JP2017220011A - Laminated film, display device, and input device - Google Patents
Laminated film, display device, and input device Download PDFInfo
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Abstract
Description
本発明は、光吸収性を有し、入力装置内の金属電極に用いられる積層膜、前記積層膜を備えた表示装置及び入力装置に関する。 The present invention relates to a laminated film that has light absorptivity and is used for a metal electrode in an input device, a display device including the laminated film, and an input device.
以下に入力装置の代表例としてタッチパネルセンサーを例に挙げて説明するが、本発明はこれに限定されない。タッチパネルセンサーは、液晶表示装置又は有機ＥＬ装置などの表示装置の表示画面上に入力装置として貼り合わせて使用される。 Hereinafter, a touch panel sensor will be described as an example of a typical input device, but the present invention is not limited to this. The touch panel sensor is used by being attached as an input device on a display screen of a display device such as a liquid crystal display device or an organic EL device.
タッチパネルセンサーの入力ポイントの検出方式には、抵抗膜方式、静電容量方式、光学式又は圧電式等が挙げられる。 Examples of the detection method of the input point of the touch panel sensor include a resistance film method, a capacitance method, an optical method, and a piezoelectric method.
静電容量方式のタッチパネルセンサーは、一例として、ガラス基板などの透明基板上に、二方向の透明電極が直交して配置され、その表面に保護ガラスなどの絶縁体であるカバーが被覆された構造を有している。 As an example, a capacitive touch panel sensor has a structure in which transparent electrodes in two directions are arranged orthogonally on a transparent substrate such as a glass substrate, and a cover that is an insulator such as protective glass is coated on the surface. have.
上記構成のタッチパネルセンサーに用いられる透明基板として、表示装置に用いられる透明基板を用いることもできる。具体的には、液晶表示装置に用いられるカラーフィルター基板又は有機ＥＬ装置に用いられるガラス基板などが例として挙げられる。 As the transparent substrate used in the touch panel sensor having the above-described configuration, a transparent substrate used in a display device can be used. Specific examples include a color filter substrate used in a liquid crystal display device or a glass substrate used in an organic EL device.
最近では、入力装置内の電極薄膜として、低抵抗な金属電極薄膜の使用が検討されている。金属電極薄膜は接触感度向上又はノイズ低減に有効である。しかし、金属電極薄膜は反射率が高く、使用者の肉眼で見える、即ち視認されるため、コントラスト比が低下する。 Recently, the use of a low-resistance metal electrode thin film as an electrode thin film in an input device has been studied. The metal electrode thin film is effective for improving contact sensitivity or reducing noise. However, since the metal electrode thin film has a high reflectance and is visible to the naked eye of the user, that is, visually recognized, the contrast ratio is lowered.
そこで、特許文献１には、導電性透明パターンセルを相互接続するブリッジ電極における視認性の問題を解決するため、基板上に相互離隔される複数の導電性パターンセルを形成し、前記導電性パターンセル上に絶縁層を形成し、前記絶縁層上に黒色の導電材料を用いて前記ブリッジ電極を形成する、ことを特徴とするタッチパネルの電極の形成方法が開示されている。具体的には、ブリッジ電極として、Ａｌ又はＴｉなどの金属を、薬品との反応により酸化物、窒化物又はフッ化物などに黒色化させる方法が例示されている。 Therefore, in Patent Document 1, in order to solve the problem of visibility in the bridge electrodes interconnecting the conductive transparent pattern cells, a plurality of conductive pattern cells spaced apart from each other are formed on the substrate, and the conductive pattern There is disclosed a method for forming an electrode of a touch panel, wherein an insulating layer is formed on a cell and the bridge electrode is formed on the insulating layer using a black conductive material. Specifically, as a bridge electrode, a method of blackening a metal such as Al or Ti into an oxide, nitride or fluoride by reaction with a chemical is exemplified.
また、特許文献２には透明性基板上に形成された反射防止膜であって、膜厚２５ｎｍにおいて波長５５０ｎｍの透過率が１０％未満であり、主成分がＡｌであるＡｌ系膜と、前記Ａｌ系膜の上層、又は／及び下層に形成され、膜厚２５ｎｍにおいて波長５５０ｎｍの透過率が１０％以上であり、かつ、主成分がＡｌであり、添加物として少なくともＮ元素を含むアルミニウム系Ｎ含有膜と、を備え、比抵抗値が１．０×１０−２Ω・ｃｍ以下であり、前記Ａｌ系Ｎ含有膜面の可視光領域における反射率が５０％以下である反射防止膜が開示されている。 Patent Document 2 discloses an antireflection film formed on a transparent substrate, which has an Al-based film whose transmittance at a wavelength of 550 nm is less than 10% at a film thickness of 25 nm and whose main component is Al, Aluminum-based N formed on the upper layer and / or lower layer of an Al-based film, having a transmittance of 10% or more at a wavelength of 550 nm at a film thickness of 25 nm, a main component being Al, and containing at least N element as an additive And an antireflection film having a specific resistance value of 1.0 × 10 −2 Ω · cm or less and a reflectance in the visible light region of the Al-based N-containing film surface of 50% or less. Has been.
しかしながら、特許文献１に記載の薬液を使用する黒化処理では、金属薄膜として膜厚が数百ｎｍ程度の薄膜を用いる場合は黒化層成長の制御が難しく黒化層を形成する化合物からなる高抵抗層の増加により配線の断線が生じ易くなり、金属部の膜厚が薄くなるため抵抗増加に繋がる。 However, in the blackening treatment using the chemical solution described in Patent Document 1, when a thin film having a thickness of about several hundreds of nanometers is used as the metal thin film, it is difficult to control the growth of the blackened layer and is made of a compound that forms the blackened layer. The increase in the high resistance layer is likely to cause disconnection of the wiring, and the thickness of the metal part is reduced, leading to an increase in resistance.
また、特許文献２に記載されるＡｌ系膜は膜厚２５ｎｍにおける透過率は通常１％以下である。そのため、比抵抗値が１．０×１０−２Ω・ｃｍ以下であり、前記Ａｌ系Ｎ含有膜面の可視光領域における反射率が５０％以下である反射防止膜をＡｌ系膜に積層しただけでは、特許文献２の実施例３−１に示されているような、上層膜面側での波長５５０ｎｍにおける反射率値１．６％という値は達成できない。 Further, the Al-based film described in Patent Document 2 generally has a transmittance of 1% or less at a film thickness of 25 nm. Therefore, an antireflection film having a specific resistance value of 1.0 × 10 −2 Ω · cm or less and a reflectance of 50% or less in the visible light region of the Al-based N-containing film surface is laminated on the Al-based film. As a result, it is impossible to achieve a reflectance value of 1.6% at a wavelength of 550 nm on the upper film surface side as shown in Example 3-1 of Patent Document 2.
そのため、従来、特許文献２に記載されるような膜厚２５ｎｍにおいて波長５５０ｎｍの透過率が１０％未満であり、主成分がＡｌであるＡｌ系膜に関しては、酸化もしくは窒化又は添加元素によって低反射化させるか、あるいは、膜厚を薄くし透過率を高くすることで反射率を下げている。主成分がＡｌであるＡｌ系膜をこのような方法で低反射化する場合、当該Ａｌ系膜を含む積層膜を配線に用いると抵抗増加につながるため、低反射かつ低抵抗な配線材料として利用することはできない。しかしながら、特許文献２では積層膜の抵抗については考慮されていない。 Therefore, conventionally, the transmittance at a wavelength of 550 nm at a film thickness of 25 nm as described in Patent Document 2 is less than 10%, and an Al-based film whose main component is Al has low reflection due to oxidation or nitridation or an additive element. Alternatively, the reflectance is lowered by reducing the film thickness and increasing the transmittance. When an Al-based film whose main component is Al is made low-reflective by such a method, use of a laminated film containing the Al-based film for wiring leads to an increase in resistance, so it is used as a wiring material with low reflection and low resistance. I can't do it. However, Patent Document 2 does not consider the resistance of the laminated film.
本発明は上記を鑑みてなされたものであり、電気抵抗率及び反射率が共に低い、積層薄膜（低反射導電膜）を提供することを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to provide a laminated thin film (low reflective conductive film) having both low electrical resistivity and reflectance.
本発明者らは、鋭意研究を重ねた結果、電気抵抗率が特定範囲以下である金属薄膜である第１層、特定の組成を有するアルミニウム又はアルミニウム合金の窒化膜である第２層、特定の組成を有するアルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜である第３層がこの順に積層された積層膜を採用することにより、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive research, the inventors of the present invention have found that a first layer that is a metal thin film whose electrical resistivity is not more than a specific range, a second layer that is a nitride film of aluminum or aluminum alloy having a specific composition, a specific layer To find out that the above problems can be solved by adopting a laminated film in which a third layer, which is an oxide film, nitride film or oxynitride film of aluminum or aluminum alloy having a composition, is laminated in this order, and to complete the present invention It came.
すなわち、本発明は、以下の［１］〜［３］に係るものである。
［１］第１層、第２層及び第３層がこの順に積層された積層膜であって、
第１層が電気抵抗率が１５μΩ・ｃｍ以下である金属薄膜であり、
第２層が４０原子％以上６１原子％以下の窒素を含むアルミニウム窒化膜又はアルミニウム合金窒化膜であり、
第３層が５０原子％以上６０原子％以下の酸素を含むアルミニウム酸化膜若しくはアルミニウム合金酸化膜、５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含むアルミニウム酸窒化膜若しくはアルミニウム合金酸窒化膜、又は５０原子％以上６０原子％以下の窒素を含むアルミニウム窒化膜若しくはアルミニウム合金窒化膜である積層膜。
［２］［１］に記載の積層膜を備えた表示装置。
［３］［１］に記載の積層膜を備えた入力装置。
That is, the present invention relates to the following [1] to [3].
[1] A laminated film in which a first layer, a second layer, and a third layer are laminated in this order,
The first layer is a metal thin film having an electrical resistivity of 15 μΩ · cm or less,
The second layer is an aluminum nitride film or an aluminum alloy nitride film containing nitrogen of 40 atomic% or more and 61 atomic% or less,
Aluminum oxide film containing aluminum oxide film or aluminum alloy oxide film in which the third layer contains oxygen of 50 atomic percent to 60 atomic percent, aluminum acid containing oxygen of 50 atomic percent to 60 atomic percent and nitrogen of 1 atomic percent to 10 atomic percent A laminated film which is a nitride film or an aluminum alloy oxynitride film, or an aluminum nitride film or an aluminum alloy nitride film containing nitrogen of 50 atomic% to 60 atomic%.
[2] A display device comprising the laminated film according to [1].
[3] An input device comprising the laminated film according to [1].
本発明によれば、前記した金属薄膜である第１層、アルミニウム又はアルミニウム合金の窒化膜である第２層、及びアルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜である第３層をこの順に積層することで、電気抵抗率が低く、低反射性、導電性及びエッチング加工性に優れ、かつ安価な光吸収薄膜及び低反射導電膜を得られるとともに、安定した製造が可能になる。 According to the present invention, the first layer that is the metal thin film, the second layer that is the nitride film of aluminum or aluminum alloy, and the third layer that is the oxide film, nitride film, or oxynitride film of aluminum or aluminum alloy are provided. By laminating in this order, it is possible to obtain a light-absorbing thin film and a low-reflective conductive film that have low electrical resistivity, excellent low reflectivity, conductivity, and etching processability, and are inexpensive, and can be stably manufactured.
以下、本発明を詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。また本明細書において数値範囲を示す「〜」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。「反射率」とは、波長４５０ｎｍ、５５０ｎｍ及び６５０ｎｍにおける反射率を意味する。また「ａｔ％」と「原子％」とは同義である。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. In the present specification, “to” indicating a numerical range is used in the sense of including the numerical values described before and after the numerical value as a lower limit value and an upper limit value. “Reflectance” means reflectance at wavelengths of 450 nm, 550 nm, and 650 nm. “At%” and “atomic%” are synonymous.
＜積層膜＞
図１〜図４に本発明の積層膜の一構造例の概略断面図を示す。図１の積層膜は、基板１上に導電層となる金属薄膜である第１層２を備え、その上にアルミニウム窒化膜又はアルミニウム合金窒化膜である第２層３を備え、その上にアルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜である第３層４を備える。第１層と第３層との間に第２層が配置されていればよく、図２で示すように基板１上に第３層４を備え、その上に第２層３を備え、その上にさらに第１層２を備えてもよい。
<Laminated film>
1 to 4 show schematic sectional views of one structural example of the laminated film of the present invention. 1 includes a first layer 2 which is a metal thin film serving as a conductive layer on a substrate 1, a second layer 3 which is an aluminum nitride film or an aluminum alloy nitride film thereon, and aluminum thereon. Alternatively, the third layer 4 which is an aluminum alloy oxide film, nitride film or oxynitride film is provided. It is only necessary that the second layer is disposed between the first layer and the third layer. As shown in FIG. 2, the third layer 4 is provided on the substrate 1, the second layer 3 is provided thereon, and the second layer 3 is provided thereon. The first layer 2 may be further provided on the top.
また、図３又は図４に示すように、密着層又は保護層５を、基板１と第１層２との界面、又は第１層２の上下層に積層してもよい。第１層２となる金属膜の種類によって、密着性の改善及び耐食性の改善を目的として、該密着層又は保護層５を設けることが好ましい。 Moreover, as shown in FIG. 3 or FIG. 4, the adhesion layer or the protective layer 5 may be laminated on the interface between the substrate 1 and the first layer 2 or on the upper and lower layers of the first layer 2. Depending on the type of the metal film to be the first layer 2, it is preferable to provide the adhesion layer or the protective layer 5 for the purpose of improving adhesion and improving corrosion resistance.
（基板）
基板の材料としては、ＰＥＴフィルム若しくはプラスチック等の樹脂基板、ガラス基板、シリコン基板又はカラーフィルター基板等、従来公知の材料から適宜選択することができる。基板の厚みは用途によっても異なるが、一般的には０．１〜３ｍｍが好ましい。
(substrate)
The material of the substrate can be appropriately selected from conventionally known materials such as a resin substrate such as a PET film or plastic, a glass substrate, a silicon substrate, or a color filter substrate. Although the thickness of a board | substrate changes with uses, generally 0.1-3 mm is preferable.
（金属薄膜：第１層）
導電層となる金属電極薄膜（以下、金属膜ともいう。）である第１層２は、単膜としての電気抵抗率が１５μΩ・ｃｍ以下であり、１０μΩ・ｃｍ以下が好ましく、８μΩ・ｃｍ以下がより好ましい。電気抵抗率の下限は特に限定されないが、通常１．５μΩ・ｃｍ以上である。金属膜の電気抵抗率が１５μΩ・ｃｍを超えると、積層膜とした時の目安であるシート抵抗が１．５Ω／ｃｍ２以下となるように厚膜を積層する必要がある。電気抵抗率及びシート抵抗は四端子法で測定する。
(Metal thin film: 1st layer)
The first layer 2, which is a metal electrode thin film (hereinafter also referred to as a metal film) serving as a conductive layer, has an electric resistivity of 15 μΩ · cm or less as a single film, preferably 10 μΩ · cm or less, and preferably 8 μΩ · cm or less. Is more preferable. The lower limit of the electrical resistivity is not particularly limited, but is usually 1.5 μΩ · cm or more. When the electrical resistivity of the metal film exceeds 15 μΩ · cm, it is necessary to laminate the thick film so that the sheet resistance, which is a standard when a laminated film is formed, is 1.5 Ω / cm 2 or less. Electrical resistivity and sheet resistance are measured by the four probe method.
金属膜としては、導電性の観点から純アルミニウム薄膜、アルミニウム合金薄膜、純銅薄膜、銅合金薄膜、純銀薄膜又は銀合金薄膜が好ましく、耐熱性及び耐薬品性を鑑みると、アルミニウム合金薄膜、銅合金薄膜又は銀合金薄膜がより好ましい。 The metal film is preferably a pure aluminum thin film, an aluminum alloy thin film, a pure copper thin film, a copper alloy thin film, a pure silver thin film or a silver alloy thin film from the viewpoint of conductivity, and in view of heat resistance and chemical resistance, an aluminum alloy thin film or a copper alloy is preferred. A thin film or a silver alloy thin film is more preferable.
金属膜の合金薄膜として含まれていてもよい合金成分としては、例えば、Ａｌ、Ｃｕ、Ａｇ、Ｎｉ、Ｌａ、Ｇｅ、Ｎｄ、Ｔａ、Ｚｒ、Ｍｎ、Ｂｉ及びＺｎ等が挙げられる。これらの主元素でない成分の合計含有量は一般的に０．１〜３．０原子％である。なお、具体的な金属膜の例とその電気抵抗率を表１に示す。 Examples of the alloy component that may be included as the alloy thin film of the metal film include Al, Cu, Ag, Ni, La, Ge, Nd, Ta, Zr, Mn, Bi, and Zn. The total content of these non-main elements is generally 0.1 to 3.0 atomic%. Table 1 shows examples of specific metal films and their electrical resistivity.
金属膜はスパッタリング法又は蒸着法等により成膜することができる。金属膜の膜厚は好ましくは５０ｎｍ以上であり、シート抵抗の点から８０ｎｍ以上がより好ましい。また、膜厚が厚くなると成膜プロセス時間が長くなるため、５００ｎｍ以下が好ましく、３５０ｎｍ以下がより好ましい。スパッタリング法を用いて金属膜を成膜する場合、スパッタリング条件を変えることで、膜厚を調整することができる。 The metal film can be formed by sputtering or vapor deposition. The thickness of the metal film is preferably 50 nm or more, and more preferably 80 nm or more from the viewpoint of sheet resistance. Moreover, since the film forming process time becomes longer as the film thickness increases, the thickness is preferably 500 nm or less, and more preferably 350 nm or less. When a metal film is formed using a sputtering method, the film thickness can be adjusted by changing sputtering conditions.
（アルミニウム窒化膜又はアルミニウム合金窒化膜：第２層）
アルミニウム窒化膜又はアルミニウム合金窒化膜である第２層３は光吸収膜として機能する。そのため、第２層は光の入射側又は視認する側に設けることが好ましい。第２層は、金属膜である第１層とアルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜である第３層との間に設ける。
(Aluminum nitride film or aluminum alloy nitride film: second layer)
The second layer 3 which is an aluminum nitride film or an aluminum alloy nitride film functions as a light absorption film. For this reason, the second layer is preferably provided on the light incident side or the viewing side. The second layer is provided between the first layer that is a metal film and the third layer that is an oxide film, nitride film, or oxynitride film of aluminum or an aluminum alloy.
第２層は、金属膜の低反射化を目的とするため、例えば図１に示すように表面側に設けてもよいし、図２に示すように基板側に設けてもよく、その位置は光の入射側又は視認する側に依存する。これにより、積層膜の低反射化を実現する。 For the purpose of reducing the reflection of the metal film, the second layer may be provided on the surface side as shown in FIG. 1, for example, or may be provided on the substrate side as shown in FIG. Depends on the light incident side or the viewing side. Thereby, low reflection of the laminated film is realized.
アルミニウム窒化膜又はアルミニウム合金窒化膜は、窒素の含有量が４０原子％以上であり、好ましくは４５原子％以上である。窒素の含有量が４０原子％未満では単膜反射率が高く、積層構造にしても反射率１５．０％以下を達成することができない。窒素の含有量は、６１原子％以下であり、好ましくは５８原子％以下である。窒素の含有量が６１原子％超では透過率が高く、積層構造にしても反射率１５．０％以下を達成することができない。 The aluminum nitride film or the aluminum alloy nitride film has a nitrogen content of 40 atomic% or more, preferably 45 atomic% or more. When the nitrogen content is less than 40 atomic%, the single film reflectance is high, and even with a laminated structure, the reflectance of 15.0% or less cannot be achieved. The nitrogen content is 61 atomic% or less, preferably 58 atomic% or less. If the nitrogen content exceeds 61 atomic%, the transmittance is high, and even with a laminated structure, a reflectance of 15.0% or less cannot be achieved.
アルミニウム窒化膜又はアルミニウム合金窒化膜の膜厚は、その組成及び積層する金属膜の種類等によっても異なるが、反射率をより低減できることから２０ｎｍ以上が好ましく、より好ましくは２５ｎｍ以上である。膜厚が厚くなりすぎると、成膜プロセス時間の超過につながるため、２００ｎｍ以下が好ましく、１５０ｎｍ以下がより好ましい。 The film thickness of the aluminum nitride film or the aluminum alloy nitride film varies depending on the composition and the type of the metal film to be laminated, but is preferably 20 nm or more, more preferably 25 nm or more because the reflectance can be further reduced. If the film thickness becomes too thick, the film formation process time will be exceeded, so 200 nm or less is preferable, and 150 nm or less is more preferable.
アルミニウム窒化膜又はアルミニウム合金窒化膜は、スパッタリング法又は蒸着法等により成膜することができる。スパッタリング法を用いてアルミニウム窒化膜又はアルミニウム合金窒化薄膜を成膜する場合、スパッタリング条件を変えることで、膜厚を調整することができる。 The aluminum nitride film or the aluminum alloy nitride film can be formed by sputtering or vapor deposition. When an aluminum nitride film or an aluminum alloy nitride thin film is formed using a sputtering method, the film thickness can be adjusted by changing the sputtering conditions.
アルミニウム窒化膜又はアルミニウム合金窒化膜は上記成分以外のその他の成分として酸素（Ｏ）、銅（Ｃｕ）、イットリウム（Ｙ）、ケイ素（Ｓｉ）、チタン（Ｔｉ）若しくはネオジム（Ｎｄ）等の元素又は不可避不純物が含まれていてもよい。その他の成分の含有量は、アルミニウム窒化膜又はアルミニウム合金窒化膜における窒素含有量又はその他の元素組成によっても異なる。 The aluminum nitride film or the aluminum alloy nitride film is an element other than the above components such as oxygen (O), copper (Cu), yttrium (Y), silicon (Si), titanium (Ti), neodymium (Nd) or the like. Inevitable impurities may be included. The content of other components varies depending on the nitrogen content or other elemental composition in the aluminum nitride film or aluminum alloy nitride film.
アルミニウム窒化膜又はアルミニウム合金窒化膜における酸素の含有量は、一般的には、１０．０原子％以下であることが好ましく、より好ましくは５．０原子％以下である。また、酸素の含有量は、３原子％以上であることが好ましく、より好ましくは５原子％以上である。 In general, the oxygen content in the aluminum nitride film or the aluminum alloy nitride film is preferably 10.0 atomic% or less, and more preferably 5.0 atomic% or less. The oxygen content is preferably 3 atomic percent or more, more preferably 5 atomic percent or more.
アルミニウム合金窒化膜におけるＣｕの含有量は、３原子％以上であることが好ましく、より好ましくは５原子％以上である。また、Ｃｕの含有量は、２０原子％以下であることが好ましく、より好ましくは１５原子％以下である。 The content of Cu in the aluminum alloy nitride film is preferably 3 atomic% or more, more preferably 5 atomic% or more. Moreover, it is preferable that content of Cu is 20 atomic% or less, More preferably, it is 15 atomic% or less.
アルミニウム合金窒化膜におけるＹの含有量は、１原子％以上であることが好ましく、より好ましくは２原子％以上である。また、Ｙの含有量は、２．９原子％以下であることが好ましく、より好ましくは２．５原子％以下である。 The Y content in the aluminum alloy nitride film is preferably 1 atomic% or more, more preferably 2 atomic% or more. Moreover, it is preferable that content of Y is 2.9 atomic% or less, More preferably, it is 2.5 atomic% or less.
アルミニウム合金窒化膜におけるＳｉの含有量は、１原子％以上であることが好ましく、より好ましくは１．５原子％以上である。また、Ｓｉの含有量は、３原子％以下であることが好ましく、より好ましくは２．５原子％以下である。 The Si content in the aluminum alloy nitride film is preferably 1 atomic% or more, more preferably 1.5 atomic% or more. Moreover, it is preferable that content of Si is 3 atomic% or less, More preferably, it is 2.5 atomic% or less.
アルミニウム合金窒化膜におけるＴｉの含有量は、０．５原子％以上であることが好ましく、より好ましくは１原子％以上である。また、Ｔｉの含有量は、７原子％以下であることが好ましく、より好ましくは５原子％以下である。 The Ti content in the aluminum alloy nitride film is preferably 0.5 atomic% or more, and more preferably 1 atomic% or more. Moreover, it is preferable that content of Ti is 7 atomic% or less, More preferably, it is 5 atomic% or less.
アルミニウム合金窒化膜におけるＮｄの含有量は、１原子％以上であることが好ましく、より好ましくは２原子％以上である。また、Ｎｄの含有量は、５原子％以下であることが好ましく、より好ましくは４．５原子％以下である。 The Nd content in the aluminum alloy nitride film is preferably 1 atomic% or more, more preferably 2 atomic% or more. Moreover, it is preferable that content of Nd is 5 atomic% or less, More preferably, it is 4.5 atomic% or less.
不可避不純物としてはＣ、Ｆｅ又はＭｇ等の金属元素が挙げられる。不可避不純物の含有量の上限は、合計で０．１原子％未満であることが好ましい。 Inevitable impurities include metal elements such as C, Fe or Mg. The upper limit of the content of inevitable impurities is preferably less than 0.1 atomic% in total.
（アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜：第３層）
アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜である第３層４は積層膜の低反射化を実現するために機能するための光学調整層として機能する。そのため、第３層は、アルミニウム又はアルミニウム合金の窒化膜である第２層の直上又は直下に設けることが好ましい。金属膜の低反射化を目的とするため、例えば、図１に示すように第３層を表面側に設けてもよいし、図２に示すように基板側に設けてもよく、その位置は光の入射側又は視認する側に依存する。
(Aluminum or aluminum alloy oxide film, nitride film or oxynitride film: third layer)
The third layer 4 that is an oxide film, nitride film, or oxynitride film of aluminum or an aluminum alloy functions as an optical adjustment layer for functioning to realize low reflection of the laminated film. Therefore, the third layer is preferably provided directly above or directly below the second layer, which is a nitride film of aluminum or aluminum alloy. In order to reduce the reflection of the metal film, for example, the third layer may be provided on the surface side as shown in FIG. 1, or may be provided on the substrate side as shown in FIG. Depends on the light incident side or the viewing side.
第３層が単層である場合、以下の（１）〜（３）のいずれか１であることを特徴とする。
（１）５０原子％以上６０原子％以下の酸素を含む、アルミニウム酸化膜又はアルミニウム合金酸化膜
（２）５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含む、アルミニウム酸窒化膜又はアルミニウム合金酸窒化膜
（３）５０原子％以上６０原子％以下の窒素を含む、アルミニウム窒化膜又はアルミニウム合金窒化膜
When the third layer is a single layer, it is any one of the following (1) to (3).
(1) Aluminum oxide film or aluminum alloy oxide film containing 50 atomic% to 60 atomic% oxygen (2) 50 atomic% to 60 atomic% oxygen and 1 atomic% to 10 atomic% nitrogen Aluminum oxynitride film or aluminum alloy oxynitride film (3) Aluminum nitride film or aluminum alloy nitride film containing nitrogen of 50 atomic% to 60 atomic%
前記（１）のアルミニウム酸化膜又はアルミニウム合金酸化膜における酸素の含有量は、５０原子％以上である。また、酸素の含有量は、６０原子％以下である。酸素の含有量が５０原子％以上であることにより、低反射性を実現することができる。また、酸素の含有量が６０原子％以下であることにより、ウェットエッチング法での加工性を確保できる。 The oxygen content in the aluminum oxide film or aluminum alloy oxide film of (1) is 50 atomic% or more. The oxygen content is 60 atomic% or less. Low reflectivity can be realized when the oxygen content is 50 atomic% or more. Moreover, when the oxygen content is 60 atomic% or less, workability by the wet etching method can be secured.
前記（２）のアルミニウム酸窒化膜又はアルミニウム合金酸窒化膜における酸素の含有量は、５０原子％以上である。また、酸素の含有量は、６０原子％以下である。酸素の含有量が５０原子％以上であることにより、低反射性を実現することができる。また、酸素の含有量が６０原子％以下であることにより、ウェットエッチング法での加工性を確保できる。 The oxygen content in the aluminum oxynitride film or aluminum alloy oxynitride film of (2) is 50 atomic% or more. The oxygen content is 60 atomic% or less. Low reflectivity can be realized when the oxygen content is 50 atomic% or more. Moreover, when the oxygen content is 60 atomic% or less, workability by the wet etching method can be secured.
前記（２）のアルミニウム酸窒化膜又はアルミニウム合金酸窒化膜における窒素の含有量は、１原子％以上である。また、窒素の含有量は、１０原子％以下であり、好ましくは７原子％以下である。窒素の含有量が上記範囲になることで、低反射性とウェットエッチング加工性を確保できる。 The nitrogen content in the aluminum oxynitride film or aluminum alloy oxynitride film of (2) is 1 atomic% or more. The nitrogen content is 10 atomic% or less, preferably 7 atomic% or less. When the nitrogen content falls within the above range, low reflectivity and wet etching processability can be ensured.
前記（２）のアルミニウム酸窒化膜又はアルミニウム合金酸窒化膜における酸素と窒素の含有量の合計は、５０原子％以上であることが好ましく、より好ましくは５５原子％以上である。また、６５原子％以下であることが好ましく、より好ましくは６２原子％以下である。酸素と窒素の含有量の合計が５５原子％以上であることにより、低反射性と高い透過性を確保できる。また、酸素と窒素の含有量の合計が６５原子％以下であることにより、ウェットエッチング加工性を確保できる。 The total content of oxygen and nitrogen in the aluminum oxynitride film or aluminum alloy oxynitride film (2) is preferably 50 atomic% or more, more preferably 55 atomic% or more. Moreover, it is preferable that it is 65 atomic% or less, More preferably, it is 62 atomic% or less. When the total content of oxygen and nitrogen is 55 atomic% or more, low reflectivity and high transparency can be secured. Moreover, wet etching processability is securable because the sum total of content of oxygen and nitrogen is 65 atomic% or less.
前記（３）のアルミニウム窒化膜又はアルミニウム合金窒化膜における窒素の含有量は、５０原子％以上であり、好ましくは５５原子％以上である。また、窒素の含有量は、６０原子％以下である。窒素の含有量が５０原子％以上であることにより、低反射性を実現することができる。また、窒素の含有量が６０原子％以下であることにより、ウェットエッチング加工性を確保できる。 The nitrogen content in the aluminum nitride film or aluminum alloy nitride film of (3) is 50 atomic% or more, preferably 55 atomic% or more. The nitrogen content is 60 atomic% or less. Low reflectivity can be realized when the nitrogen content is 50 atomic% or more. Further, wet etching processability can be ensured when the nitrogen content is 60 atomic% or less.
アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜の膜厚は、その組成及び積層する金属膜の種類等によっても異なるが、反射率をより低減できることから２０ｎｍ以上が好ましく、より好ましくは２５ｎｍ以上である。膜厚が厚くなりすぎると、成膜プロセス時間の超過につながるため、２００ｎｍ以下が好ましく、より好ましくは１５０ｎｍ以下である。 The film thickness of the oxide film, nitride film or oxynitride film of aluminum or aluminum alloy varies depending on the composition and the type of metal film to be laminated, but is preferably 20 nm or more, more preferably 25 nm because the reflectance can be further reduced. That's it. If the film thickness becomes too thick, the film formation process time will be exceeded, so 200 nm or less is preferable, and more preferably 150 nm or less.
アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜は、スパッタリング法又は蒸着法等により成膜することができる。スパッタリング法を用いてアルミニウム合金窒化薄膜を成膜する場合、スパッタリング条件を変えることで、膜厚を調整することができる。 An oxide film, a nitride film, or an oxynitride film of aluminum or an aluminum alloy can be formed by a sputtering method, an evaporation method, or the like. When an aluminum alloy nitride thin film is formed using a sputtering method, the film thickness can be adjusted by changing the sputtering conditions.
アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜は上記成分以外のその他の成分として銅（Ｃｕ）、ネオジム（Ｎｄ）、鉄（Ｆｅ）、炭素（Ｃ）等の元素又は不可避不純物が含まれていてもよい。その他の成分の含有量は、アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜における酸素含有量若しくは窒素含有量又はその他の元素組成によっても異なる。 The oxide film, nitride film or oxynitride film of aluminum or aluminum alloy contains elements such as copper (Cu), neodymium (Nd), iron (Fe), carbon (C) or inevitable impurities as other components besides the above components. It may be. The content of other components varies depending on the oxygen content or nitrogen content or other elemental composition in the oxide film, nitride film, or oxynitride film of aluminum or aluminum alloy.
アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜におけるＣｕの含有量は３原子％以上であることが好ましく、より好ましくは５原子％以上である。Ｃｕの含有量は、２０原子％以下であることが好ましく、より好ましくは１５原子％以下である。 The Cu content in the oxide film, nitride film or oxynitride film of aluminum or aluminum alloy is preferably 3 atomic% or more, more preferably 5 atomic% or more. The Cu content is preferably 20 atomic% or less, and more preferably 15 atomic% or less.
アルミニウム合金の酸化膜、窒化膜又は酸窒化膜におけるＮｄの含有量は１原子％以上であることが好ましく、より好ましくは２．０原子％以上である。Ｎｄの含有量は、５原子％以下であることが好ましく、より好ましくは４．５原子％以下である。 The Nd content in the oxide film, nitride film, or oxynitride film of the aluminum alloy is preferably 1 atomic% or more, and more preferably 2.0 atomic% or more. The Nd content is preferably 5 atomic percent or less, and more preferably 4.5 atomic percent or less.
不可避不純物としてはＣ、Ｆｅ又はＭｇ等の金属元素が挙げられる。不可避不純物の含有量の上限は、合計で０．１原子％未満であることが好ましい。 Inevitable impurities include metal elements such as C, Fe or Mg. The upper limit of the content of inevitable impurities is preferably less than 0.1 atomic% in total.
（密着層又は保護層）
密着層又は保護層５は、金属電極薄膜の種類によって、密着性の改善又は耐食性の改善を目的として適宜設ける。具体的には、例えば、金属電極薄膜が純アルミニウム薄膜又はアルミニウム合金薄膜である場合には、加熱によるヒロック発生を抑制するため、保護層としてＴｉ、Ｍｏ、ＴｉＮ又はＭｏＮを積層することが好ましい。
(Adhesion layer or protective layer)
The adhesion layer or protective layer 5 is appropriately provided for the purpose of improving adhesion or improving corrosion resistance depending on the type of the metal electrode thin film. Specifically, for example, when the metal electrode thin film is a pure aluminum thin film or an aluminum alloy thin film, it is preferable to stack Ti, Mo, TiN or MoN as a protective layer in order to suppress generation of hillocks due to heating.
また、例えば、金属電極薄膜が純Ｃｕ薄膜又はＣｕ合金薄膜である場合には、密着性の向上又は耐熱性向上を目的としてＴｉ、ＴｉＮ、Ｔａ、ＴａＮ、ＳｉＮ又はＳｉＣＮを積層することが好ましい。また、例えば、金属電極薄膜が純Ａｇ薄膜又はＡｇ合金薄膜である場合には、密着性の向上又は耐熱性向上を目的としてＩＴＯ薄膜又はＩＺＯ薄膜に代表される透明導電膜を積層することが好ましい。 For example, when the metal electrode thin film is a pure Cu thin film or a Cu alloy thin film, it is preferable to stack Ti, TiN, Ta, TaN, SiN or SiCN for the purpose of improving adhesion or heat resistance. For example, when the metal electrode thin film is a pure Ag thin film or an Ag alloy thin film, a transparent conductive film typified by an ITO thin film or an IZO thin film is preferably laminated for the purpose of improving adhesion or heat resistance. .
密着層又は保護層はスパッタリング法、ＣＶＤ法又は蒸着法等により成膜することができる。密着層又は保護層の膜厚は、金属電極薄膜の種類等にもよっても異なるが、連続的に表面が平坦な膜を得るためには１０ｎｍ以上が好ましく、より好ましくは１５ｎｍ以上である。また膜厚の増加は成膜プロセス時間が長くなるため、５００ｎｍ以下が好ましく、より好ましくは３００ｎｍ以下である。スパッタリング法を用いて密着層又は保護層を成膜する場合、スパッタリング条件を変えることで、膜厚を調整することができる。 The adhesion layer or the protective layer can be formed by a sputtering method, a CVD method, an evaporation method, or the like. The film thickness of the adhesion layer or the protective layer varies depending on the type of the metal electrode thin film, but is preferably 10 nm or more, more preferably 15 nm or more in order to obtain a film having a continuously flat surface. Further, since the increase in the film thickness increases the film forming process time, it is preferably 500 nm or less, more preferably 300 nm or less. When the adhesion layer or the protective layer is formed using a sputtering method, the film thickness can be adjusted by changing the sputtering conditions.
以下に、実施例及び比較例を挙げて本発明をさらに具体的に説明するが、本発明は、これらの実施例に限定されるものではなく、その趣旨に適合し得る範囲で変更を加えて実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples, and modifications are made within a range that can be adapted to the gist thereof. It is also possible to carry out and they are all included in the technical scope of the present invention.
［評価方法］
（１）窒化薄膜中の窒素量
純アルミニウム窒化薄膜及びアルミニウム合金窒化薄膜における膜中窒素量（膜中Ｎ濃度）（原子％）はＰｅｒｋｉｎＥｌｍｅｒ社製のＰＨＩ６５０走査型オージェ電子分光装置を用いて、エネルギー ３ｋｅＶ、電流 約５０ｎＡの電子線を７５°の角度で膜表面に照射し、オージェ（Ａｕｇｅｒ）スペクトルを測定した。膜の深さ方向については、Ａｒ＋のイオンスパッタでエッチングしながら、上記と同様の条件で測定を行った。
[Evaluation method]
(1) Nitrogen amount in nitride thin film The amount of nitrogen (N concentration in the film) (atomic%) in pure aluminum nitride thin film and aluminum alloy nitride thin film was measured using a PHI650 scanning Auger electron spectrometer manufactured by PerkinElmer. The surface of the film was irradiated with an electron beam of 3 keV and a current of about 50 nA at an angle of 75 °, and an Auger spectrum was measured. For the depth direction of the film, measurement was performed under the same conditions as described above while etching by Ar + ion sputtering.
（２）単膜の反射率、透過率及び吸収率
純アルミニウム窒化薄膜及びアルミニウム合金窒化薄膜における反射率及び透過率は、日本分光社製Ｖ−５７０分光光度計を用い、波長４００ｎｍ〜８００ｎｍの反射率スペクトルと透過率スペクトルを測定した。表１には波長４５０ｎｍ、５５０ｎｍ及び６５０ｎｍにおける反射率と透過率を記載した。また各波長における吸収率は下記式より求めた。
吸収率（％）＝１００−反射率（％）−透過率（％）
(2) Reflectivity, transmittance, and absorptivity of single film Reflectance and transmittance in pure aluminum nitride thin film and aluminum alloy nitride thin film are reflected at wavelengths of 400 nm to 800 nm using a V-570 spectrophotometer manufactured by JASCO Corporation. The rate spectrum and transmittance spectrum were measured. Table 1 shows the reflectance and transmittance at wavelengths of 450 nm, 550 nm, and 650 nm. Moreover, the absorptance in each wavelength was calculated | required from the following formula.
Absorptivity (%) = 100-reflectance (%)-transmittance (%)
（３）窒化薄膜、金属電極薄膜及びアルミニウム合金窒化積層薄膜の電気抵抗率及びシート抵抗
窒化薄膜、金属電極薄膜及びアルミニウム合金窒化積層薄膜のシート抵抗はそれぞれ四端子法で測定した。なお窒化薄膜及び金属電極薄膜の単膜の電気抵抗率は、上記で得られたシート抵抗の値に膜厚を掛けることにより算出した。
(3) Electrical resistivity and sheet resistance of nitride thin film, metal electrode thin film and aluminum alloy nitride laminated thin film Sheet resistance of the nitride thin film, metal electrode thin film and aluminum alloy nitride laminated thin film was measured by a four-terminal method. The electrical resistivity of the single film of the nitride thin film and the metal electrode thin film was calculated by multiplying the sheet resistance value obtained above by the film thickness.
（４）積層薄膜の反射率
積層薄膜の反射率は、日本分光社製Ｖ−５７０分光光度計を用い、波長４００ｎｍ〜８００ｎｍの反射率スペクトルを測定した。
(4) Reflectance of laminated thin film The reflectance of the laminated thin film was measured using a V-570 spectrophotometer manufactured by JASCO Corporation, and a reflectance spectrum having a wavelength of 400 nm to 800 nm was measured.
［金属電極薄膜の評価：試験例１−１〜１−２２］
金属電極薄膜の評価を行うため、表１に示す組成となるように、下記条件でスパッタリング法により金属電極薄膜を成膜した。基板には厚みが０．７ｍｍのＣｏｒｎｉｎｇ社製ＥＡＧＬＥ ＸＧガラスを用いた。
[Evaluation of Metal Electrode Thin Film: Test Examples 1-1 to 1-22]
In order to evaluate the metal electrode thin film, the metal electrode thin film was formed by sputtering under the following conditions so as to have the composition shown in Table 1. Corning EAGLE XG glass with a thickness of 0.7 mm was used for the substrate.
（スパッタリング条件）
・成膜装置：ＵＬＶＡＣ社製 型式ＣＳ−２００
・ガス圧：２ｍＴｏｒｒ
・成膜ガス：Ａｒガス
・成膜パワー：ＤＣ５００Ｗ
・基板温度：室温
(Sputtering conditions)
・ Film forming apparatus: Model CS-200 manufactured by ULVAC
・ Gas pressure: 2mTorr
・ Deposition gas: Ar gas ・ Deposition power: DC500W
・ Substrate temperature: Room temperature
なお、アルミニウム合金窒化薄膜及び金属電極薄膜の膜厚は成膜時間を変更することで調整した。得られた薄膜の膜厚は触針式段差計により測定した。得られた試験例１−１〜１−２２の金属電極薄膜の組成及び評価結果を表１に示す。 The film thicknesses of the aluminum alloy nitride thin film and the metal electrode thin film were adjusted by changing the film formation time. The film thickness of the obtained thin film was measured with a stylus type step gauge. Table 1 shows the compositions and evaluation results of the obtained metal electrode thin films of Test Examples 1-1 to 1-22.
表１に示すように、いずれの金属電極薄膜も電気抵抗率が１５μΩ・ｃｍ以下であって、高い導電性を示し、第１層として利用可能であることがわかった。 As shown in Table 1, it was found that any of the metal electrode thin films had an electrical resistivity of 15 μΩ · cm or less, showed high conductivity, and could be used as the first layer.
［アルミニウム合金窒化薄膜の評価：試験例２−１〜２−２９］
アルミニウム合金窒化薄膜の光吸収特性についての評価を行うため、純アルミニウム窒化薄膜（試験例２−１〜２−４）及びアルミニウム合金窒化薄膜（試験例試験例２−５〜２−２９）を表２に記載の組成となるように下記条件でスパッタリング法により成膜した。基板には厚みが０．７ｍｍのＣｏｒｎｉｎｇ社製ＥＡＧＬＥ ＸＧガラスを用いた。
[Evaluation of Aluminum Alloy Nitride Thin Film: Test Examples 2-1 to 2-29]
In order to evaluate the light absorption characteristics of the aluminum alloy nitride thin film, pure aluminum nitride thin films (Test Examples 2-1 to 2-4) and aluminum alloy nitride thin films (Test Examples Test Examples 2-5 to 2-29) are shown. The film was formed by sputtering under the following conditions so that the composition described in 2 was obtained. Corning EAGLE XG glass with a thickness of 0.7 mm was used for the substrate.
（スパッタリング条件）
・成膜装置：ＵＬＶＡＣ社製 型式ＣＳ−２００
・ガス圧：２ｍＴｏｒｒ
・成膜ガス：Ａｒガス及びＮ２ガスからなる混合ガス
・成膜パワー：ＤＣ５００Ｗ
・基板温度：室温
(Sputtering conditions)
・ Film forming apparatus: Model CS-200 manufactured by ULVAC
・ Gas pressure: 2mTorr
・ Film formation gas: Mixed gas consisting of Ar gas and N 2 gas ・ Film formation power: DC500W
・ Substrate temperature: Room temperature
なお、表２に示す膜中窒素量（膜中Ｎ濃度）（原子％）になるように、Ａｒガス及びＮ２ガスの混合量を変化させた成膜ガスにより成膜した。得られた試験例２−１〜２−２９の純アルミニウム窒化薄膜又はアルミニウム合金窒化薄膜の組成及び評価結果を表２に示す。表２中、波長４５０ｎｍ、５５０ｎｍ及び６５０ｎｍにおける反射率が５０％以下であれば、評価を「○」とした。 It should be noted that the film was formed with a film forming gas in which the mixed amount of Ar gas and N 2 gas was changed so that the nitrogen amount in the film (N concentration in the film) (atomic%) shown in Table 2 was obtained. Table 2 shows the compositions and evaluation results of the pure aluminum nitride thin films or aluminum alloy nitride thin films obtained in Test Examples 2-1 to 2-29. In Table 2, when the reflectance at wavelengths of 450 nm, 550 nm, and 650 nm was 50% or less, the evaluation was “◯”.
表２に示すように、試験例２−１〜２−４は純アルミニウム窒化薄膜である。膜中の窒素量が４０原子％以上である試験例２−４は、反射率が５０％以下であり、要求を満たした。一方、膜中の窒素量が４０原子％未満である試験例２−１〜２−３は、反射率が５０％超であり、要求を満たさなかった。 As shown in Table 2, Test Examples 2-1 to 2-4 are pure aluminum nitride thin films. Test Example 2-4 in which the amount of nitrogen in the film was 40 atomic% or more had a reflectance of 50% or less and satisfied the requirement. On the other hand, Test Examples 2-1 to 2-3, in which the amount of nitrogen in the film was less than 40 atomic%, had a reflectance of more than 50% and did not satisfy the requirement.
試験例２−５〜２−１０はＡｌとＣｕからなるアルミニウム合金窒化薄膜である。膜中の窒素量が４０原子％以上である試験例２−７〜２−１０は、反射率が５０％以下であり、要求を満たした。一方、膜中の窒素量が４０原子％未満である試験例２−５〜２−６は、反射率が５０％超であった。 Test Examples 2-5 to 2-10 are aluminum alloy nitride thin films made of Al and Cu. In Test Examples 2-7 to 2-10 in which the amount of nitrogen in the film was 40 atomic% or more, the reflectance was 50% or less, and the requirement was satisfied. On the other hand, Test Examples 2-5 to 2-6 in which the amount of nitrogen in the film was less than 40 atomic% had a reflectance of more than 50%.
試験例２−１１〜２−２７はＡｌとＣｕを含み、Ｙ、Ｓｉ、Ｔｉ及びＮｄから選ばれる少なくとも１種を含むアルミニウム合金窒化薄膜である。膜中の窒素量が４０原子％以上である試験例２−１２〜２−２７は、反射率が５０％以下であり、要求を満たした。一方、膜中の窒素量が４０原子％未満である試験例２−１１は、反射率が５０％超であり、要求を満たさなかった。 Test Examples 2-11 to 2-27 are aluminum alloy nitride thin films containing Al and Cu and containing at least one selected from Y, Si, Ti, and Nd. In Test Examples 2-12 to 2-27 in which the amount of nitrogen in the film was 40 atomic% or more, the reflectance was 50% or less, and the requirement was satisfied. On the other hand, Test Example 2-11 in which the amount of nitrogen in the film was less than 40 atomic% had a reflectance of more than 50% and did not satisfy the requirement.
これらの結果から、アルミニウム又はアルミニウム合金の窒化膜中の窒素量を４０原子％以上とすることにより、反射率が５０％以下となることがわかった。 From these results, it was found that the reflectance was 50% or less when the amount of nitrogen in the nitride film of aluminum or aluminum alloy was 40 atomic% or more.
［アルミニウム合金酸化膜、窒化膜又は酸窒化膜：試験例３−１〜３−１１］
アルミニウム合金酸化膜、窒化膜又は酸窒化膜の分光特性を評価するため、純アルミニウム窒化薄膜（試験例３−１〜３−３）及びアルミニウム合金窒化薄膜（試験例３−４〜３−１１）を表３に示す組成となるように下記条件でスパッタリング法により成膜した。基板には厚みが０．７ｍｍのＣｏｒｎｉｎｇ社製ＥＡＧＬＥ ＸＧガラスを用いた。
[Aluminum alloy oxide film, nitride film or oxynitride film: Test examples 3-1 to 11-11]
In order to evaluate the spectral characteristics of the aluminum alloy oxide film, nitride film, or oxynitride film, pure aluminum nitride thin films (Test Examples 3-1 to 3-3) and aluminum alloy nitride thin films (Test Examples 3-4 to 3-11) Was formed by sputtering under the following conditions so as to have the composition shown in Table 3. Corning EAGLE XG glass with a thickness of 0.7 mm was used for the substrate.
（スパッタリング条件）
・成膜装置：ＵＬＶＡＣ社製 型式ＣＳ−２００
・ガス圧：２ｍＴｏｒｒ
・成膜ガス：Ａｒガス、Ｎ２ガス及びＯ２ガスからなる混合ガス
・成膜パワー：ＤＣ５００Ｗ
・基板温度：室温
(Sputtering conditions)
・ Film forming apparatus: Model CS-200 manufactured by ULVAC
・ Gas pressure: 2mTorr
・ Film forming gas: Mixed gas consisting of Ar gas, N 2 gas and O 2 gas ・ Film forming power: DC500W
・ Substrate temperature: Room temperature
なお、成膜ガスは表３に示す膜中窒素量（膜中Ｎ濃度）（原子％）になるように、ＡｒガスとＮ２ガス及びＯ２ガスの混合量を変えて成膜を行った。得られた試験例３−１〜３−１１の薄膜の組成及び評価結果を表３に示す。表３中、反射率が３５％以下で、電気抵抗率が１．０×１０７μΩ・ｃｍ以上であれば、評価を「○」とした。 The film formation gas was formed by changing the mixed amount of Ar gas, N 2 gas and O 2 gas so that the nitrogen amount in the film (N concentration in the film) (atomic%) shown in Table 3 was obtained. . Table 3 shows the compositions and evaluation results of the obtained thin films of Test Examples 3-1 to 3-11. In Table 3, when the reflectance was 35% or less and the electrical resistivity was 1.0 × 10 7 μΩ · cm or more, the evaluation was “◯”.
表３に示すように、５０原子％以上６０原子％以下の酸素を含むアルミニウム酸化膜又はアルミニウム合金酸化膜である試験例３−１、３−４及び３−１０は、反射率が３５％以下、電気抵抗率が１．０×１０７μΩ・ｃｍ以上であり、要求を満たした。 As shown in Table 3, in Test Examples 3-1, 3-4, and 3-10, which are aluminum oxide films or aluminum alloy oxide films containing 50 atomic% or more and 60 atomic% or less of oxygen, the reflectance is 35% or less. The electrical resistivity was 1.0 × 10 7 μΩ · cm or more, satisfying the requirements.
また、５０原子％以上６０原子％以下の酸素、１原子％以上１０原子％以下の窒素を含むアルミニウム酸窒化膜又はアルミニウム合金酸窒化膜である試験例３−２、３−５〜３−７及び３−１１は、反射率が３５％以下、電気抵抗率が１．０×１０７μΩ・ｃｍ以上であり、要求を満たした。 Further, Test Examples 3-2 and 3-5 to 3-7, which are an aluminum oxynitride film or an aluminum alloy oxynitride film containing oxygen of 50 atomic% to 60 atomic% and nitrogen of 1 atomic% to 10 atomic%. And No. 3-11 had a reflectance of 35% or less and an electric resistivity of 1.0 × 10 7 μΩ · cm or more, which satisfied the requirements.
さらに、５０原子％以上６０原子％以下の窒素を含むアルミニウム窒化膜又はアルミニウム合金窒化膜である試験例３−１及び３−４は、反射率が３５％以下、電気抵抗率が１．０×１０７μΩ・ｃｍ以上であり、要求を満たした。 Furthermore, Test Examples 3-1 and 3-4, which are aluminum nitride films or aluminum alloy nitride films containing nitrogen of 50 atomic% or more and 60 atomic% or less, have a reflectance of 35% or less and an electrical resistivity of 1.0 ×. It was 10 7 μΩ · cm or more, which satisfied the requirement.
一方、膜中の窒素濃度が５０原子％未満のアルミニウム合金窒化膜である試験例３−８は、反射率が３５％超と高く、電気抵抗率が１．０×１０７μΩ・ｃｍ未満であり、要求を満たさなかった。 On the other hand, Test Example 3-8, which is an aluminum alloy nitride film having a nitrogen concentration of less than 50 atomic% in the film, has a high reflectance of more than 35% and an electrical resistivity of less than 1.0 × 10 7 μΩ · cm. Yes, did not meet the requirements.
表４に、第１層を表１で示した各金属電極薄膜として、該第１層に表４に示す第２層及び第３層を積層した場合の積層膜の例を示す。表４において、ウェットエッチング加工性は、一括ウェットエッチング加工が可能であれば「ＯＫ」とした。 Table 4 shows an example of a laminated film when the first layer is the metal electrode thin film shown in Table 1 and the second layer and the third layer shown in Table 4 are laminated on the first layer. In Table 4, the wet etching processability is set to “OK” if collective wet etching process is possible.
表４に示すように、電気抵抗率が１５μΩ・ｃｍ以下である金属薄膜である第１層、４０原子％以上６１原子％以下の窒素を含むアルミニウム合金窒化膜である第２層、並びに５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含むアルミニウム酸窒化膜である第３層を積層することで低反射性、導電性及びエッチング加工性を両立する積層膜が得られることがわかった。 As shown in Table 4, a first layer that is a metal thin film having an electrical resistivity of 15 μΩ · cm or less, a second layer that is an aluminum alloy nitride film containing nitrogen of 40 atomic% to 61 atomic%, and 50 atoms Laminated film that achieves both low reflectivity, electrical conductivity, and etching processability by laminating a third layer, which is an aluminum oxynitride film containing oxygen in the range of 60% to 60% by atom and nitrogen in the range of 1% to 10% by atom. Was found to be obtained.
表５に、第２層を表２で示したアルミニウム窒化膜又はアルミニウム合金窒化膜として、該第２層に表５に示す第１層及び第３層を積層した積層膜の例を示す。表５において、ウェットエッチング加工性は、一括ウェットエッチング加工が可能であれば「ＯＫ」とした。 Table 5 shows an example of a laminated film in which the second layer is the aluminum nitride film or aluminum alloy nitride film shown in Table 2 and the first layer and the third layer shown in Table 5 are laminated on the second layer. In Table 5, the wet etching processability was set to “OK” if collective wet etching process was possible.
表５に示すように、試験例５−１〜５−３、５−５、５−６及び５−１１は、第２層の単膜反射率が５０％以上と高いことから、第１層及び第３層を積層しても反射率が１５．０％超と高く、要求する低反射性を満たすことができないことがわかった。 As shown in Table 5, in Test Examples 5-1 to 5-3, 5-5, 5-6, and 5-11, since the single-film reflectance of the second layer is as high as 50% or more, the first layer And even if the third layer was laminated, it was found that the reflectivity was as high as 15.0% and the required low reflectivity could not be satisfied.
表６には、第３層を表３で示した、アルミニウム合金酸化膜、窒化膜又は酸窒化膜とし、該第３層に表６に示す第１層及び第２層を積層した積層膜の例を示す。表６において、ウェットエッチング加工性は、ウェットエッチング法で一括加工可能であれば「ＯＫ」、一括加工できなければ「ＮＧ」とした。 Table 6 shows a laminated film in which the third layer is an aluminum alloy oxide film, nitride film, or oxynitride film shown in Table 3, and the first layer and the second layer shown in Table 6 are stacked on the third layer. An example is shown. In Table 6, the wet etching processability was set to “OK” if batch processing was possible by the wet etching method, and “NG” if batch processing was not possible.
表６において、反射率（４５０ｎｍ、５５０ｎｍ及び６５０ｎｍ）が１５．０％以下であり且つウェットエッチング加工性が「ＯＫ」であれば「○」、反射率（４５０ｎｍ、５５０ｎｍ及び６５０ｎｍ）が１５．０％以下であり且つウェットエッチング加工性が「ＮＧ」であれば「△」、反射率（４５０ｎｍ、５５０ｎｍ及び６５０ｎｍ）が１５．０％超である場合は「×」と評価した。 In Table 6, if the reflectance (450 nm, 550 nm, and 650 nm) is 15.0% or less and the wet etching processability is “OK”, “◯”, and the reflectance (450 nm, 550 nm, and 650 nm) is 15.0. % When the wet etching processability is “NG”, and “X” when the reflectance (450 nm, 550 nm and 650 nm) is more than 15.0%.
表６に示すように、電気抵抗率が１５μΩ・ｃｍ以下である金属薄膜である第１層、４０原子％以上６１原子％以下の窒素を含むアルミニウム合金窒化膜である第２層、並びに５０原子％以上６０原子％以下の酸素を含むアルミニウム酸化膜若しくはアルミニウム合金酸化膜、５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含むアルミニウム酸窒化膜若しくはアルミニウム合金酸窒化膜、又は５０原子％以上６０原子％以下の窒素を含むアルミニウム窒化膜若しくはアルミニウム合金窒化膜である第３層を積層した試験例６−２〜６−９及び６−１１〜６−２２は、低反射性、導電性及びエッチング加工性を両立する積層膜が得られることがわかった。 As shown in Table 6, the first layer, which is a metal thin film having an electrical resistivity of 15 μΩ · cm or less, the second layer, which is an aluminum alloy nitride film containing 40 atomic% to 61 atomic% of nitrogen, and 50 atoms Aluminum Oxide Nitride Film or Aluminum Alloy Oxide Film Containing 50% to 60 At% Oxygen, Aluminum Oxynitride Film or Aluminum Alloy Acid Containing 50 At% to 60 At% Oxygen and 1 At% to 10 At% Nitrogen Test examples 6-2 to 6-9 and 6-11 to 6-22 in which a third layer which is a nitride film, or an aluminum nitride film or an aluminum alloy nitride film containing nitrogen of 50 atomic% to 60 atomic% is laminated, It was found that a laminated film having both low reflectivity, conductivity and etching processability can be obtained.
一方、試験例６−１は反射率が１５．０％以上と高く、要求を満たさなかった。また、単膜反射率が高い試験例３−８の第３層を積層した試験例６−１０は、反射率が１５．０％以上と高く、要求を満たさなかった。 On the other hand, Test Example 6-1 had a high reflectance of 15.0% or more and did not satisfy the requirement. In addition, Test Example 6-10 in which the third layer of Test Example 3-8 having a high single-film reflectance was stacked had a high reflectance of 15.0% or more and did not satisfy the requirements.
１ 基板
２ 第１層（導電層）
３ 第２層（アルミニウム窒化膜又はアルミニウム合金窒化膜）
４ 第３層（アルミニウム又はアルミニウム合金の酸化膜、窒化膜又は酸窒化膜）
５ 密着層又は保護層
1 Substrate 2 First layer (conductive layer)
3 Second layer (aluminum nitride film or aluminum alloy nitride film)
4 Third layer (aluminum or aluminum alloy oxide film, nitride film or oxynitride film)
5 adhesion layer or protective layer
本発明者らは、鋭意研究を重ねた結果、電気抵抗率が特定範囲以下である金属薄膜である第１層、特定の組成を有するアルミニウム又はアルミニウム合金の窒化膜である第２層、特定の組成を有するアルミニウム合金の酸化膜、又はアルミニウム若しくはアルミニウム合金の酸窒化膜である第３層がこの順に積層された積層膜を採用することにより、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive research, the inventors of the present invention have found that a first layer that is a metal thin film whose electrical resistivity is not more than a specific range, a second layer that is a nitride film of aluminum or aluminum alloy having a specific composition, a specific layer oxide film of the luer aluminum alloy having a composition, or the third layer is a oxynitride film of the aluminum or aluminum alloy by employing a laminated film laminated in this order, can solve the above problems, the present invention It came to complete.
すなわち、本発明は、以下の［１］〜［３］に係るものである。
［１］第１層、第２層及び第３層がこの順に積層された積層膜であって、
第１層が、電気抵抗率が１５μΩ・ｃｍ以下である金属薄膜であり、
第２層が４０原子％以上６１原子％以下の窒素を含むアルミニウム窒化膜又は４０原子％以上６１原子％以下の窒素と、酸素（Ｏ）、銅（Ｃｕ）、イットリウム（Ｙ）、ケイ素（Ｓｉ）、チタン（Ｔｉ）、ネオジム（Ｎｄ）うち少なくとも１つを含むアルミニウム合金窒化膜であり、
第３層が５０原子％以上６０原子％以下の酸素と、銅（Ｃｕ）、ネオジム（Ｎｄ）、鉄（Ｆｅ）、炭素（Ｃ）の少なくとも１つを含むアルミニウム合金酸化膜、５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含むアルミニウム酸窒化膜、又は５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素と、銅（Ｃｕ）、ネオジム（Ｎｄ）、鉄（Ｆｅ）、炭素（Ｃ）の少なくとも１つを含むアルミニウム合金酸窒化膜であり、
前記第２層の膜厚が２０ｎｍ〜２００ｎｍ、かつ、前記第３層の膜厚が１５ｎｍ〜２００ｎｍである積層膜。
［２］［１］に記載の積層膜を備えた表示装置。
［３］［１］に記載の積層膜を備えた入力装置。
That is, the present invention relates to the following [1] to [3].
[1] A laminated film in which a first layer, a second layer, and a third layer are laminated in this order,
The first layer is a metal thin film having an electrical resistivity of 15 μΩ · cm or less,
The second layer is an aluminum nitride film containing nitrogen of 40 atomic% to 61 atomic% or nitrogen of 40 atomic% to 61 atomic%, oxygen (O), copper (Cu), yttrium (Y), silicon (Si ), An aluminum alloy nitride film containing at least one of titanium (Ti) and neodymium (Nd) ,
An aluminum alloy oxide film in which the third layer contains oxygen of 50 atomic% to 60 atomic% and at least one of copper (Cu), neodymium (Nd), iron (Fe), and carbon (C); Aluminum oxynitride film containing oxygen of 60 atomic% or less and nitrogen of 1 atomic% or more and 10 atomic% or less , or oxygen of 50 atomic% or more and 60 atomic% or less and nitrogen of 1 atomic% or more and 10 atomic% or less, and copper ( Cu), neodymium (Nd), iron (Fe), an aluminum alloy oxynitride film containing at least one of carbon (C) ,
A laminated film in which the second layer has a thickness of 20 nm to 200 nm, and the third layer has a thickness of 15 nm to 200 nm.
[2] A display device comprising the laminated film according to [1].
[3] An input device comprising the laminated film according to [1].
本発明によれば、前記した金属薄膜である第１層、アルミニウム又はアルミニウム合金の窒化膜である第２層、及びアルミニウム合金の酸化膜、又はアルミニウム若しくはアルミニウム合金の酸窒化膜である第３層をこの順に積層することで、電気抵抗率が低く、低反射性、導電性及びエッチング加工性に優れ、かつ安価な光吸収薄膜及び低反射導電膜を得られるとともに、安定した製造が可能になる。 According to the present invention, the first layer is a metallic thin film described above, the second layer is a nitride film of aluminum or an aluminum alloy, an oxide film or oxynitride film of the aluminum or aluminum alloy及beauty A aluminum alloy first By laminating three layers in this order, it is possible to obtain an inexpensive light-absorbing thin film and low-reflective conductive film with low electrical resistivity, excellent low reflectivity, conductivity and etching processability, and stable production is possible. become.
アルミニウム合金窒化膜は上記成分以外のその他の成分として酸素（Ｏ）、銅（Ｃｕ）、イットリウム（Ｙ）、ケイ素（Ｓｉ）、チタン（Ｔｉ）若しくはネオジム（Ｎｄ）等の元素又は不可避不純物が含まれていてもよい。その他の成分の含有量は、アルミニウム合金窒化膜における窒素含有量又はその他の元素組成によっても異なる。 A aluminum alloy nitride film oxygen as components other than the component (O), copper (Cu), yttrium (Y), silicon (Si), titanium (Ti) or neodymium (Nd) elements such or unavoidable impurities It may be included. The content of the other components will vary depending nitrogen content or other element compositions in A aluminum alloy nitride film.
（アルミニウム合金の酸化膜、アルミニウム若しくはアルミニウム合金の窒化膜又は酸窒化膜：第３層）
アルミニウム合金の酸化膜、アルミニウム若しくはアルミニウム合金の窒化膜又は酸窒化膜である第３層４は積層膜の低反射化を実現するために機能するための光学調整層として機能する。そのため、第３層は、アルミニウム又はアルミニウム合金の窒化膜である第２層の直上又は直下に設けることが好ましい。金属膜の低反射化を目的とするため、例えば、図１に示すように第３層を表面側に設けてもよいし、図２に示すように基板側に設けてもよく、その位置は光の入射側又は視認する側に依存する。
(Oxide film of A aluminum alloy, aluminum or a nitride film of an aluminum alloy or an oxynitride film: third layer)
Oxide film of A aluminum alloy, a third layer 4 is a nitride film or an oxynitride film of aluminum or aluminum alloy functioning as the optical adjustment layer to function in order to realize low reflection of the multilayer film. Therefore, the third layer is preferably provided directly above or directly below the second layer, which is a nitride film of aluminum or aluminum alloy. In order to reduce the reflection of the metal film, for example, the third layer may be provided on the surface side as shown in FIG. 1, or may be provided on the substrate side as shown in FIG. Depends on the light incident side or the viewing side.
第３層が単層である場合、以下の（１）〜（３）のいずれか１であることを特徴とする。
（１）５０原子％以上６０原子％以下の酸素を含む、アルミニウム合金酸化膜
（２）５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含む、アルミニウム酸窒化膜又はアルミニウム合金酸窒化膜
（３）５０原子％以上６０原子％以下の窒素を含む、アルミニウム窒化膜又はアルミニウム合金窒化膜
When the third layer is a single layer, it is any one of the following (1) to (3).
(1) 50 to 60 atom% comprising the following oxygen, including A aluminum alloy oxide film (2) 50 atom% to 60 atom% oxygen and 1 atom% to 10 atom% of nitrogen, aluminum acid Nitride film or aluminum alloy oxynitride film (3) Aluminum nitride film or aluminum alloy nitride film containing nitrogen of 50 atomic% to 60 atomic%
前記（１）のアルミニウム合金酸化膜における酸素の含有量は、５０原子％以上である。また、酸素の含有量は、６０原子％以下である。酸素の含有量が５０原子％以上であることにより、低反射性を実現することができる。また、酸素の含有量が６０原子％以下であることにより、ウェットエッチング法での加工性を確保できる。 The oxygen content in the A aluminum alloy oxide film of the (1) is 50 atomic% or more. The oxygen content is 60 atomic% or less. Low reflectivity can be realized when the oxygen content is 50 atomic% or more. Moreover, when the oxygen content is 60 atomic% or less, workability by the wet etching method can be secured.
アルミニウム合金の酸化膜、又はアルミニウム若しくはアルミニウム合金の窒化膜又は酸窒化膜の膜厚は、その組成及び積層する金属膜の種類等によっても異なるが、反射率をより低減できることから２０ｎｍ以上が好ましく、より好ましくは２５ｎｍ以上である。膜厚が厚くなりすぎると、成膜プロセス時間の超過につながるため、２００ｎｍ以下が好ましく、より好ましくは１５０ｎｍ以下である。 Oxide film of A aluminum alloy, or aluminum or thickness of the nitride film or an oxynitride film of aluminum alloy, varies depending on the type of metal film whose composition and lamination, preferably not less than 20nm because it can further reduce the reflectance More preferably, it is 25 nm or more. If the film thickness becomes too thick, the film formation process time will be exceeded, so 200 nm or less is preferable, and more preferably 150 nm or less.
アルミニウム合金の酸化膜、又はアルミニウム若しくはアルミニウム合金の窒化膜又は酸窒化膜は、スパッタリング法又は蒸着法等により成膜することができる。スパッタリング法を用いてアルミニウム合金窒化薄膜を成膜する場合、スパッタリング条件を変えることで、膜厚を調整することができる。 Oxide film, or an aluminum or a nitride film or an oxynitride film of the aluminum alloy of the A aluminum alloy can be deposited by sputtering or vapor deposition method. When an aluminum alloy nitride thin film is formed using a sputtering method, the film thickness can be adjusted by changing the sputtering conditions.
アルミニウム合金の酸化膜、アルミニウム合金の窒化膜又は酸窒化膜は上記成分以外のその他の成分として銅（Ｃｕ）、ネオジム（Ｎｄ）、鉄（Ｆｅ）、炭素（Ｃ）等の元素又は不可避不純物が含まれていてもよい。その他の成分の含有量は、アルミニウム合金の酸化膜、アルミニウム合金の窒化膜又は酸窒化膜における酸素含有量若しくは窒素含有量又はその他の元素組成によっても異なる。 Oxide film of A aluminum alloy, copper nitride film or an oxynitride film of an aluminum alloy as the other components other than the above components (Cu), neodymium (Nd), iron (Fe), elements or inevitable impurities such as carbon (C) May be included. The content of the other components will vary depending oxide film, the oxygen content in the nitride film or an oxynitride film of an aluminum alloy or nitrogen content or other elemental composition of A aluminum alloy.
アルミニウム合金の酸化膜、窒化膜又は酸窒化膜におけるＣｕの含有量は３原子％以上であることが好ましく、より好ましくは５原子％以上である。Ｃｕの含有量は、２０原子％以下であることが好ましく、より好ましくは１５原子％以下である。 Preferably the oxide film of A aluminum alloy, the content of Cu in the nitride film or oxynitride film is 3 atomic% or more, more preferably 5 atomic% or more. The Cu content is preferably 20 atomic% or less, and more preferably 15 atomic% or less.
表６に示すように、電気抵抗率が１５μΩ・ｃｍ以下である金属薄膜である第１層、４０原子％以上６１原子％以下の窒素を含むアルミニウム合金窒化膜である第２層、並びに５０原子％以上６０原子％以下の酸素を含むアルミニウム合金酸化膜、５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含むアルミニウム酸窒化膜若しくはアルミニウム合金酸窒化膜、又は５０原子％以上６０原子％以下の窒素を含むアルミニウム窒化膜若しくはアルミニウム合金窒化膜である第３層を積層した試験例６−２〜６−９及び６−１１〜６−２２は、低反射性、導電性及びエッチング加工性を両立する積層膜が得られることがわかった。 As shown in Table 6, the first layer, which is a metal thin film having an electrical resistivity of 15 μΩ · cm or less, the second layer, which is an aluminum alloy nitride film containing 40 atomic% to 61 atomic% of nitrogen, and 50 atoms % to 60 atom% of oxygen including a aluminum alloy oxide film, an aluminum oxynitride film or an aluminum alloy oxynitride film containing 50 atom% to 60 atom% oxygen and 1 atom% to 10 atom% of nitrogen Alternatively, Test Examples 6-2 to 6-9 and 6-11 to 6-22 in which a third layer that is an aluminum nitride film or an aluminum alloy nitride film containing nitrogen of 50 atomic% or more and 60 atomic% or less is low It was found that a laminated film having both reflectivity, conductivity and etching processability can be obtained.
１ 基板
２ 第１層（導電層）
３ 第２層（アルミニウム窒化膜又はアルミニウム合金窒化膜）
４ 第３層（アルミニウム合金の酸化膜、又はアルミニウム若しくはアルミニウム合金の窒化膜又は酸窒化膜）
５ 密着層又は保護層
1 Substrate 2 First layer (conductive layer)
3 Second layer (aluminum nitride film or aluminum alloy nitride film)
4 third layer (oxide film A aluminum alloy, or aluminum or a nitride film of an aluminum alloy or an oxynitride film)
5 adhesion layer or protective layer
Claims (3)
第１層が電気抵抗率が１５μΩ・ｃｍ以下である金属薄膜であり、
第２層が４０原子％以上６１原子％以下の窒素を含むアルミニウム窒化膜又はアルミニウム合金窒化膜であり、
第３層が５０原子％以上６０原子％以下の酸素を含むアルミニウム酸化膜若しくはアルミニウム合金酸化膜、５０原子％以上６０原子％以下の酸素及び１原子％以上１０原子％以下の窒素を含むアルミニウム酸窒化膜若しくはアルミニウム合金酸窒化膜、又は５０原子％以上６０原子％以下の窒素を含むアルミニウム窒化膜若しくはアルミニウム合金窒化膜である積層膜。 The first layer, the second layer, and the third layer are stacked films in this order,
The first layer is a metal thin film having an electrical resistivity of 15 μΩ · cm or less,
The second layer is an aluminum nitride film or an aluminum alloy nitride film containing nitrogen of 40 atomic% or more and 61 atomic% or less,
Aluminum oxide film containing aluminum oxide film or aluminum alloy oxide film in which the third layer contains oxygen of 50 atomic percent to 60 atomic percent, aluminum acid containing oxygen of 50 atomic percent to 60 atomic percent and nitrogen of 1 atomic percent to 10 atomic percent A laminated film which is a nitride film or an aluminum alloy oxynitride film, or an aluminum nitride film or an aluminum alloy nitride film containing nitrogen of 50 atomic% to 60 atomic%.
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201743178A (en) | 2017-12-16 |
| TW201833749A (en) | 2018-09-16 |
| WO2017212970A1 (en) | 2017-12-14 |
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