に削り取られる。エッチングが基板面に到達した段階で、引き続き酸素系ガスでエッチングすることも可能であるが、その他のガス（例えばフッ素系ガス）でエッチングすることができ、それにより基板に凹凸を形成し粗面化することができる。 The organic resin layer (B) is formed on the substrate and the organic resin layer (A) is formed thereon, or the organic resin layer (A) is formed without forming the organic resin layer (B). Then, the surface of the substrate is roughened by etching with gas from above the substrate. This etching gas is preferably first etched with an oxygen-based gas, whereby the portion where the inorganic particles (a1) are not present is scraped off in the vertical direction. When the etching reaches the substrate surface, it is possible to continue etching with an oxygen-based gas. However, etching can be performed with other gases (for example, fluorine-based gas), thereby forming irregularities on the substrate and roughening the surface. Can be
上記基板は基板自体や基板上にＳｉＯ２等を被覆した被覆基板も含み、基板や被覆基板の表面を粗化することができる。 The substrate includes a substrate itself and a coated substrate obtained by coating SiO 2 or the like on the substrate, and the surface of the substrate or the coated substrate can be roughened.
酸素系ガスとしては、酸素、酸素と窒素の混合ガス、酸素とアルゴンの混合ガス等が挙げられる。 Examples of the oxygen-based gas include oxygen, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and argon.
その他のガスとしてフッ素系ガスや塩素系ガスが挙げられる。ＣＦ４、Ｃ４Ｆ８、Ｃ４Ｆ６、ＣＨＦ３、ＣＨ２Ｆ２等のフッ素含有ガスが挙げられる。また、Ｃｌ２等の塩素系ガスを用いることもできる。 Other gases include fluorine-based gas and chlorine-based gas. Fluorine-containing gases such as CF 4 , C 4 F 8 , C 4 F 6 , CHF 3 , and CH 2 F 2 can be mentioned. A chlorine-based gas such as Cl 2 can also be used.
また、本発明にあっては、基板上に有機樹脂層（Ｂ）を形成しその上に有機樹脂層（Ａ）を形成するか、又は有機樹脂層（Ｂ）を形成せずに基板上に有機樹脂層（Ａ）を形成し、上記条件で硬化させた後、基板の上方から上記酸性水溶液でエッチングを行って同基板の表面を粗化する。この湿式エッチングにより無機粒子（ａ１）が存在しない部分が垂直方向に削り取られる。エッチングが基板面に到達した段階で、引き続き酸性水溶液でエッチングすることも可能であり、それにより基板に凹凸を形成し粗面化することができる。 In the present invention, the organic resin layer (B) is formed on the substrate and the organic resin layer (A) is formed thereon, or the organic resin layer (B) is not formed on the substrate. After the organic resin layer (A) is formed and cured under the above conditions, the surface of the substrate is roughened by etching with the acidic aqueous solution from above the substrate. By this wet etching, the portion where the inorganic particles (a1) do not exist is scraped off in the vertical direction. When the etching reaches the substrate surface, it is also possible to continue etching with an acidic aqueous solution, thereby forming irregularities on the substrate and roughening the surface.
上記基板は基板自体や基板上にＳｉＯ２等を被覆した被覆基板も含み、基板や被覆基板の表面を粗化することができる。 The substrate includes a substrate itself and a coated substrate obtained by coating SiO 2 or the like on the substrate, and the surface of the substrate or the coated substrate can be roughened.
ガス又は酸性水溶液によるエッチングが基板上に形成された（高さ）／（直径）で示される孔のアスペクト比で０．１～２０、又は０．１～１０の範囲に形成するまで行われるが、通常はエッチング時間としては１秒～１時間である。 Etching with a gas or an acidic aqueous solution is performed until the aspect ratio of the hole indicated by (height) / (diameter) formed on the substrate is 0.1 to 20, or 0.1 to 10 is formed. Usually, the etching time is 1 second to 1 hour.
さらにこのようにして得られた粗化表面をマスクとして下層に存在する基材を加工することができる。下層基材の加工にはガスによるドライエッチングもしくは湿式エッチングを用いることができる。 Further, the base material existing in the lower layer can be processed using the roughened surface thus obtained as a mask. For the processing of the lower layer base material, dry etching or wet etching using gas can be used.
ドライエッチング用のガスとしてフッ素系ガスや塩素系ガスが挙げられる。ＣＦ４、Ｃ４Ｆ８、Ｃ４Ｆ６、ＣＨＦ３、ＣＨ２Ｆ２等のフッ素含有ガスが挙げられる。また、Ｃｌ２等の塩素系ガスを用いることもできる。その他のガスとして、アルゴン、窒素、水素、酸素などが挙げられる。 Examples of the dry etching gas include a fluorine-based gas and a chlorine-based gas. Fluorine-containing gases such as CF 4 , C 4 F 8 , C 4 F 6 , CHF 3 , and CH 2 F 2 can be mentioned. A chlorine-based gas such as Cl 2 can also be used. Other gases include argon, nitrogen, hydrogen, oxygen, and the like.
基板としては例えばシリコン、酸化シリコン、ガラス、サファイアなどが挙げられる。 Examples of the substrate include silicon, silicon oxide, glass, and sapphire.
＜合成例１＞
１００ｍｌフラスコにフロログルシノール（東京化成工業（株）製）１２．０ｇ、４－ヒドロキシベンズアルデヒド（東京化成工業（株）製）７．３ｇ、メタンスルホン酸（東京化成工業（株）製）０．５９ｇ、プロピレングリコールモノメチルエーテル ４６．５ｇを入れた。その後加熱還流下で約３時間還流撹拌した。反応終了後、イオン交換処理を行い、茶褐色のフロログルシノール樹脂溶液を得た。得られたポリマーは式（１－１）に相当した。ＧＰＣによりポリスチレン換算で測定される重量平均分子量Ｍｗは６８０、多分散度Ｍｗ／Ｍｎは１．３であった。
<Synthesis Example 1>
In a 100 ml flask, 12.0 g of phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.3 g of 4-hydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. 59 g and 46.5 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was stirred under reflux for about 3 hours under heating and reflux. After completion of the reaction, an ion exchange treatment was performed to obtain a brown phloroglucinol resin solution. The obtained polymer corresponded to Formula (1-1). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 680, and the polydispersity Mw / Mn was 1.3.
＜合成例２＞
３００ｍｌフラスコにフロログルシノール（東京化成工業（株）製）２５．０ｇ、テレフタルアルデヒド酸（東京化成工業（株）製）２５．４ｇ、プロピレングリコールモノメチルエーテル １５１．１ｇを入れた。その後加熱還流下で約２時間還流撹拌した。反応終了後、イオン交換処理を行い、茶褐色のフロログルシノール樹脂溶液を得た。得られたポリマーは式（１－２）に相当した。ＧＰＣによりポリスチレン換算で測定される重量平均分子量Ｍｗは２，４００、多分散度Ｍｗ／Ｍｎは１．６であった。
<Synthesis Example 2>
A 300 ml flask was charged with 25.0 g of phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.4 g of terephthalaldehyde acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 151.1 g of propylene glycol monomethyl ether. Thereafter, the mixture was stirred under reflux for about 2 hours under heating and reflux. After completion of the reaction, an ion exchange treatment was performed to obtain a brown phloroglucinol resin solution. The obtained polymer corresponded to Formula (1-2). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 2,400, and the polydispersity Mw / Mn was 1.6.
＜合成例３＞
スチレン７．０ｇ（東京化成工業（株）製）、ヒドロキシエチルメタクリレート８．７ｇ（東京化成工業（株）製）、２，２’－アゾビスイソブチロニトリル０．７９ｇ、プロピレングリコールモノメチルエーテルアセテート３８．６ｇを溶解させた後、この溶液を加熱し、８５℃で約２０時間撹拌した。得られたポリマーは上記式（１－３）に相当した。ＧＰＣによりポリスチレン換算で測定される重量平均分子量Ｍｗは９，７００であった。
<Synthesis Example 3>
7.0 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.7 g of hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.79 g of 2,2′-azobisisobutyronitrile, propylene glycol monomethyl ether acetate After dissolving 38.6 g, the solution was heated and stirred at 85 ° C. for about 20 hours. The obtained polymer corresponded to the above formula (1-3). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 9,700.
＜合成例４＞
１００ｍｌナスフラスコにカルバゾール（東京化成工業（株）製）８．０ｇ、１－ナフトアルデヒド（東京化成工業（株）製）２８．０ｇ、ｐ－トルエンスルホン酸一水和物（東京化成工業（株）製）３．６ｇ、トルエン（関東化学（株）製）１４３．８ｇを入れた。その後フラスコ内を窒素置換した後加熱し、約２７時間還流撹拌した。反応終了後、テトラヒドロフラン（関東化学（株）製）９０．５ｇで希釈した。希釈液をメタノール２０００ｍｌへ滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物をメタノールで洗浄後、８５℃で一晩減圧乾燥しノボラック樹脂を３７．９ｇ得た。得られたポリマーは式（１－４）に相当した。ＧＰＣによりポリスチレン換算で測定される重量平均分子量Ｍｗは、３，８００であった。
<Synthesis Example 4>
In a 100 ml eggplant flask, 8.0 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 28.0 g of 1-naphthaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) )) 3.6 g and toluene (Kanto Chemical Co., Ltd.) 143.8 g. Thereafter, the atmosphere in the flask was replaced with nitrogen, and the mixture was heated and stirred at reflux for about 27 hours. After completion of the reaction, the reaction mixture was diluted with 90.5 g of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.). The diluted solution was dropped into 2000 ml of methanol and reprecipitated. The obtained precipitate was filtered by suction, and the filtrate was washed with methanol and dried under reduced pressure at 85 ° C. overnight to obtain 37.9 g of a novolak resin. The obtained polymer corresponded to the formula (1-4). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 3,800.
＜組成物（ａ３）に相当する表面粗化材調製例１＞
合成例１で得た樹脂０．６６ｇを、オルガノシリカゾル（日産化学工業（株）製〔商品名〕ＰＧＭ－ＳＴ、分散媒はプロピレングリコールモノメチルエーテル、シリカ濃度は３０質量％、平均粒子径１０～１５ｎｍ）０．３７ｇ、テトラメトキシメチルグリコールウリル０．１３ｇ、プロピレングリコールモノメチルエーテル２６．２ｇ、プロピレングリコールモノメチルエーテルアセテート２．６ｇ、に添加し溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ａ３－１）の溶液を調製した。
<Surface roughening material preparation example 1 corresponding to composition (a3)>
0.66 g of the resin obtained in Synthesis Example 1 was added to organosilica sol (manufactured by Nissan Chemical Industries, Ltd. [trade name] PGM-ST, the dispersion medium was propylene glycol monomethyl ether, the silica concentration was 30% by mass, and the average particle size was 10 to 10%. 15 nm) 0.37 g, tetramethoxymethyl glycoluril 0.13 g, propylene glycol monomethyl ether 26.2 g, and propylene glycol monomethyl ether acetate 2.6 g. Thereafter, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.2 μm to prepare a solution of the composition (a3-1).
＜組成物（ａ３）に相当する表面粗化材調製例２＞
合成例２で得た樹脂０．６４ｇを、オルガノシリカゾル（日産化学工業（株）製〔商品名〕ＰＧＭ－ＳＴ、分散媒はプロピレングリコールモノメチルエーテル、シリカ濃度は３０質量％、平均粒子径１０～１５ｎｍ）０．４３ｇ、テトラメトキシメチルグリコールウリル０．１３ｇ、プロピレングリコールモノメチルエーテル２０．４ｇ、プロピレングリコールモノメチルエーテルアセテート８．４ｇ、に添加し溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ａ３－２）の溶液を調製した。
<Surface roughening material preparation example 2 corresponding to composition (a3)>
0.64 g of the resin obtained in Synthesis Example 2 was added to organosilica sol (manufactured by Nissan Chemical Industries, Ltd. [trade name] PGM-ST, the dispersion medium was propylene glycol monomethyl ether, the silica concentration was 30% by mass, and the average particle size was 10 to 10%. 15 nm) 0.43 g, tetramethoxymethyl glycoluril 0.13 g, propylene glycol monomethyl ether 20.4 g, and propylene glycol monomethyl ether acetate 8.4 g. Thereafter, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.2 μm to prepare a solution of the composition (a3-2).
＜組成物（ａ３）に相当する表面粗化材調製例３＞
合成例３で得た樹脂０．６４ｇを、オルガノシリカゾル溶液（日産化学工業（株）製〔商品名〕ＰＧＭ－ＳＴ、分散媒はプロピレングリコールモノメチルエーテル、シリカ濃度は３０質量％、平均粒子径１０～１５ｎｍ）０．４３ｇ、テトラメトキシメチルグリコールウリル０．１３ｇ、プロピレングリコールモノメチルエーテル２３．３ｇ、プロピレングリコールモノメチルエーテルアセテート５．５ｇ、に添加し溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ａ３－３）の溶液を調製した。
<Surface roughening material preparation example 3 corresponding to composition (a3)>
0.64 g of the resin obtained in Synthesis Example 3 was added to an organosilica sol solution (product name: PGM-ST, manufactured by Nissan Chemical Industries, Ltd.), the dispersion medium was propylene glycol monomethyl ether, the silica concentration was 30% by mass, and the average particle size was 10 To 15 nm) 0.43 g, tetramethoxymethyl glycoluril 0.13 g, propylene glycol monomethyl ether 23.3 g, propylene glycol monomethyl ether acetate 5.5 g to obtain a solution. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a solution of the composition (a3-3).
＜組成物（ａ３）に相当する表面粗化材調製例４＞
合成例１で得た樹脂０．６５ｇを、オルガノシリカゾル溶液（日産化学工業（株）製〔商品名〕ＩＰＡ－ＳＴ、分散媒はイソプロパノール、シリカ濃度は３０質量％、平均粒子径１０～１５ｎｍ）０．３８ｇ、テトラメトキシメチルグリコールウリル０．１３ｇ、プロピレングリコールモノメチルエーテル２８．８ｇに添加し溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ａ３－４）の溶液を調製した。
<Surface roughening material preparation example 4 corresponding to composition (a3)>
0.65 g of the resin obtained in Synthesis Example 1 was added to an organosilica sol solution (trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd., the dispersion medium was isopropanol, the silica concentration was 30% by mass, and the average particle size was 10 to 15 nm) The solution was added to 0.38 g, tetramethoxymethyl glycoluril 0.13 g, and propylene glycol monomethyl ether 28.8 g. Thereafter, the solution was filtered using a polyethylene microfilter having a pore diameter of 0.2 μm to prepare a solution of the composition (a3-4).
＜組成物（ａ３）に相当する表面粗化材調製例５＞
合成例１で得た樹脂０．６５ｇを、オルガノシリカゾル溶液（日産化学工業（株）製〔商品名〕ＭＩＢＫ－ＳＴ、分散媒はメチルイソブチルケトン、シリカ濃度は３０質量％、平均粒子径１０～１５ｎｍ）０．３８ｇ、テトラメトキシメチルグリコールウリル０．１３ｇ、プロピレングリコールモノメチルエーテル２８．８ｇに添加し溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ａ３－５）の溶液を調製した。
<Surface roughening material preparation example 5 corresponding to composition (a3)>
0.65 g of the resin obtained in Synthesis Example 1 was added to an organosilica sol solution (manufactured by Nissan Chemical Industries, Ltd. [trade name] MIBK-ST, the dispersion medium was methyl isobutyl ketone, the silica concentration was 30% by mass, and the average particle size was 10 to 10%. 15 nm) 0.38 g, tetramethoxymethyl glycoluril 0.13 g, and propylene glycol monomethyl ether 28.8 g to obtain a solution. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a solution of the composition (a3-5).
＜組成物（ａ３）に相当する表面粗化材調製例６＞
合成例１で得た樹脂０．６５ｇを、オルガノシリカゾル溶液（日産化学工業（株）製〔商品名〕ＩＰＡ－ＳＴ－Ｌ、分散媒はイソプロパノール、シリカ濃度は３０質量％、平均粒子径４０～５０ｎｍ）０．３８ｇ、テトラメトキシメチルグリコールウリル０．１３ｇ、プロピレングリコールモノメチルエーテル２８．８ｇに添加し溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ａ３－６）の溶液を調製した。
<Surface roughening material preparation example 6 corresponding to composition (a3)>
0.65 g of the resin obtained in Synthesis Example 1 was added to an organosilica sol solution (manufactured by Nissan Chemical Industries, Ltd. [trade name] IPA-ST-L, the dispersion medium was isopropanol, the silica concentration was 30% by mass, and the average particle size was 40 to 40%. 50 nm) 0.38 g, tetramethoxymethyl glycoluril 0.13 g, and propylene glycol monomethyl ether 28.8 g to obtain a solution. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a solution of the composition (a3-6).
＜組成物（ａ３）に相当する表面粗化材調製例７＞
合成例１で得た樹脂０．６５ｇを、オルガノシリカゾル溶液（日産化学工業（株）製〔商品名〕ＭＩＢＫ－ＳＴ－Ｌ、分散媒はメチルイソブチルケトン、シリカ濃度は３０質量％、平均粒子径４０～５０ｎｍ）０．６５ｇ、テトラメトキシメチルグリコールウリル０．１３ｇ、プロピレングリコールモノメチルエーテル２８．８ｇ、に添加し溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ａ３－７）の溶液を調製した。
<Surface roughening material preparation example 7 corresponding to composition (a3)>
0.65 g of the resin obtained in Synthesis Example 1 was added to an organosilica sol solution (manufactured by Nissan Chemical Industries, Ltd. [trade name] MIBK-ST-L, the dispersion medium was methyl isobutyl ketone, the silica concentration was 30% by mass, and the average particle size) 40 to 50 nm) was added to 0.65 g, tetramethoxymethyl glycoluril 0.13 g, and propylene glycol monomethyl ether 28.8 g to obtain a solution. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a solution of the composition (a3-7).
＜組成物（ｂ３）に相当する有機ハードマスク材調製例１＞
合成例４で得た樹脂２ｇに、テトラメトキシメチルグリコールウリル０．３ｇ、ピリジニウム－ｐ－トルエンスルホナート０．０３ｇ、界面活性剤（ＤＩＣ（株）製、品名：メガファック〔商品名〕Ｒ－４０、成分はフッ素系界面活性剤）０．００２ｇ、プロピレングリコールモノメチルエーテルアセテート６．８ｇ、プロピレングリコールモノメチルエーテル１５．８ｇに溶解させ溶液とした。その後、孔径０．２μｍのポリエチレン製ミクロフィルターを用いてろ過し、組成物（ｂ３－１）の溶液を調製した。
<Organic hard mask material preparation example 1 corresponding to a composition (b3)>
To 2 g of the resin obtained in Synthesis Example 4, 0.3 g of tetramethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R- 40, component is fluorine surfactant) 0.002 g, propylene glycol monomethyl ether acetate 6.8 g, propylene glycol monomethyl ether 15.8 g dissolved in solution. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a solution of the composition (b3-1).
＜実施例１＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し１５０ｎｍの有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。得られた有機樹脂層（Ｂ）（有機ハードマスク層）上に表面粗化材調製例１で得られた組成物（ａ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 1>
A solution of the composition (b3-1) obtained in Organic Hard Mask Material Preparation Example 1 was applied to a substrate with a spin coater, and baked at 240 ° C. for 1 minute, and a 150 nm organic resin layer (B) (organic hard mask layer) Formed. On the obtained organic resin layer (B) (organic hard mask layer), the solution of the composition (a3-1) obtained in Surface Roughening Material Preparation Example 1 was applied to a substrate with a spin coater, and the temperature was set at 240 ° C. The organic resin layer (A) (surface roughening layer) was formed by baking for a minute.
＜実施例２＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し１５０ｎｍの有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。得られた有機樹脂層（Ｂ）（有機ハードマスク層）上に表面粗化材調製例２で得られた組成物（ａ３－２）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 2>
A solution of the composition (b3-1) obtained in Organic Hard Mask Material Preparation Example 1 was applied to a substrate with a spin coater, and baked at 240 ° C. for 1 minute, and a 150 nm organic resin layer (B) (organic hard mask layer) Formed. On the obtained organic resin layer (B) (organic hard mask layer), a solution of the composition (a3-2) obtained in Surface Roughening Material Preparation Example 2 was applied to a substrate with a spin coater, and the temperature was set at 240 ° C. The organic resin layer (A) (surface roughening layer) was formed by baking for a minute.
＜実施例３＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し１５０ｎｍの有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。得られた有機樹脂層（Ｂ）（有機ハードマスク層）上に表面粗化材調製例３で得られた組成物（ａ３－３）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 3>
A solution of the composition (b3-1) obtained in Organic Hard Mask Material Preparation Example 1 was applied to a substrate with a spin coater, and baked at 240 ° C. for 1 minute, and a 150 nm organic resin layer (B) (organic hard mask layer) Formed. On the obtained organic resin layer (B) (organic hard mask layer), a solution of the composition (a3-3) obtained in Surface Roughening Material Preparation Example 3 was applied to a substrate with a spin coater, and 240 ° C. 1 The organic resin layer (A) (surface roughening layer) was formed by baking for a minute.
＜実施例４＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し１５０ｎｍの有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。得られた有機樹脂層（Ｂ）（有機ハードマスク層）上に表面粗化材調製例４で得られた組成物（ａ３－４）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 4>
A solution of the composition (b3-1) obtained in Organic Hard Mask Material Preparation Example 1 was applied to a substrate with a spin coater, and baked at 240 ° C. for 1 minute, and a 150 nm organic resin layer (B) (organic hard mask layer) Formed. On the obtained organic resin layer (B) (organic hard mask layer), a solution of the composition (a3-4) obtained in Surface Roughening Material Preparation Example 4 was applied to a substrate with a spin coater, and 240 ° C. 1 The organic resin layer (A) (surface roughening layer) was formed by baking for a minute.
＜実施例５＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し１５０ｎｍの有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。得られた有機樹脂層（Ｂ）（有機ハードマスク層）上に表面粗化材調製例５で得られた組成物（ａ３－５）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 5>
A solution of the composition (b3-1) obtained in Organic Hard Mask Material Preparation Example 1 was applied to a substrate with a spin coater, and baked at 240 ° C. for 1 minute, and a 150 nm organic resin layer (B) (organic hard mask layer) Formed. On the obtained organic resin layer (B) (organic hard mask layer), a solution of the composition (a3-5) obtained in Surface Roughening Material Preparation Example 5 was applied to a substrate with a spin coater, and 240 ° C. 1 The organic resin layer (A) (surface roughening layer) was formed by baking for a minute.
＜実施例６＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し１５０ｎｍの有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。得られた有機樹脂層（Ｂ）（有機ハードマスク層）上に表面粗化材調製例６で得られた組成物（ａ３－６）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 6>
A solution of the composition (b3-1) obtained in Organic Hard Mask Material Preparation Example 1 was applied to a substrate with a spin coater, and baked at 240 ° C. for 1 minute, and a 150 nm organic resin layer (B) (organic hard mask layer) Formed. On the obtained organic resin layer (B) (organic hard mask layer), a solution of the composition (a3-6) obtained in Surface Roughening Material Preparation Example 6 was applied to a substrate with a spin coater, and 240 ° C. 1 The organic resin layer (A) (surface roughening layer) was formed by baking for a minute.
＜実施例７＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し１５０ｎｍの有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。得られた有機樹脂層（Ｂ）（有機ハードマスク層）上に表面粗化材調製例７で得られた組成物（ａ３－７）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 7>
A solution of the composition (b3-1) obtained in Organic Hard Mask Material Preparation Example 1 was applied to a substrate with a spin coater, and baked at 240 ° C. for 1 minute, and a 150 nm organic resin layer (B) (organic hard mask layer) Formed. On the obtained organic resin layer (B) (organic hard mask layer), a solution of the composition (a3-7) obtained in Surface Roughening Material Preparation Example 7 was applied to a substrate with a spin coater, and 240 ° C. 1 The organic resin layer (A) (surface roughening layer) was formed by baking for a minute.
＜実施例８＞
表面粗化材調製例１で得られた組成物（ａ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ａ）（表面粗化層）を形成した。
<Example 8>
A solution of the composition (a3-1) obtained in Surface Roughening Material Preparation Example 1 is applied to a substrate with a spin coater and baked at 240 ° C. for 1 minute to form an organic resin layer (A) (surface roughening layer). did.
＜比較例１＞
有機ハードマスク材調製例１で得られた組成物（ｂ３－１）の溶液をスピンコーターにて基板に塗布し、２４０℃１分間焼成し有機樹脂層（Ｂ）（有機ハードマスク層）を形成した。
<Comparative Example 1>
The composition (b3-1) solution obtained in Organic Hard Mask Material Preparation Example 1 is applied to a substrate with a spin coater and baked at 240 ° C. for 1 minute to form an organic resin layer (B) (organic hard mask layer). did.
［表面粗化評価］
実施例１～８から得られた表面粗化層が形成されたウェハーをＲＩＥ－１０ＮＲ（サムコ（株）製）にて用いてエッチングを行なった。エッチングガスとしてＯ２ガスを使用して実施例１～７では９０秒間エッチングし、実施例８と比較例１では６０秒間エッチングすることで、表面粗化層の有機成分のみを優先的にエッチングした。実施例１～７では有機ハードマスク層をエッチングすることで表面粗化層を形成した。
得られた有機樹脂層（Ａ）又は有機樹脂層（Ａ）と有機樹脂層（Ｂ）による表面粗化層について走査型電子顕微鏡（Ｈｉｔａｃｈi Ｓ－４８００）を用いて形状を観察した（図１～図５を参照）。
同様に有機樹脂層（Ｂ）のみによる表面粗化の形状を観察した（図６）。
[Surface roughening evaluation]
Etching was performed using RIE-10NR (manufactured by Samco Co., Ltd.) on the wafer on which the surface roughened layer obtained from Examples 1 to 8 was formed. Etching was performed for 90 seconds in Examples 1 to 7 using O 2 gas as an etching gas, and for 60 seconds in Example 8 and Comparative Example 1, only the organic component of the surface roughened layer was preferentially etched. . In Examples 1 to 7, the surface roughened layer was formed by etching the organic hard mask layer.
The shape of the obtained organic resin layer (A) or the roughened surface layer of the organic resin layer (A) and the organic resin layer (B) was observed using a scanning electron microscope (Hitachi S-4800) (FIG. 1 to FIG. 1). (See FIG. 5).
Similarly, the shape of surface roughening only by the organic resin layer (B) was observed (FIG. 6).
［下地ＴＥＯＳ加工評価］
実施例１から得られた有機樹脂層（Ａ）と有機樹脂層（Ｂ）による表面粗化層が形成されたウェハーをＲＩＥ－１０ＮＲ（サムコ（株）製）にて用いてエッチングを行なった。エッチングガスとしてＯ２ガスを使用して９０秒間エッチングすることで、表面粗化層の有機成分のみを優先的にエッチングし、さらに有機ハードマスク層をエッチングすることで表面粗化層を形成した。続いて表面粗化層を、エッチングガスとしてＣ４Ｆ８／Ａｒ／Ｏ２ガスを使用して１８０秒間エッチングすることで下層のＴＥＯＳ（テトラエトキシシランの加水分解縮合物によるＳｉＯ２被膜）の加工を行った。
得られた基板について走査型電子顕微鏡（Ｈｉｔａｃｈi Ｓ－４８００）を用いて形状を観察した（図７～図８を参照）。
[Base TEOS processing evaluation]
Etching was performed using RIE-10NR (manufactured by Samco Corporation) on the wafer on which the surface roughened layer formed of the organic resin layer (A) and the organic resin layer (B) obtained from Example 1 was formed. By etching for 90 seconds using O 2 gas as an etching gas, only the organic component of the surface roughened layer was preferentially etched, and the organic hard mask layer was further etched to form the surface roughened layer. Subsequently, the surface roughened layer is etched for 180 seconds using C 4 F 8 / Ar / O 2 gas as an etching gas, thereby processing the lower layer TEOS (SiO 2 film by tetraethoxysilane hydrolysis condensate). Went.
The shape of the obtained substrate was observed using a scanning electron microscope (Hitachi S-4800) (see FIGS. 7 to 8).
本発明により、基板の表面を粗化する新規な方法が提供される。特に、本発明の方法は、基板上に無機物と有機物が混在する層を利用することができるので、無機物と有機物の酸素ガス又は酸性水溶液のエッチング速度差を利用して基板の表面に酸素ガス又は酸性水溶液によりエッチングされる部分とエッチングされない表面粗化層とを形成することができ、そして更にその表面粗化層をマスクとして酸素ガス又はフッ素系ガス等のガスや、酸性水溶液のエッチングにより基板表面を粗化、例えば基板上に微細な凹凸を形成することができる。また、これらの性質を利用してＬＥＤ等の光取り出し層に適用することができる。 The present invention provides a novel method for roughening the surface of a substrate. In particular, since the method of the present invention can use a layer in which an inorganic substance and an organic substance are mixed on the substrate, the oxygen gas or the oxygen gas or A portion etched with an acidic aqueous solution and a surface roughened layer that is not etched can be formed. Further, using the surface roughened layer as a mask, a gas such as oxygen gas or fluorine-based gas or an acidic aqueous solution is used to etch the substrate surface. For example, fine irregularities can be formed on the substrate. Moreover, it can apply to light extraction layers, such as LED, using these characteristics.
Claims (14)
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| KR1020167020998A KR102358180B1 (en) | 2014-03-28 | 2015-03-27 | Surface roughening method |
| CN201580011270.5A CN106061627B (en) | 2014-03-28 | 2015-03-27 | Surface roughening method |
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| CN118117019A (en) * | 2015-09-15 | 2024-05-31 | 日产化学工业株式会社 | Surface roughening method based on wet treatment |
| TWI803390B (en) * | 2022-07-15 | 2023-05-21 | 三福化工股份有限公司 | Etching composition and etching method thereof |
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| CN106061627A (en) | 2016-10-26 |
| TWI651017B (en) | 2019-02-11 |
| KR102358180B1 (en) | 2022-02-04 |
| CN106061627B (en) | 2020-08-04 |
| TW201611659A (en) | 2016-03-16 |
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| JPWO2015147294A1 (en) | 2017-04-13 |
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