JP2007156017A - Transparent film, optical member and manufacturing method of transparent film - Google Patents
Transparent film, optical member and manufacturing method of transparent film Download PDFInfo
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Abstract
Description
本発明は、透明膜、光学部材及び透明膜の製造方法に関し、特に、アルミニウム及び窒素を含有し反射防止膜として使用可能な透明膜、この透明膜がその表面に形成された光学部材、及び透明膜の製造方法に関する。 The present invention relates to a transparent film, an optical member, and a method for producing the transparent film, and in particular, a transparent film that contains aluminum and nitrogen and can be used as an antireflection film, an optical member on which the transparent film is formed, and a transparent film The present invention relates to a film manufacturing method.
従来より、太陽電池のフロントパネル、ディスプレイのプロントパネル、光ディスク、レンズ及びプリズム等の光が入射される透明部材の表面に、光の反射を抑え透過率を高めるために、反射防止膜を設ける技術が知られている。このような反射防止膜としては、屈折率が相互に異なる複数の層を積層し、光の干渉効果を利用して反射を抑制するものが一般的である(例えば、特許文献1参照。)。 Conventionally, a technique of providing an antireflection film on the surface of a transparent member on which light is incident, such as a front panel of a solar cell, a front panel of a display, an optical disc, a lens, and a prism, in order to suppress light reflection and increase transmittance. It has been known. As such an antireflection film, a film in which a plurality of layers having different refractive indexes are stacked and reflection is suppressed by using an optical interference effect is generally used (see, for example, Patent Document 1).
しかしながら、このような積層膜からなる反射防止膜は、入射する光の波長によって透過率が大きく異なるという問題点がある。このため、幅広い波長の光について効果的に反射を防止することが困難であると共に、反射防止膜の反射光が着色されてしまう。 However, the antireflection film made of such a laminated film has a problem that the transmittance varies greatly depending on the wavelength of incident light. For this reason, it is difficult to effectively prevent the reflection of light having a wide wavelength, and the reflected light of the antireflection film is colored.
そこで、透明部材の表面にモスアイ構造を形成することにより、光の反射を抑制する技術が開発されている。「モスアイ構造」とは、透明部材の表面に光の波長よりも短い周期で突起が形成された構造である。このような突起構造があると、光は個々の突起を識別することができないため、光学的には、透明部材の表面に突起と空気の中間的な光学的特性を持ちその膜厚が突起の高さに等しい薄膜が存在する場合と等価となる。このようなモスアイ構造を形成することにより、波長依存性が小さい反射防止構造を実現することができる(例えば、特許文献2及び非特許文献1参照。)。 Therefore, a technique for suppressing the reflection of light by forming a moth-eye structure on the surface of the transparent member has been developed. The “moth eye structure” is a structure in which protrusions are formed on the surface of the transparent member with a period shorter than the wavelength of light. With such a protrusion structure, light cannot distinguish individual protrusions, so optically, the surface of the transparent member has an intermediate optical characteristic between protrusions and air, and the film thickness is that of the protrusions. This is equivalent to the case where a thin film having the same height exists. By forming such a moth-eye structure, an antireflection structure with small wavelength dependency can be realized (see, for example, Patent Document 2 and Non-Patent Document 1).
しかしながら、上述の従来の技術には以下に示すような問題点がある。
すなわち、特許文献2には、上述のモスアイ構造を形成する方法として、スタンパーによる転写成型、微粒子の吹き付けによるブラスト加工、化学薬品によるエッチング、微粒子の貼り付けが例示されている。しかしながら、特許文献2には、これらの方法の具体的な実施方法については開示されておらず、具体的にどのようにしてモスアイ構造を形成すればよいかは不明である。例えば、ブラスト加工及び微粒子の貼り付けによる場合は、被加工物が太陽電池及びディスプレイのフラットパネルのように大面積の板状部材の場合は、全体に均一に加工を施すことが難しく、レンズ及びプリズムのような立体的な形状を持つ部材の場合も、任意の表面に所望の加工を施すことが難しい。また、転写成型による場合も、立体的な部材の任意の表面に所望の加工を施すことが難しい。更に、エッチングによる場合は、被加工物の材料によってその加工性が大きく左右され、例えば被加工物がセラミックスからなる場合は、加工が困難である。一方、非特許文献1には、金型を使用してモスアイ構造を形成することが記載されている。しかしながら、この場合は、被加工物の形状に合わせて専用の金型を作製しなくてはならず、加工コストが高くなる。
However, the conventional techniques described above have the following problems.
That is, Patent Document 2 exemplifies transfer molding with a stamper, blasting by spraying fine particles, etching with chemicals, and attaching fine particles as methods for forming the above-described moth-eye structure. However, Patent Document 2 does not disclose a specific implementation method of these methods, and it is unclear how the moth-eye structure should be specifically formed. For example, in the case of blasting and pasting of fine particles, when the workpiece is a plate-shaped member having a large area such as a solar cell and a flat panel of a display, it is difficult to uniformly process the entire lens, Even in the case of a member having a three-dimensional shape such as a prism, it is difficult to perform desired processing on an arbitrary surface. In addition, also by transfer molding, it is difficult to perform desired processing on an arbitrary surface of a three-dimensional member. Further, in the case of etching, the workability is greatly affected by the material of the work piece. For example, when the work piece is made of ceramics, the work is difficult. On the other hand, Non-Patent Document 1 describes that a moth-eye structure is formed using a mold. However, in this case, a dedicated die must be prepared in accordance with the shape of the workpiece, which increases the processing cost.
本発明は、かかる課題の認識に基づいてなされたものであり、その目的は、波長依存性が小さく幅広い波長の光の反射を抑制することができ、製造が容易な透明膜、この透明膜を備えた光学部材、及び透明膜の製造方法を提供することにある。 The present invention has been made on the basis of recognition of such a problem, and an object of the present invention is to provide a transparent film that has a small wavelength dependency and can suppress reflection of light of a wide wavelength and is easy to manufacture. It is in providing the optical member provided and the manufacturing method of a transparent film.
本発明に係る透明膜は、アルミニウムを含有するターゲットを使用し窒素を含有するガス中でスパッタリングを行うことにより基体上に成膜されアルミニウムの一部が窒化された窒素含有アルミニウム膜を水中で加熱することにより形成されたことを特徴とする。 The transparent film according to the present invention heats a nitrogen-containing aluminum film in which a part of aluminum is nitrided by being sputtered in a nitrogen-containing gas using a target containing aluminum and is partially nitrided in water. It was formed by doing.
本発明に係る透明膜は、スパッタリングにより成膜した膜を水中で加熱することにより形成できるため、製造が容易である。 The transparent film according to the present invention can be formed easily by heating a film formed by sputtering in water.
また、前記透明膜の表面にモスアイ構造が形成されていることが好ましい。これにより、光の反射を抑制し、基体における光の透過率を高めることができる。更に、前記モスアイ構造は、その平均間隔が1.0ミクロン(μm)以下である複数の突起が形成された構造であってもよい。これにより、可視光の反射をより効率的に抑制することができる。 Moreover, it is preferable that a moth-eye structure is formed on the surface of the transparent film. Thereby, reflection of light can be suppressed and the light transmittance in the substrate can be increased. Further, the moth-eye structure may be a structure in which a plurality of protrusions having an average interval of 1.0 micron (μm) or less are formed. Thereby, reflection of visible light can be more efficiently suppressed.
このとき、前記突起における前記基体の表面に平行な断面の面積は、前記突起の根元部から先端部に向かって連続的に小さくなっていることが好ましい。これにより、透明膜の平均屈折率が膜厚方向に沿って連続的に変化するため、幅広い波長の光に対して、反射を抑制することができる。 At this time, it is preferable that an area of a cross section of the protrusion parallel to the surface of the base body is continuously reduced from the base portion to the tip portion of the protrusion. Thereby, since the average refractive index of a transparent film changes continuously along a film thickness direction, reflection can be suppressed for light having a wide wavelength.
本発明に係る光学部材は、
透明な基体と、
アルミニウムを含有するターゲットを使用し窒素を含有するガス中でスパッタリングを行うことにより前記基体上に成膜されアルミニウムの一部が窒化された窒素含有アルミニウム膜を水中で加熱することにより前記基体上に形成された透明膜と、
を備えたことを特徴とする
The optical member according to the present invention is
A transparent substrate,
Sputtering is performed in a nitrogen-containing gas using a target containing aluminum, and a nitrogen-containing aluminum film in which a part of aluminum is nitrided is heated in water on the substrate by sputtering on the substrate. A formed transparent film;
It is characterized by having
本発明に係る透明膜の製造方法は、
アルミニウムを含有するターゲットを使用し、窒素を含有するガス中でスパッタリングを行うことにより基体上にアルミニウムの一部が窒化された窒素含有アルミニウム膜を形成する工程と、
前記窒素含有アルミニウム膜を水中で加熱する工程と、
を備えたことを特徴とする。
The method for producing a transparent film according to the present invention includes:
Forming a nitrogen-containing aluminum film in which a part of aluminum is nitrided on a substrate by performing sputtering in a nitrogen-containing gas using a target containing aluminum; and
Heating the nitrogen-containing aluminum film in water;
It is provided with.
また、前記ガスは、窒素ガス及び希ガスの混合ガスであってもよい。 The gas may be a mixed gas of nitrogen gas and rare gas.
更に、前記水中で加熱する工程は、前記窒素含有アルミニウム膜を水中で煮沸する工程を含むことが好ましい。これにより、加熱温度を均一に保つことが容易になる。 Furthermore, it is preferable that the step of heating in water includes a step of boiling the nitrogen-containing aluminum film in water. This makes it easy to keep the heating temperature uniform.
本発明によれば、波長依存性が小さく幅広い波長の光の反射を抑制することができ、製造が容易な透明膜を得ることができる。 According to the present invention, it is possible to obtain a transparent film that has a small wavelength dependency and can suppress reflection of light having a wide range of wavelengths and can be easily manufactured.
以下、本発明の実施形態について、添付の図面を参照して具体的に説明する。
図1は、本実施形態に係る光学部材を示す断面図である。
本実施形態に係る光学部材1においては、透明または不透明な基体2が設けられており、この基体2の表面上に、透明膜3が設けられている。透明膜3は、例えば、近紫外光領域から赤外光領域に亘り高い光透過率を有する。透明膜3においては、連続膜である基部4と、この基部4上に形成されたモスアイ構造部5とが設けられている。モスアイ構造部5においては、複数の突起6が基体2の表面に垂直な方向(以下、上方という)に向かって起立しており、突起6間は空気層となっている。突起6の高さは例えば0.1〜1.0μmであり、突起6間の平均間隔は例えば1.0μm以下であり、例えば0.1〜1.0μmである。また、突起6間の平均間隔に対する高さの比率は例えば0.3以上である。この比率が大きいほど、光学部材1の反射率は低下する。
Hereinafter, embodiments of the present invention will be specifically described with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view showing an optical member according to this embodiment.
In the optical member 1 according to the present embodiment, a transparent or opaque base 2 is provided, and a transparent film 3 is provided on the surface of the base 2. For example, the transparent film 3 has a high light transmittance from the near ultraviolet light region to the infrared light region. In the transparent film 3, a base portion 4 that is a continuous film and a moth-eye structure portion 5 formed on the base portion 4 are provided. In the moth-eye structure 5, a plurality of protrusions 6 stand up in a direction perpendicular to the surface of the base 2 (hereinafter referred to as “upward”), and an air layer is formed between the protrusions 6. The height of the protrusions 6 is, for example, 0.1 to 1.0 μm, and the average distance between the protrusions 6 is, for example, 1.0 μm or less, for example, 0.1 to 1.0 μm. Further, the ratio of the height to the average interval between the protrusions 6 is, for example, 0.3 or more. The greater this ratio, the lower the reflectivity of the optical member 1.
光学部材1は、例えば、太陽電池のフロントパネル、ディスプレイのプロントパネル、光ディスク、レンズ又はプリズム等の光が入射される部材である。従って、基体2は、例えば、太陽電池セル、ガラス若しくは透明樹脂等の透明材料により形成された板材、レンズ本体、又はプリズム本体などである。また、透明膜3は、アルミニウム(Al)及び窒素(N)を含有している。更に、突起6の形状は、例えば丸みを帯びた円錐形である。即ち、突起6における基体2の表面に平行な断面の面積は、突起の根元部から先端部に向かって連続的に小さくなっている。 The optical member 1 is a member on which light such as a front panel of a solar cell, a front panel of a display, an optical disc, a lens, or a prism is incident. Accordingly, the substrate 2 is, for example, a solar battery cell, a plate material formed of a transparent material such as glass or transparent resin, a lens body, or a prism body. The transparent film 3 contains aluminum (Al) and nitrogen (N). Furthermore, the shape of the protrusion 6 is, for example, a rounded cone. That is, the area of the cross section of the protrusion 6 parallel to the surface of the base 2 is continuously reduced from the base portion of the protrusion toward the tip portion.
次に、本実施形態に係る透明膜の製造方法について説明する。
図2は、本実施形態に係る透明膜の製造方法を示すフローチャート図である。
先ず、図2のステップS1に示すように、スパッタリング装置のチャンバー内に、ターゲットとしてアルミニウム板を装着する。また、このターゲットに対向する位置に、基板として基体2を装着する。次に、チャンバー内を排気した後、チャンバー内に窒素とアルゴンの混合ガスを導入する。そして、ターゲットと基体2との間に電圧を印加して、イオン化したアルゴン原子をターゲットに衝突させる。これにより、ターゲットを形成するアルミニウム原子を基体2に向けて飛来させ、基体2上に堆積させる。このとき、アルミニウムと窒素とが反応して、アルミニウムの一部が窒化される。
Next, the manufacturing method of the transparent film which concerns on this embodiment is demonstrated.
FIG. 2 is a flowchart showing the transparent film manufacturing method according to the present embodiment.
First, as shown in step S1 of FIG. 2, an aluminum plate is mounted as a target in the chamber of the sputtering apparatus. In addition, the base 2 is mounted as a substrate at a position facing the target. Next, after evacuating the chamber, a mixed gas of nitrogen and argon is introduced into the chamber. Then, a voltage is applied between the target and the base 2 to cause ionized argon atoms to collide with the target. As a result, aluminum atoms forming the target fly toward the substrate 2 and are deposited on the substrate 2. At this time, aluminum and nitrogen react and a part of aluminum is nitrided.
このようにして、基体2の表面上に、反応性スパッタリングにより、アルミニウムの一部が窒化された窒素含有アルミニウム膜(以下、Al−N膜ともいう)が形成される。Al−N膜の膜厚は、例えば、0.1〜1.0μmとする。その後、チャンバーから、表面上にAl−N膜が形成された基体2を取り出す。このとき、Al−N膜は不透明な黒色の膜となっている。 In this manner, a nitrogen-containing aluminum film (hereinafter also referred to as an Al—N film) in which a part of aluminum is nitrided is formed on the surface of the substrate 2 by reactive sputtering. The thickness of the Al—N film is, for example, 0.1 to 1.0 μm. Thereafter, the substrate 2 having an Al—N film formed on the surface is taken out from the chamber. At this time, the Al—N film is an opaque black film.
次に、ステップS2に示すように、この基体2及びAl−N膜を水中に浸漬し、煮沸する。煮沸時間はAl−N膜の膜厚によって調整し、例えば、Al−N膜の膜厚が100nmのときは、煮沸時間を32分間以上とする。これにより、Al−N膜は透明化し、透明膜3となる。そして、基体2及び透明膜3を水中から取り出し、冷却及び乾燥させる。このようにして、基体2上に透明膜3が形成され、光学部材1が製造される。 Next, as shown in step S2, the substrate 2 and the Al—N film are immersed in water and boiled. The boiling time is adjusted according to the film thickness of the Al—N film. For example, when the film thickness of the Al—N film is 100 nm, the boiling time is set to 32 minutes or more. As a result, the Al—N film becomes transparent and becomes the transparent film 3. Then, the substrate 2 and the transparent film 3 are taken out of the water, cooled and dried. In this way, the transparent film 3 is formed on the substrate 2 and the optical member 1 is manufactured.
次に、本実施形態の動作について説明する。
スパッタリングにより、基体2上にAl−N膜を成膜すると、このAl−N膜の表面に、微細な突起が複数形成される。そして、このAl−N膜を煮沸すると、Al−N膜の表面に形成されている微細な突起が、より大きな突起6に変形する。これにより、突起6がモスアイ構造部5を構成する。このとき、Al−N膜においては、下記化学式(1)〜(3)の少なくとも1つに示す反応が生じているものと推測される。
AlN+3H2O→Al(OH)3+NH3 (1)
2Al+3H2O→Al2O3+3H2 (2)
2Al+6H2O→2Al(OH)3+3H2 (3)
Next, the operation of this embodiment will be described.
When an Al—N film is formed on the substrate 2 by sputtering, a plurality of fine protrusions are formed on the surface of the Al—N film. When the Al—N film is boiled, fine protrusions formed on the surface of the Al—N film are deformed into larger protrusions 6. Thereby, the protrusion 6 constitutes the moth-eye structure 5. At this time, in the Al—N film, it is presumed that the reaction represented by at least one of the following chemical formulas (1) to (3) occurs.
AlN + 3H 2 O → Al (OH) 3 + NH 3 (1)
2Al + 3H 2 O → Al 2 O 3 + 3H 2 (2)
2Al + 6H 2 O → 2Al (OH) 3 + 3H 2 (3)
このようにして製造された光学部材1における透明膜3が形成されている表面に、可視光などの光を入射させると、この光は個々の突起6を識別できず、膜厚が突起6の高さと等しく、光学的特性が突起6と空気との中間である仮想的な薄膜が存在する場合と等価な光学的挙動を示す。この結果、光学部材1の表面においては、光の反射が抑制され、その分、光学部材1の透過率が向上する。 When light such as visible light is incident on the surface of the optical member 1 manufactured in this way on which the transparent film 3 is formed, the light cannot identify individual protrusions 6 and the film thickness of the protrusions 6 is The optical behavior is equivalent to the case where there is a virtual thin film that is equal to the height and whose optical characteristics are intermediate between the protrusion 6 and air. As a result, light reflection is suppressed on the surface of the optical member 1, and the transmittance of the optical member 1 is improved accordingly.
次に、本実施形態の効果について説明する。
本実施形態によれば、透明膜3の表面にモスアイ構造部5が形成されているため、光学部材1の表面における反射率が低下し、光学部材1の透過率が向上する。また、突起6の平均間隔が0.1〜1.0μmであるため、可視光から近赤外光の反射をより効率的に抑制することができる。更に、突起6においては、基体2の表面に平行な断面の面積が、突起6の根元部から先端部に向かって連続的に小さくなっている。このため、透明膜3の膜厚方向の任意の位置における平均屈折率は、透明膜3の下面から上面に向かって、基部4の屈折率から空気の屈折率まで連続的に減少する。これにより、幅広い波長の光に対して、反射を抑制することができる。
Next, the effect of this embodiment will be described.
According to the present embodiment, since the moth-eye structure portion 5 is formed on the surface of the transparent film 3, the reflectance on the surface of the optical member 1 is reduced, and the transmittance of the optical member 1 is improved. Moreover, since the average space | interval of the processus | protrusion 6 is 0.1-1.0 micrometer, reflection of near infrared light from visible light can be suppressed more efficiently. Further, in the projection 6, the area of the cross section parallel to the surface of the base 2 is continuously reduced from the base portion to the tip portion of the projection 6. For this reason, the average refractive index at an arbitrary position in the film thickness direction of the transparent film 3 continuously decreases from the refractive index of the base 4 to the refractive index of air from the lower surface to the upper surface of the transparent film 3. Thereby, reflection can be suppressed with respect to light having a wide range of wavelengths.
また、本実施形態によれば、スパッタリング及び煮沸により、モスアイ構造を備えた透明膜を形成することができるため、基体の形状によらず、容易に透明膜を形成することができる。これにより、大面積の基体及び立体的な形状を持つ基体の表面にも透明膜3を均一に形成することができる。更に、Al−N膜を煮沸しているため、加熱温度を均一に保つことが容易であり、温度調節器等を設ける必要がない。なお、この加熱温度は水の沸点であり、水が純水であり気圧が1気圧である場合には100℃となる。このように、本実施形態によれば、波長依存性が小さく幅広い波長の光の反射を抑制することができ、製造が容易な透明膜を得ることができる。 Moreover, according to this embodiment, since the transparent film | membrane provided with the moth eye structure can be formed by sputtering and boiling, a transparent film | membrane can be formed easily irrespective of the shape of a base | substrate. Thereby, the transparent film 3 can be uniformly formed on the surface of a large-area substrate and a three-dimensional substrate. Furthermore, since the Al—N film is boiled, it is easy to keep the heating temperature uniform, and there is no need to provide a temperature controller or the like. The heating temperature is the boiling point of water, and when the water is pure water and the atmospheric pressure is 1 atm, the heating temperature is 100 ° C. As described above, according to the present embodiment, it is possible to obtain a transparent film that is small in wavelength dependency and can suppress reflection of light having a wide wavelength and can be easily manufactured.
なお、スパッタリングを行うためのスパッタリング装置は、DCスパッタリング装置であってもよく、RFスパッタリング装置であってもよい。また、本実施形態においては、Al−N膜を水中で煮沸する例を示したが、水は必ずしも沸騰させなくてもよく、水中において上述の反応が発生するような温度及び時間で加熱処理を行えばよい。例えば、アルミニウムの水和反応は80℃以上であれば進行するため、加熱温度は80℃以上とすることが好ましい。 Note that a sputtering apparatus for performing sputtering may be a DC sputtering apparatus or an RF sputtering apparatus. Moreover, in this embodiment, although the example which boils an Al-N film | membrane was shown in water, water does not necessarily need to boil and heat processing is performed at the temperature and time which the above-mentioned reaction generate | occur | produces in water. Just do it. For example, since the hydration reaction of aluminum proceeds at 80 ° C. or higher, the heating temperature is preferably 80 ° C. or higher.
以下、本発明に関連して本発明者が実施した試験例について説明する。 Hereinafter, test examples conducted by the present inventors in connection with the present invention will be described.
(試験例1)
試験例1では、スパッタリング時にチャンバー内に導入するAr−N2ガス(以下、スパッタガスという)における窒素濃度(CN2)がAl−N膜の外観及び表面形態に及ぼす影響を調査した。
(Test Example 1)
In Test Example 1, the influence of the nitrogen concentration (C N2 ) in Ar—N 2 gas (hereinafter referred to as sputtering gas) introduced into the chamber during sputtering on the appearance and surface morphology of the Al—N film was investigated.
図3は、本試験例において使用したスパッタリング装置を示すブロック図である。
図4(a)〜(d)は、成膜後のAl−N膜及びAl膜の外観を示す写真であり、(a)は窒素濃度CN2を0.0体積%とした場合、即ち、スパッタガスとして純アルゴンガスを使用した場合を示し、(b)は窒素濃度CN2を6.0体積%とした場合を示し、(c)は窒素濃度CN2を10体積%とした場合を示し、(d)は窒素濃度CN2を13体積%とした場合を示す。なお、図4は、方眼紙の上に試料を載置して撮影したものであり、膜が透明である場合は、背後の方眼紙が透けて見える。方眼紙の最小目盛りは1mmである。
FIG. 3 is a block diagram showing the sputtering apparatus used in this test example.
FIGS. 4A to 4D are photographs showing the appearance of the Al—N film and the Al film after film formation, and FIG. 4A shows the case where the nitrogen concentration C N2 is 0.0 vol%, that is, The case where pure argon gas is used as the sputtering gas is shown, (b) shows the case where the nitrogen concentration C N2 is 6.0 vol%, and (c) shows the case where the nitrogen concentration C N2 is 10 vol%. , (D) shows the case where the nitrogen concentration C N2 is set to 13% by volume. Note that FIG. 4 is a photograph of a sample placed on graph paper, and when the film is transparent, the graph paper behind can be seen through. The minimum scale of graph paper is 1 mm.
図5(a)〜(d)は、成膜後のAl−N膜及びAl膜のAFM測定結果を示す図であり、(a)は窒素濃度CN2を0.0体積%とした場合を示し、(b)は窒素濃度CN2を6.0体積%とした場合を示し、(c)は窒素濃度CN2を10体積%とした場合を示し、(d)は窒素濃度CN2を13体積%とした場合を示す。なお、スケールは図5(a)にしか示していないが、図5(b)〜(d)のスケールも、図5(a)のスケールと同様である。
図6は、CN2が6%であるAl−N膜の基板の表面に平行な各断面における空気(Air)とAl−N膜との割合を示す図である。
図7は、横軸に光の消衰係数及び屈折率をとり、縦軸に基板表面からの高さをとって、光の消衰係数及び屈折率の変化を示すグラフ図である。消衰係数及び屈折率は、各断面における平均値である。
FIGS. 5A to 5D are diagrams showing the AFM measurement results of the Al—N film and the Al film after film formation, and FIG. 5A shows the case where the nitrogen concentration C N2 is 0.0 volume%. (B) shows the case where the nitrogen concentration C N2 is 6.0% by volume, (c) shows the case where the nitrogen concentration C N2 is 10% by volume, and (d) shows the nitrogen concentration C N2 being 13%. The case of volume% is shown. Although the scale is shown only in FIG. 5 (a), the scales in FIGS. 5 (b) to 5 (d) are the same as the scale in FIG. 5 (a).
FIG. 6 is a diagram showing the ratio between air (Air) and the Al—N film in each cross section parallel to the surface of the substrate of the Al—N film with CN 2 of 6%.
FIG. 7 is a graph showing changes in the extinction coefficient and refractive index of light, with the horizontal axis representing the light extinction coefficient and refractive index and the vertical axis representing the height from the substrate surface. The extinction coefficient and the refractive index are average values in each cross section.
図3に示すように、このスパッタリング装置11においては、真空チャンバー12が設けられており、この真空チャンバー12には、スパッタガス導入管13及び排気管14が接続されている。スパッタガス導入管13は、その上流側が2本の支管13a及び13bに分岐しており、支管13aの途中にニードルバルブ15aが介在しており、支管13bの途中にニードルバルブ15bが介在している。そして、支管13aには純度が99.999%の窒素ガス(N2ガス)が供給され、支管13bには純度が99.9995%のアルゴンガス(Arガス)が供給されるようになっている。 As shown in FIG. 3, the sputtering apparatus 11 is provided with a vacuum chamber 12, and a sputtering gas introduction pipe 13 and an exhaust pipe 14 are connected to the vacuum chamber 12. The upstream side of the sputter gas introduction pipe 13 is branched into two branch pipes 13a and 13b, a needle valve 15a is interposed in the middle of the branch pipe 13a, and a needle valve 15b is interposed in the middle of the branch pipe 13b. . The branch pipe 13a is supplied with 99.999% purity nitrogen gas (N 2 gas), and the branch pipe 13b is supplied with 99.9995% purity argon gas (Ar gas). .
また、スパッタリング装置11にはロータリーポンプ(RP)16及びターボ分子ポンプ(TMP)17が設けられており、それぞれ排気管14を介して真空チャンバー12に接続されている。RP16と真空チャンバー12との間には粗引バルブ18が設けられており、TMP17と真空チャンバー12との間にはメインバルブ19が設けられている。更に、RP16とTMP17ともフォアバルブ20を介して接続されている。更に、真空チャンバー12内には、基板21及びターゲット22が相互に対向するように装着されるようになっている。 Further, the sputtering apparatus 11 is provided with a rotary pump (RP) 16 and a turbo molecular pump (TMP) 17, and each is connected to the vacuum chamber 12 via an exhaust pipe 14. A roughing valve 18 is provided between the RP 16 and the vacuum chamber 12, and a main valve 19 is provided between the TMP 17 and the vacuum chamber 12. Further, the RP 16 and the TMP 17 are also connected via the forevalve 20. Further, the substrate 21 and the target 22 are mounted in the vacuum chamber 12 so as to face each other.
本試験例においては、基板21として、コーニング(Corning)社製コード7059のバリウム・ホウケイ酸ガラス板を、真空チャンバー12内に装着した。なお、このガラス板における波長が589.3ナノメートル(nm)の光に対する屈折率は1.5333である。また、ターゲット22として、純アルミニウムからなるターゲットを真空チャンバー12内に装着した。 In this test example, a barium borosilicate glass plate of Corning Code 7059 was mounted in the vacuum chamber 12 as the substrate 21. In addition, the refractive index with respect to the light whose wavelength in this glass plate is 589.3 nanometer (nm) is 1.5333. A target made of pure aluminum was mounted in the vacuum chamber 12 as the target 22.
次に、真空チャンバー12を閉じ、RP16及びTMP17を順次作動させて、真空チャンバー12内の圧力を5.3×10−5〜1.1×10−4Pa(4.0〜8.0×10−7Torr)とした後、ニードルバルブ15a及び15bを調節することにより、スパッタガスとして真空チャンバー12内にAr−N2混合ガスを導入した。また、rf(Radio Frequency)出力は200Wとし、基板温度は373Kとした。なお、基板温度を室温よりも高くすることにより、膜厚を薄くしても、膜の表面に適度な凹凸を形成することができる。そして、スパッタガスの圧力を1.33Pa(10mTorr)で一定として、スパッタガス中の窒素濃度(CN2)が相互に異なる条件でスパッタリングを行い、厚さが300nmのAl−N膜又はAl膜を成膜した。成膜条件を表1に示す。 Next, the vacuum chamber 12 is closed, the RP 16 and the TMP 17 are sequentially operated, and the pressure in the vacuum chamber 12 is set to 5.3 × 10 −5 to 1.1 × 10 −4 Pa (4.0 to 8.0 ×). 10 −7 Torr), an Ar—N 2 mixed gas was introduced into the vacuum chamber 12 as a sputtering gas by adjusting the needle valves 15a and 15b. The rf (Radio Frequency) output was 200 W and the substrate temperature was 373K. Note that by making the substrate temperature higher than room temperature, moderate unevenness can be formed on the surface of the film even if the film thickness is reduced. Then, the sputtering gas pressure is kept constant at 1.33 Pa (10 mTorr), and sputtering is performed under conditions in which the nitrogen concentrations (C N2 ) in the sputtering gas are different from each other, and an Al—N film or an Al film having a thickness of 300 nm is formed. A film was formed. The film forming conditions are shown in Table 1.
成膜後に真空チャンバー12を開けて基板21を取り出し、Al−N膜又はAl膜の外観を観察した。観察結果を表1及び図4に示す。また、成膜後のAl−N膜又はAl膜の表面形態をAFM(Atomic Force Microscope:原子間力顕微鏡)によって測定した。測定結果を表1及び図5に示す。更に、成膜後のAl−N膜又はAl膜の結晶構造をX線回折法により同定した。測定結果を表1に示す。 After the film formation, the vacuum chamber 12 was opened, the substrate 21 was taken out, and the appearance of the Al—N film or the Al film was observed. The observation results are shown in Table 1 and FIG. Further, the surface morphology of the Al—N film or the Al film after film formation was measured with an AFM (Atomic Force Microscope). The measurement results are shown in Table 1 and FIG. Furthermore, the crystal structure of the Al—N film or Al film after film formation was identified by X-ray diffraction. The measurement results are shown in Table 1.
表1並びに図4及び図5に示すように、スパッタガスとして窒素濃度CN2が0体積%のガス、即ち、純アルゴンガスを使用すると、Al膜が形成されるが、このAl膜は表面に凹凸があり、白色に見えている。また、スパッタガスとして窒素濃度CN2が13体積%のガスを使用すると、アルミニウムがほぼ完全に窒化され、アルミニウムと窒素の原子組成比が1:1のAlN膜が形成される。このAlN膜の表面形態は平坦であり、透明に見える。これに対して、スパッタガスとして窒素濃度CN2が6体積%及び10体積%のガスを使用すると、アルミニウムが不完全に窒化された窒素含有アルミニウム膜(Al−N膜)が形成される。このAl−N膜は不透明である。そして、このAl−N膜を基板21側から見ると金属光沢を呈しており、露出面側から見ると光沢のない黒色である。このことから、Al−N膜には金属アルミニウムが存在しており、このAl−N膜の基板21側の表面は基板21の表面にならって平坦になるため金属光沢が認められ、露出面側の表面は凹凸が形成されているため金属光沢が失われているものと考えられる。また、窒素濃度CN2が6体積%の場合は表面の凹凸が大きく、窒素濃度CN2が10体積%の場合は表面の凹凸が小さい。 As shown in Table 1 and FIGS. 4 and 5, when a gas having a nitrogen concentration CN2 of 0% by volume, that is, pure argon gas is used as a sputtering gas, an Al film is formed. There are irregularities and it looks white. Further, when a gas having a nitrogen concentration CN2 of 13% by volume is used as the sputtering gas, aluminum is almost completely nitrided, and an AlN film having an atomic composition ratio of aluminum to nitrogen of 1: 1 is formed. The surface form of this AlN film is flat and appears transparent. On the other hand, when a gas having a nitrogen concentration CN2 of 6% by volume and 10% by volume is used as the sputtering gas, a nitrogen-containing aluminum film (Al—N film) in which aluminum is incompletely nitrided is formed. This Al—N film is opaque. The Al—N film exhibits a metallic luster when viewed from the substrate 21 side, and is black with no luster when viewed from the exposed surface side. Thus, metallic aluminum is present in the Al—N film, and the surface of the Al—N film on the substrate 21 side becomes flat following the surface of the substrate 21, so that metallic luster is recognized, and the exposed surface side It is thought that the metallic luster is lost because the surface of the surface is uneven. Further, when the nitrogen concentration C N2 is 6% by volume, the surface unevenness is large, and when the nitrogen concentration C N2 is 10% by volume, the surface unevenness is small.
また、図6に示すように、Al−N膜においては、各突起の基板表面に平行な断面の面積が、突起の根元部から先端部に向かって連続的に小さくなっているため、基板表面に平行な断面におけるAl−N膜が占める面積の割合は、下方から上方に向かって連続的に小さくなっている。逆に、基板表面に平行な断面における空気層が占める割合は、下方から上方に向かって連続的に大きくなっている。
このため、図7に示すように、Al−N膜の平均屈折率及び平均消衰係数は、Al−N膜の上面から下面に向かって連続的に増加している。この結果、Al−N膜の外観は黒色を呈している。
Further, as shown in FIG. 6, in the Al-N film, the area of the cross section parallel to the substrate surface of each protrusion is continuously reduced from the base portion of the protrusion toward the tip portion. The ratio of the area occupied by the Al—N film in the cross section parallel to is continuously decreasing from the bottom to the top. Conversely, the proportion of the air layer in the cross section parallel to the substrate surface increases continuously from the bottom to the top.
For this reason, as shown in FIG. 7, the average refractive index and the average extinction coefficient of the Al—N film continuously increase from the upper surface to the lower surface of the Al—N film. As a result, the appearance of the Al—N film is black.
このように、本試験例においては、スパッタガス中の窒素濃度CN2を6体積%とすることにより、表面の凹凸が大きいAl−N膜を形成することができた。しかしながら、この窒素濃度CN2の値は絶対的なものではなく、例えば基板温度等の他の条件が変われば、変化する。 As described above, in this test example, by setting the nitrogen concentration C N2 in the sputtering gas to 6% by volume, an Al—N film having large surface irregularities could be formed. However, the value of the nitrogen concentration C N2 is not absolute, and changes if other conditions such as the substrate temperature change.
(試験例2)
試験例2では、Al−N膜の膜厚が、Al−N膜の表面形態及び光学的特性に及ぼす影響を調査した。即ち、試験例1と同じ条件で、膜厚が相互に異なる複数種類のAl−N膜を形成し、その表面形態、並びに光の吸収率及び鏡面反射率を測定した。スパッタガス中の窒素濃度CN2は6.0体積%とした。
(Test Example 2)
In Test Example 2, the influence of the film thickness of the Al—N film on the surface morphology and optical characteristics of the Al—N film was investigated. That is, a plurality of types of Al—N films having different film thicknesses were formed under the same conditions as in Test Example 1, and the surface morphology, light absorption rate and specular reflectance were measured. The nitrogen concentration C N2 in the sputtering gas was 6.0% by volume.
図8(a)〜(c)は、試験例2において形成したAl−N膜のAFM測定結果を示す図であり、(a)は膜厚dを55nmとした場合を示し、(b)は膜厚dを200nmとした場合を示し、(c)は膜厚dを300nmとした場合を示す。なお、スケールは図8(c)にしか示していないが、図8(a)及び(b)のスケールも、図8(c)のスケールと同様である。
また、図9は、横軸に入射光の波長をとり、縦軸にこの入射光の吸収率及び鏡面反射率をとって、Al−N膜の光学的特性の膜厚依存性を示すグラフ図である。
8A to 8C are diagrams showing the AFM measurement results of the Al—N film formed in Test Example 2. FIG. 8A shows the case where the film thickness d is 55 nm, and FIG. The case where the film thickness d is 200 nm is shown, and (c) shows the case where the film thickness d is 300 nm. Although the scale is shown only in FIG. 8C, the scales in FIGS. 8A and 8B are the same as the scale in FIG. 8C.
FIG. 9 is a graph showing the film thickness dependence of the optical characteristics of the Al—N film, with the horizontal axis representing the wavelength of incident light and the vertical axis representing the absorption rate and specular reflectance of the incident light. It is.
図8(a)に示すように、膜厚dが55nmであると、Al−N膜の表面はほぼ平坦であったが、図8(b)に示すように、膜厚dが200nmになると、表面にサブミクロンオーダーの凹凸が形成された。そして、膜厚dが300nmになると、表面の凹凸はより大きくなった。即ち、Al−N膜の膜厚が増大するにつれて、表面の凹凸が増大した。
また、図9に示すように、膜厚dが増大するにつれて、可視領域の鏡面反射率が減少し、それを補償するように、吸収率が増加した。
As shown in FIG. 8A, when the film thickness d is 55 nm, the surface of the Al—N film is almost flat. However, as shown in FIG. 8B, when the film thickness d is 200 nm. Sub-micron-order irregularities were formed on the surface. And when the film thickness d was 300 nm, the unevenness of the surface became larger. That is, as the thickness of the Al—N film increased, the surface irregularities increased.
Further, as shown in FIG. 9, as the film thickness d increased, the specular reflectance in the visible region decreased, and the absorptance increased to compensate for it.
(試験例3)
試験例3では、スパッタリングにより形成されたAl−N膜を純水中で煮沸して、煮沸前後の膜の表面形態及び光学的特性を調査した。
図10は、各光学特性値の定義を示す図であり、
図11は、本試験例において使用した煮沸装置を示す断面図であり、
図12は、横軸に入射光の周波数をとり、縦軸に膜の全透過率をとって、煮沸中における全透過率の経時変化を示すグラフ図であり、
図13は、横軸に入射光の周波数をとり、縦軸に膜の全透過率をとって、煮沸による膜の全透過率の変化を示すグラフ図であり、
図14は、横軸に入射光の周波数をとり、縦軸に膜の鏡面反射率をとって、煮沸による膜の鏡面反射率の変化を示すグラフ図であり、
図15は、横軸に入射光の周波数をとり、縦軸に膜の拡散反射率をとって、煮沸による膜の拡散反射率の変化を示すグラフ図であり、
図16は、煮沸前後の膜の外観を示す写真であり、
図17(a)及び(b)は煮沸前後の膜のAFM測定結果を示す図であり、(a)は煮沸前を示し、(b)は煮沸後を示す。
(Test Example 3)
In Test Example 3, the Al—N film formed by sputtering was boiled in pure water, and the surface morphology and optical characteristics of the film before and after boiling were investigated.
FIG. 10 is a diagram showing the definition of each optical characteristic value.
FIG. 11 is a cross-sectional view showing the boiling apparatus used in this test example,
FIG. 12 is a graph showing the change over time in total transmittance during boiling, with the frequency of incident light on the horizontal axis and the total transmittance of the film on the vertical axis.
FIG. 13 is a graph showing the change in the total transmittance of the film due to boiling, with the frequency of incident light on the horizontal axis and the total transmittance of the film on the vertical axis.
FIG. 14 is a graph showing changes in the specular reflectance of the film due to boiling, with the frequency of incident light on the horizontal axis and the specular reflectance of the film on the vertical axis.
FIG. 15 is a graph showing the change in the diffuse reflectance of the film due to boiling, with the frequency of incident light on the horizontal axis and the diffuse reflectance of the film on the vertical axis.
FIG. 16 is a photograph showing the appearance of the film before and after boiling,
17 (a) and 17 (b) are diagrams showing the AFM measurement results of the membrane before and after boiling, (a) showing before boiling, and (b) showing after boiling.
図10に示すように、ガラス基板32上に膜33が形成された試料31を想定する。そして、試料31に膜33側から入射光Iを入射させたときに、試料31内で拡散されることなく試料31を透過して、試料31から入射光Iの入射方向と同じ方向に出射する光を前方透過光といい、入射光Iの強度に対する前方透過光の強度の比率を前方透過率Toとする。また、試料31内で拡散されながら透過して、試料31から入射光Iの入射方向とは異なる方向に出射する光を拡散透過光といい、入射光Iの強度に対する拡散透過光の強度の比率を拡散透過率Tdとする。そして、前方透過率To及び拡散透過率Tdの合計を全透過率Ttとする。更に、試料31の表面で拡散されずに反射した光を鏡面反射光といい、入射光Iの強度に対する鏡面反射光の強度の比率を鏡面反射率Roとする。更にまた、試料31の表面で拡散されて反射した光を拡散反射光といい、入射光Iの強度に対する拡散反射光の強度の比率をRdとする。 As shown in FIG. 10, a sample 31 in which a film 33 is formed on a glass substrate 32 is assumed. When the incident light I is incident on the sample 31 from the film 33 side, it is transmitted through the sample 31 without being diffused in the sample 31, and is emitted from the sample 31 in the same direction as the incident direction of the incident light I. refers to light and forward transmitted light, the ratio of the intensity of the forward transmitted light to the intensity of the incident light I and the front transmittance T o. Further, light that is transmitted while being diffused in the sample 31 and is emitted from the sample 31 in a direction different from the incident direction of the incident light I is referred to as diffuse transmitted light, and the ratio of the intensity of the diffuse transmitted light to the intensity of the incident light I. Is the diffuse transmittance Td . Then, the total transmittance T t the sum of the forward transmission T o and diffuse transmittance T d. Further, the light reflected without being diffused in the surface of the sample 31 is called a specular reflection light, the ratio of the intensity of the specular reflected light to the intensity of the incident light I and specular reflectance R o. Furthermore, the light diffused and reflected by the surface of the sample 31 is called diffuse reflection light, and the ratio of the intensity of the diffuse reflection light to the intensity of the incident light I is R d .
本試験例においては、試験例1において説明した方法により、ガラス基板(コーニング社製コード7059)上にスパッタリングによりAl−N膜を形成した。このとき、スパッタガス中の窒素濃度CN2は6体積%とし、膜厚dは100nmとした。これにより、試料31(図10参照)を作製した。そして、この試料31の全透過率を測定し、外観写真を撮影し、AFMにより表面形態を測定した。AFMによる測定は縦が10μm、横が10μmの正方形の領域について行った。 In this test example, an Al—N film was formed by sputtering on a glass substrate (Corning Code 7059) by the method described in Test Example 1. At this time, the nitrogen concentration CN2 in the sputtering gas was 6% by volume, and the film thickness d was 100 nm. Thereby, the sample 31 (refer FIG. 10) was produced. And the total transmittance of this sample 31 was measured, the external appearance photograph was image | photographed, and the surface form was measured by AFM. The measurement by AFM was performed on a square region having a length of 10 μm and a width of 10 μm.
次に、図11に示すように、ヒーター41上にビーカー42を載せ、このビーカー42内に台43を置き、ビーカー42内に、純水44を注入した。そして、ヒーター41を作動させて純水44を加熱し、純水44を沸騰させた。純水44が沸騰している状態で、ビーカー42内の台43上に、上述の試料31を載置し、試料31が純水44中に没するようにした。そして、ビーカー42に蓋45をかぶせた。このようにして、試料31を純水中で煮沸した。 Next, as shown in FIG. 11, a beaker 42 was placed on the heater 41, a table 43 was placed in the beaker 42, and pure water 44 was injected into the beaker 42. And the heater 41 was operated and the pure water 44 was heated, and the pure water 44 was boiled. In a state where the pure water 44 is boiling, the sample 31 is placed on the table 43 in the beaker 42 so that the sample 31 is immersed in the pure water 44. Then, a lid 45 was placed on the beaker 42. In this way, the sample 31 was boiled in pure water.
そして、試料31の合計の煮沸時間が1分、2分、4分、8分、16分及び32分に達したときにそれぞれ、ビーカー42から試料31を取り出し、全透過率を測定した後、試料31をビーカー42内に戻し、煮沸を再開した。そして、試料31の合計の煮沸時間が48分に達したときに、ビーカー42から試料31を取り出し、全透過率、鏡面反射率及び拡散反射率を測定した。また、試料31の外観の写真を撮影し、AFMにより表面形態を測定した。AFMの測定結果を表2に示す。なお、表2に示す「RMS」とは「root-mean-aquare粗さ」を示し、「頂点の数」とは測定領域内に含まれる頂点の総数を示し、「頂点間距離」とは、頂点間の平均距離を示す。 And when the total boiling time of the sample 31 reached 1 minute, 2 minutes, 4 minutes, 8 minutes, 16 minutes and 32 minutes, respectively, after taking out the sample 31 from the beaker 42 and measuring the total transmittance, Sample 31 was returned to beaker 42 and boiling was resumed. When the total boiling time of the sample 31 reached 48 minutes, the sample 31 was taken out from the beaker 42, and the total transmittance, specular reflectance, and diffuse reflectance were measured. In addition, a photograph of the appearance of the sample 31 was taken, and the surface morphology was measured by AFM. Table 2 shows the measurement results of AFM. In addition, “RMS” shown in Table 2 indicates “root-mean-aquare roughness”, “Number of vertices” indicates the total number of vertices included in the measurement region, and “Distance between vertices” Indicates the average distance between vertices.
図12に示すように、煮沸開始時点(t=0分)から合計の煮沸時間tが32分に達するまでの期間においては、煮沸時間tの増加に伴い、全透過率Ttも増加した。これに対して、図12において、t=32分の全透過率を示す線とt=48分の全透過率を示す線とは相互に重なっており、煮沸時間tが32分から48分になっても、全透過率Ttはほとんど変化しなかった。即ち、膜33の変化は、煮沸時間tが32分の時点で既に飽和していた。なお、図12に示すt=0分の測定結果は、煮沸前(as depo.)の測定結果である。
そして、図13に示すように、合計で48分間煮沸した後の試料31の全透過率は、ガラス基板32単独の全透過率よりも高くなった。
As shown in FIG. 12, in the period from the boiling start time (t = 0 minutes) to the total boiling time t reaching 32 minutes, the total transmittance T t also increased as the boiling time t increased. On the other hand, in FIG. 12, the line indicating the total transmittance at t = 32 minutes and the line indicating the total transmittance at t = 48 minutes overlap each other, and the boiling time t is changed from 32 minutes to 48 minutes. However, the total transmittance T t hardly changed. That is, the change in the film 33 was already saturated when the boiling time t was 32 minutes. In addition, the measurement result of t = 0 minutes shown in FIG. 12 is a measurement result before boiling (as depo.).
And as shown in FIG. 13, the total transmittance of the sample 31 after boiling for 48 minutes in total was higher than the total transmittance of the glass substrate 32 alone.
また、図14に示すように、煮沸前(t=0分、as depo.)の試料31の鏡面反射率は、可視領域で低かった。このため、この膜は黒色に見えた。そして、近赤外領域では波長が長くなるほど、鏡面反射率は高くなっていた。この試料31を間欠的に48分間煮沸することより、試料31の鏡面反射率が全波長領域で煮沸前よりも減少し、波長が0.55μm以上の領域においては、ガラス基板の鏡面反射率よりも低くなった。 Moreover, as shown in FIG. 14, the specular reflectance of the sample 31 before boiling (t = 0 minutes, as depo.) Was low in the visible region. This film therefore appeared black. And in the near-infrared region, the longer the wavelength, the higher the specular reflectance. By boiling this sample 31 for 48 minutes intermittently, the specular reflectivity of the sample 31 decreases in the entire wavelength region before boiling, and in the region where the wavelength is 0.55 μm or more, the specular reflectivity of the glass substrate. Was also lower.
更に、図15に示すように、煮沸前の試料31の拡散反射率は、可視領域でやや高く、近赤外領域で低くなっていた。近赤外領域で拡散反射率が低いのは、近赤外線は、膜33の表面の凹凸(図17(a)参照)を個々に認識することができず、平坦とみなしてしまうことに起因している。そして、この試料31を間欠的に48分間煮沸することより、試料31の拡散反射率が煮沸前よりも減少した。但し、煮沸後も試料31の拡散反射率はガラス基板32の拡散反射率よりは高かった。 Furthermore, as shown in FIG. 15, the diffuse reflectance of the sample 31 before boiling was slightly high in the visible region and low in the near infrared region. The reason why the diffuse reflectance is low in the near-infrared region is that near-infrared light cannot be individually recognized as the irregularities on the surface of the film 33 (see FIG. 17A) and is regarded as flat. ing. And by boiling this sample 31 for 48 minutes intermittently, the diffuse reflectance of the sample 31 decreased from before boiling. However, the diffuse reflectance of sample 31 was higher than that of glass substrate 32 even after boiling.
更にまた、図16に示すように、煮沸前の試料31の外観は不透明で黒色であるのに対して、48分間煮沸した後の試料31は透明になっていた。これは、図13に示す結果と整合している。更にまた、上述の如くAl−N膜を煮沸することにより、図11に示す純水44はややアルカリ性になった。これは、上述の化学式(1)に示すように、水がAlNと反応してアンモニアが生成したためと推定される。 Furthermore, as shown in FIG. 16, the appearance of the sample 31 before boiling was opaque and black, whereas the sample 31 after boiling for 48 minutes was transparent. This is consistent with the results shown in FIG. Furthermore, by boiling the Al—N film as described above, the pure water 44 shown in FIG. 11 became slightly alkaline. This is presumably because, as shown in the above chemical formula (1), water reacted with AlN to generate ammonia.
更にまた、表2並びに図17(a)及び(b)に示すように、煮沸することにより、試料31の表面の凹凸は大きくなった。即ち、煮沸することにより、RMS粗さは約2倍になり、頂点の数は約(1/3)倍になり、頂点間距離は約2倍になった。このように、煮沸により、試料31の表面の凹凸の形は変化したが、メゾスコピック凹凸が存在するという点は変わらなかった。試験例1で説明したように、煮沸前のAl−N膜は金属光沢を呈することから、金属アルミニウムが存在していると考えられる。これに対して、煮沸後の膜33は透明化していることから、煮沸前のAl−N膜に存在していた単体のアルミニウムが酸化、窒化、酸窒化及び/又は水酸化され、自由電子が失われたものと考えられる。 Furthermore, as shown in Table 2 and FIGS. 17 (a) and 17 (b), the unevenness of the surface of the sample 31 was increased by boiling. That is, by boiling, the RMS roughness was approximately doubled, the number of vertices was approximately (1/3) times, and the distance between vertices was approximately doubled. Thus, although the shape of the unevenness | corrugation of the surface of the sample 31 changed by boiling, the point that a mesoscopic unevenness | corrugation exists was not changed. As described in Test Example 1, since the Al—N film before boiling exhibits a metallic luster, it is considered that metallic aluminum is present. On the other hand, since the film 33 after boiling is transparent, the single aluminum existing in the Al—N film before boiling is oxidized, nitrided, oxynitrided and / or hydroxylated, and free electrons are generated. It is thought to have been lost.
一方、比較のために、スパッタガスとして純アルゴンガスを使用してスパッタリングを行ってガラス基板上にAl膜を形成し、このAl膜を48分間煮沸した。しかしながら、Al膜は透明化しなかった。また、スパッタガスとして窒素濃度CN2が13体積%のガスを使用してスパッタリングを行い、ガラス基板上にAlN膜、即ち、アルミニウムがほぼ完全に窒化され、アルミニウムと窒素の原子組成比が1:1である膜を形成した。この膜の外観は透明であるが、その透過率は試料31の透過率よりも低かった。また、このAlN膜を煮沸したが、やはりその透過率は試料31の透過率よりも低かった。 On the other hand, for comparison, sputtering was performed using pure argon gas as a sputtering gas to form an Al film on a glass substrate, and this Al film was boiled for 48 minutes. However, the Al film was not made transparent. Sputtering is performed using a gas having a nitrogen concentration of CN 2 of 13% by volume as a sputtering gas, and an AlN film, that is, aluminum is almost completely nitrided on the glass substrate, and the atomic composition ratio of aluminum to nitrogen is 1: 1 was formed. The appearance of this film was transparent, but its transmittance was lower than that of sample 31. Further, although the AlN film was boiled, its transmittance was still lower than that of the sample 31.
なお、膜を透明化するために必要な煮沸時間は、煮沸条件及びAl−N膜の膜厚により異なっていた。例えば、本試験例においては、全透過率の煮沸時間依存性を調べるために、煮沸の途中で試料を水中から取り出して、全透過率を測定した。このため、試料31を間欠的に煮沸することになった。そして、この場合には、全透過率の変化が飽和するまでに32分間の煮沸時間を要した。しかしながら、途中で中断せずに連続的に煮沸すれば、より短い時間で飽和状態(透明状態)にすることができた。また、Al−N膜が厚くなるほど、必要な煮沸時間が長くなった。例えば、本試験例においては、Al−N膜の膜厚を100nmとしたが、Al−N膜の膜厚が200nmである場合には、間欠的に煮沸する場合で512分よりも長い煮沸時間が必要であり、連続的に煮沸する場合でも180分よりも長い煮沸時間が必要であった。 In addition, the boiling time required in order to make a film | membrane transparent differed with the boiling conditions and the film thickness of the Al-N film | membrane. For example, in this test example, in order to examine the dependency of the total transmittance on the boiling time, a sample was taken out of the water during the boiling, and the total transmittance was measured. For this reason, the sample 31 was boiled intermittently. In this case, a boiling time of 32 minutes was required until the change in total transmittance was saturated. However, if it boiled continuously without interruption on the way, it could be saturated (transparent state) in a shorter time. Further, the thicker the Al—N film, the longer the required boiling time. For example, in this test example, the film thickness of the Al—N film is 100 nm, but when the film thickness of the Al—N film is 200 nm, the boiling time is longer than 512 minutes when boiling intermittently. In the case of continuous boiling, boiling time longer than 180 minutes was required.
1 光学部材
2 基体
3 透明膜
4 基部
5 モスアイ構造部
6 突起
11 スパッタリング装置
12 真空チャンバー
13 スパッタガス導入管
13a、13b 支管
14 排気管
15a、15b ニードルバルブ
16 ロータリーポンプ(RP)
17 ターボ分子ポンプ(TMP)
18 粗引バルブ
19 メインバルブ
20 フォアバルブ
21 基板
22 ターゲット
31 試料
32 ガラス基板
33 膜
41 ヒーター
42 ビーカー
43 台
44 純水
45 蓋
DESCRIPTION OF SYMBOLS 1 Optical member 2 Base | substrate 3 Transparent film 4 Base part 5 Moss eye structure part 6 Protrusion 11 Sputtering device 12 Vacuum chamber 13 Sputtering gas introduction pipes 13a and 13b Branch pipe 14 Exhaust pipes 15a and 15b Needle valve 16 Rotary pump (RP)
17 Turbo molecular pump (TMP)
18 Roughing valve 19 Main valve 20 Fore valve 21 Substrate 22 Target 31 Sample 32 Glass substrate 33 Film 41 Heater 42 Beaker 43 Unit 44 Pure water 45 Lid
Claims (8)
アルミニウムを含有するターゲットを使用し窒素を含有するガス中でスパッタリングを行うことにより前記基体上に成膜されアルミニウムの一部が窒化された窒素含有アルミニウム膜を水中で加熱することにより前記基体上に形成された透明膜と、を備えたことを特徴とする光学部材。 A transparent substrate,
Sputtering is performed in a nitrogen-containing gas using a target containing aluminum, and a nitrogen-containing aluminum film in which a part of aluminum is nitrided is heated in water on the substrate by sputtering on the substrate. An optical member comprising: a formed transparent film.
前記窒素含有アルミニウム膜を水中で加熱する工程と、
を備えたことを特徴とする透明膜の製造方法。 Forming a nitrogen-containing aluminum film in which a part of aluminum is nitrided on a substrate by performing sputtering in a nitrogen-containing gas using a target containing aluminum; and
Heating the nitrogen-containing aluminum film in water;
A method for producing a transparent film, comprising:
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