JP7196372B2 - LAMINATED STRUCTURE AND METHOD FOR MANUFACTURING LAMINATED STRUCTURE - Google Patents

LAMINATED STRUCTURE AND METHOD FOR MANUFACTURING LAMINATED STRUCTURE Download PDF

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JP7196372B2
JP7196372B2 JP2022550351A JP2022550351A JP7196372B2 JP 7196372 B2 JP7196372 B2 JP 7196372B2 JP 2022550351 A JP2022550351 A JP 2022550351A JP 2022550351 A JP2022550351 A JP 2022550351A JP 7196372 B2 JP7196372 B2 JP 7196372B2
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祐輔 氏原
雅文 若井
淳三 須川
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Description

本発明は、第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体及び積層構造体の製造方法に関する。 The present invention relates to a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated, and a method for manufacturing the laminated structure.

この種の積層構造体は、ディスプレイ、スマートフォンや電子ペーパーなどの電子デバイスにて、スイッチング素子（薄膜トランジスタ）のソース／ドレイン電極として用いられている（例えば特許文献１参照）。一方、近年の可撓性を有する電子デバイスの開発に伴い、比較的高硬度のチタン層を有する積層構造体に対し、高い屈曲耐性が要求されるようになっている。 Laminated structures of this type are used as source/drain electrodes of switching elements (thin film transistors) in electronic devices such as displays, smartphones, and electronic paper (see, for example, Patent Document 1). On the other hand, with the development of flexible electronic devices in recent years, there has been a demand for high bending resistance for laminated structures having relatively high-hardness titanium layers.

一般に、積層構造体のチタン層やアルミニウム層は、真空雰囲気中でスパッタリング法により一貫して成膜される（例えば、特許文献１参照）。例えば、チタン層やアルミニウム層の成膜に際しては、チタン製またはアルミニウム製のターゲットと基材とを対向配置した真空チャンバ内を所定圧力まで真空排気した後、真空チャンバ内に希ガス（例えば、アルゴンガス）を導入し、ターゲットに負の電位を持つ直流電力を投入してプラズマを形成し、プラズマ中で電離した希ガスのイオンによりターゲットをスパッタリングし、ターゲットから飛散したスパッタ粒子を基材に付着、堆積させて、所望の膜厚（例えば、第１のチタン層を５０ｎｍ、アルミニウム層を５００ｎｍ、第２のチタン層を５０ｎｍ）でチタン層やアルミニウム層が成膜される。このとき、ターゲットへの投入電力、希ガスのガス導入量や成膜中の真空チャンバ内の全圧といった各種のスパッタ条件は、生産性や膜厚分布を考慮して設定される（例えば、投入電力２０～４０ｋＷ、全圧が０．２～１．０Ｐａ）。 In general, a titanium layer and an aluminum layer of a laminated structure are consistently formed by a sputtering method in a vacuum atmosphere (see, for example, Patent Document 1). For example, when forming a titanium layer or an aluminum layer, after evacuating a vacuum chamber in which a titanium or aluminum target and a substrate are arranged to face each other to a predetermined pressure, a rare gas (for example, argon) is introduced into the vacuum chamber. gas) is introduced, DC power with a negative potential is applied to the target to form plasma, the target is sputtered by ionized noble gas ions in the plasma, and the sputtered particles scattered from the target adhere to the substrate. , to form a titanium layer or an aluminum layer with a desired film thickness (eg, a first titanium layer of 50 nm, an aluminum layer of 500 nm, and a second titanium layer of 50 nm). At this time, various sputtering conditions such as input power to the target, amount of rare gas introduced, and total pressure in the vacuum chamber during film formation are set in consideration of productivity and film thickness distribution (for example, input power 20-40 kW, total pressure 0.2-1.0 Pa).

ここで、積層構造体の屈曲耐性を確認するために、所定形状の試験基材を用い、試験基材表面に第１のチタン層、アルミニウム層、第２のチタン層を所定のスパッタ条件で順次積層した後、試験基材から剥離した積層構造体に対し、引張試験を実施したところ、５％の伸び量を与えるのに必要な引張荷重を加えただけで、積層構造体が倍以上に伸びることが判明した。また、引張試験後の積層構造体の表面（即ち、チタン層表面）状態を観察したところ、チタン層に厚さ方向にのびるクラックが多数発生していることが判明した。そこで、本発明者らは、鋭意研究を重ね、比較的小さい結晶粒が膜厚方向に整列して結晶粒界がその膜厚方向にのびるように繋がった結晶構造を有すると共に、成膜時にチタン層内に取り込まれた窒素分子や酸素分子といった不純物により結晶粒界に硬くてもろい窒化チタンや酸化チタンといったチタン化合物が形成されていると、積層構造体に強い屈曲耐性が得られないことを知見するのに至った。 Here, in order to confirm the bending resistance of the laminated structure, a test substrate having a predetermined shape was used, and a first titanium layer, an aluminum layer, and a second titanium layer were sequentially formed on the surface of the test substrate under predetermined sputtering conditions. After lamination, when a tensile test was performed on the laminated structure peeled from the test base material, the laminated structure elongated by more than double just by applying a tensile load necessary to give an elongation amount of 5%. It has been found. Further, when the state of the surface of the laminated structure (that is, the surface of the titanium layer) after the tensile test was observed, it was found that many cracks extending in the thickness direction were generated in the titanium layer. Therefore, the present inventors have made intensive studies and found that the crystal structure has a crystal structure in which relatively small crystal grains are aligned in the film thickness direction and the crystal grain boundaries are connected so as to extend in the film thickness direction. It was discovered that when hard and brittle titanium compounds such as titanium nitride and titanium oxide were formed at the grain boundaries due to impurities such as nitrogen molecules and oxygen molecules taken into the layers, the laminated structure could not obtain strong bending resistance. I came to do it.

特開２０１５－１７７１０５号公報JP 2015-177105 A

本発明は、上記知見に基づきなされたものであり、強い屈曲耐性を有する積層構造体及び積層構造体の製造方法を提供することをその課題とするものである。 The present invention has been made based on the above findings, and an object of the present invention is to provide a laminated structure having strong bending resistance and a method for producing the laminated structure.

上記課題を解決するために、第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した本発明の積層構造体は、第１及び第２の各チタン層が、Ｘ線回折測定によるミラー指数における（００２）面及び（１００）面に回析ピークを持つ結晶構造を有し、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であることを特徴とする。この場合、前記アルミニウム層は、Ｘ線回折測定によるミラー指数における（１１１）面に回析ピークを持つ結晶構造を有することが好ましい。 In order to solve the above problems, a laminated structure of the present invention in which a first titanium layer, an aluminum layer, and a second titanium layer are laminated in this order is provided. It has a crystal structure with diffraction peaks on the (002) plane and the (100) plane in the Miller index measured by diffraction measurement, the half width of the diffraction peak on the (002) plane is 1.0 deg or less, and the (100) plane The diffraction peak has a half width of 0.6 deg or less. In this case, the aluminum layer preferably has a crystal structure having a diffraction peak in the (111) plane in the Miller index measured by X-ray diffraction.

また、上記課題を解決するために、第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体を製造する本発明の積層構造体の製造方法は、スパッタリング法により、基材上に第１のチタン層を成膜する第１工程と、第１のチタン層の上にアルミニウム層を成膜する第２工程と、アルミニウム層の上に第２のチタン層を成膜する第３工程とを含み、第１及び第３の各工程は、窒素ガスの分圧が３．０×１０－４Ｐａ以下、酸素ガスの分圧が９．０×１０－５Ｐａ以下、水蒸気ガスの分圧が８．０×１０－４Ｐａ以下、水素ガスの分圧が５．０×１０－５Ｐａ以下に夫々達するまで、チタン製のターゲットと基材とが配置された真空チャンバ内を真空排気する真空排気工程と、真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、チタン製のターゲットに所定電力を投入して３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内の成膜速度で第１及び第２の各チタン層を成膜する成膜工程と、を更に含むことを特徴とする。この場合、前記第２工程は、アルミニウム製のターゲットと基材とが配置された真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、アルミニウム製のターゲットに所定電力を投入して７ｎｍ／ｓｅｃ～１０ｎｍ／ｓｅｃの範囲内の成膜速度でアルミニウム層を成膜する成膜工程を更に含むことが好ましい。Further, in order to solve the above problems, a method for manufacturing a laminated structure according to the present invention for producing a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated includes a sputtering method. A first step of forming a first titanium layer on the base material, a second step of forming an aluminum layer on the first titanium layer, and a second titanium layer on the aluminum layer by In each of the first and third steps, the partial pressure of nitrogen gas is 3.0 × 10 -4 Pa or less and the partial pressure of oxygen gas is 9.0 × 10 -5 Pa. Thereafter, the titanium target and the substrate were placed until the partial pressure of water vapor gas reached 8.0×10 −4 Pa or less and the partial pressure of hydrogen gas reached 5.0×10 −5 Pa or less. An evacuation step of evacuating the inside of the vacuum chamber, introducing a rare gas so that the total pressure in the vacuum chamber is maintained within the range of 0.2 Pa to 0.5 Pa, and applying a predetermined power to the titanium target. and a film forming step of forming the first and second titanium layers at a film forming rate within the range of 3 nm/sec to 5 nm/sec. In this case, the second step includes introducing a rare gas such that the total pressure in the vacuum chamber in which the aluminum target and the base material are arranged is maintained within a range of 0.2 Pa to 0.5 Pa, It is preferable to further include a film forming step of applying a predetermined electric power to a target made of aluminum to form an aluminum layer at a film forming rate within the range of 7 nm/sec to 10 nm/sec.

以上によれば、真空雰囲気中にて真空チャンバ内で第１のチタン層、アルミニウム層及び第２のチタン層をスパッタリング法により成膜するのに先立って、真空チャンバ内を不純物ガス（例えば窒素ガス、酸素ガス、水蒸気ガス、水素ガス）の分圧が所定値以下に達するまで真空排気することで、第１及び第２の各チタン層の結晶粒界に、窒化チタンや酸化チタンといったチタン化合物が形成されることが可及的に抑制される。そして、第１及び第２の各チタン層の成膜時には、その成膜速度を３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内にすれば、第１及び第２の各チタン層を、粒径の大きい結晶粒がその膜厚方向に不揃いに重なって結晶粒界が膜厚方向に繋がらない結晶構造を有するものにできる。 According to the above, prior to depositing the first titanium layer, the aluminum layer, and the second titanium layer in the vacuum chamber in a vacuum atmosphere, an impurity gas (for example, nitrogen gas) is introduced into the vacuum chamber. , oxygen gas, water vapor gas, and hydrogen gas) is evacuated until the partial pressure reaches a predetermined value or less, whereby titanium compounds such as titanium nitride and titanium oxide are formed at the grain boundaries of the first and second titanium layers. formation is suppressed as much as possible. Then, when the first and second titanium layers are formed, if the film formation rate is set within the range of 3 nm/sec to 5 nm/sec, the first and second titanium layers can be formed with a large grain size. It can have a crystal structure in which the crystal grains overlap irregularly in the film thickness direction and the crystal grain boundaries do not connect in the film thickness direction.

上記のようにして成膜したチタン層をＸ線回折したところ、（００２）面での回折ピークと、（１００）面での回折ピークとが確認され、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２０以上であった。このとき、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であり、これから、上記回析パターンを有していれば、第１及び第２の各チタン層の結晶粒界に、チタン化合物が形成されることが抑制され、粒径の大きい結晶粒がその膜厚方向に不揃いに重なって結晶粒界が繋がらない結晶構造を有するものとなる。そして、上記同様の積層構造体に対する引張試験にて５％または１０％の伸び量を与えるのに必要な引張荷重を加えても、積層構造体の伸び量は１０％以内に抑制され、しかも、引張試験後の積層構造体の表面観察でも、クラックが発生していないことが確認された。その結果、本発明の積層構造体は、従来例のものと比較して強い屈曲耐性を有する。 When the titanium layer formed as described above was subjected to X-ray diffraction, a diffraction peak on the (002) plane and a diffraction peak on the (100) plane were confirmed. The intensity ratio of diffraction peaks on the 100) plane was 0.20 or more. At this time, the half-value width of the diffraction peak on the (002) plane is 1.0 deg or less, and the half-value width of the diffraction peak on the (100) plane is 0.6 deg or less. This suppresses the formation of a titanium compound at the crystal grain boundaries of the first and second titanium layers, and crystal grains having a large grain size overlap unevenly in the film thickness direction, preventing the crystal grain boundaries from connecting. It has a crystal structure. Further, even when a tensile load necessary to give an elongation of 5% or 10% is applied to the laminated structure similar to the above, the elongation of the laminated structure is suppressed to within 10%, and Observation of the surface of the laminated structure after the tensile test also confirmed that no cracks occurred. As a result, the laminate structure of the present invention has a higher resistance to bending than that of the conventional example.

本発明の実施形態の積層構造体を模式的に説明する図。BRIEF DESCRIPTION OF THE DRAWINGS The figure which illustrates typically the laminated structure of embodiment of this invention. 本発明の実施形態の積層構造体の製造方法を実施するスパッタリング装置を模式的に説明する図。BRIEF DESCRIPTION OF THE DRAWINGS The figure which illustrates typically the sputtering apparatus which enforces the manufacturing method of the laminated structure of embodiment of this invention. 図２に示す成膜チャンバＰｃ１を模式的に説明する図。FIG. 3 is a diagram schematically explaining a film forming chamber Pc1 shown in FIG. 2; 本発明の効果を確認する実験結果を示すグラフ。The graph which shows the experimental result which confirms the effect of this invention. （ａ）～（ｃ）は、比較実験１～比較実験３で成膜したチタン層の結晶構造を模式的に説明する図。4(a) to 4(c) are diagrams for schematically explaining the crystal structures of titanium layers deposited in Comparative Experiments 1 to 3. FIG.

以下、図面を参照して、本発明の積層構造体及び積層構造体の製造方法の実施形態について説明する。 Hereinafter, embodiments of the laminated structure and the method for manufacturing the laminated structure of the present invention will be described with reference to the drawings.

図１に示すように、本実施形態の積層構造体ＬＳは、基材Ｓｗを例えばガラス基板Ｓｇの表面にポリイミドフィルムＰｆを貼付したものとし（ガラス基板ＳｇとポリイミドフィルムＰｆとの界面で剥離可能）、基材Ｓｗ表面に、真空雰囲気中でスパッタリング法により一貫して順次成膜（積層）される第１のチタン層Ｌ１と、アルミニウム層Ｌ２と、第２のチタン層Ｌ３とを備える。 As shown in FIG. 1, in the laminated structure LS of the present embodiment, the substrate Sw is made by attaching a polyimide film Pf to the surface of a glass substrate Sg (separable at the interface between the glass substrate Sg and the polyimide film Pf). ), a first titanium layer L1, an aluminum layer L2, and a second titanium layer L3 are formed (stacked) in sequence on the surface of the substrate Sw consistently by sputtering in a vacuum atmosphere.

図２に示すように、上記積層構造体ＬＳの成膜に利用できるスパッタリング装置Ｓｍは、所謂クラスターツール式のものであり、搬送ロボットＲを有する中央の搬送チャンバＴｃを備え、搬送チャンバＴｃの周囲に、ゲートバルブＧｖを介して、ロードロックチャンバＬｃと、第１のチタン層Ｌ１を成膜する真空チャンバ（以下「成膜チャンバ」という）Ｐｃ１と、アルミ二ウム層Ｌ２を成膜する成膜チャンバＰｃ２と、第２のチタン層Ｌ３を成膜する成膜チャンバＰｃ３とが夫々連結されている。ここで、成膜チャンバＰｃ１，Ｐｃ２，Ｐｃ３内には、使用されるターゲットを除き、同一の構造部品が設けられるため、図３を参照して、成膜チャンバＰｃ１を例に説明すると、成膜チャンバＰｃ１には、ターボ分子ポンプやロータリーポンプなどからなる真空ポンプユニットＰｕに通じる排気管１１が接続され、成膜チャンバＰｃ１を所定の真空度（例えば１×１０－６Ｐａ）まで真空排気することができる。真空チャンバＰｃ１の側壁には、マスフローコントローラ１２が介設されたガス管１３が接続され、流量制御された希ガス（例えばアルゴンガス）を成膜チャンバＰｃ１内に導入することができる。成膜チャンバＰｃ１の上部には、チタン製のターゲット２（成膜チャンバＰｃ２では、アルミニウム製のターゲット）が基材Ｓｗを臨む姿勢で配置され、その上方に公知の磁石ユニット３が配置されている。As shown in FIG. 2, the sputtering apparatus Sm that can be used for film formation of the laminated structure LS is of a so-called cluster tool type, and includes a central transfer chamber Tc having a transfer robot R. Then, through the gate valve Gv, a load lock chamber Lc, a vacuum chamber (hereinafter referred to as "deposition chamber") Pc1 for depositing a first titanium layer L1, and a deposition for depositing an aluminum layer L2. The chamber Pc2 and the deposition chamber Pc3 for depositing the second titanium layer L3 are connected to each other. Here, since the same structural parts are provided in the deposition chambers Pc1, Pc2, and Pc3 except for the targets used, the deposition chamber Pc1 will be described as an example with reference to FIG. The chamber Pc1 is connected to an exhaust pipe 11 leading to a vacuum pump unit Pu composed of a turbomolecular pump, a rotary pump, or the like, and the film formation chamber Pc1 is evacuated to a predetermined degree of vacuum (eg, 1×10 −6 Pa). can be done. A gas pipe 13 in which a mass flow controller 12 is interposed is connected to the side wall of the vacuum chamber Pc1, and a rare gas (for example, argon gas) whose flow rate is controlled can be introduced into the deposition chamber Pc1. A target 2 made of titanium (a target made of aluminum in the film formation chamber Pc2) is arranged in the upper part of the film formation chamber Pc1 so as to face the substrate Sw, and a known magnet unit 3 is arranged above it. .

チタン製のターゲット２としては、純度が９９．９％以上のものが、また、アルミニウム製のターゲットとしては、純度が９９．９９％以上のものが利用される。ターゲット２には、スパッタ電源Ｐｓからの出力が接続され、負の電位を持つ直流電力をターゲット２に投入できる。成膜チャンバＰｃ１の下部には、ターゲット２に対向させて、ステージ４が配置され、基材Ｓｗを設置することができる。成膜チャンバＰｃ１には、その内部の全圧と不純物ガス（例えば、窒素ガス、酸素ガス、水蒸気ガス、水素ガス）の分圧とを測定する測定器５が設けられている。このような測定器５としては、電離真空計や質量分析計などの公知のものが利用できるため、これ以上の説明は省略する。以下に、スパッタリング装置Ｓｍによる積層構造体ＬＳの製造方法を具体的に説明する。 The titanium target 2 has a purity of 99.9% or higher, and the aluminum target has a purity of 99.99% or higher. An output from a sputtering power source Ps is connected to the target 2 , and DC power having a negative potential can be supplied to the target 2 . A stage 4 is arranged in the lower part of the film forming chamber Pc1 so as to face the target 2, and the substrate Sw can be placed thereon. The deposition chamber Pc1 is provided with a measuring instrument 5 for measuring the total internal pressure and the partial pressures of impurity gases (for example, nitrogen gas, oxygen gas, water vapor gas, and hydrogen gas). Known devices such as an ionization vacuum gauge and a mass spectrometer can be used as such a measuring device 5, so further explanation is omitted. A method for manufacturing the laminated structure LS by the sputtering apparatus Sm will be specifically described below.

大気雰囲気のロードロックチャンバＬｃに基材Ｓｗを投入し、ロードロックチャンバＬｃを真空排気した後、搬送ロボットＲにより基材Ｓｗを成膜チャンバＰｃ１に搬送する。なお、ロードロックチャンバＬｃへの基材Ｓｗの投入に先立ち、搬送チャンバＴｃ及び各成膜チャンバＰｃ１，Ｐｃ２，Ｐｃ３は予め所定圧力（１×１０－３Ｐａ）まで真空排気され、待機状態となっている。基材Ｓｗが成膜チャンバＰｃ１のステージ４上に設置されると、真空排気を続行し、質量分析計５により測定される窒素ガスの分圧が３．０×１０－４Ｐａ以下、酸素ガスの分圧が９．０×１０－５Ｐａ以下、水蒸気ガスの分圧が８．０×１０－４Ｐａ以下、水素ガスの分圧が５．０×１０－５Ｐａ以下に達するまで成膜チャンバＰｃ１内を真空排気する（第１工程の真空排気工程）。The substrate Sw is put into the load-lock chamber Lc in the atmosphere, and the load-lock chamber Lc is evacuated. Prior to loading the substrate Sw into the load lock chamber Lc, the transfer chamber Tc and each of the film forming chambers Pc1, Pc2, and Pc3 are previously evacuated to a predetermined pressure (1×10 −3 Pa) and are in a standby state. ing. When the substrate Sw is placed on the stage 4 of the deposition chamber Pc1, the evacuation is continued, and the partial pressure of the nitrogen gas measured by the mass spectrometer 5 is 3.0 × 10 -4 Pa or less, and the oxygen gas film formation until the partial pressure of 9.0 × 10 -5 Pa or less, the partial pressure of water vapor gas reaches 8.0 × 10 -4 Pa or less, and the partial pressure of hydrogen gas reaches 5.0 × 10 -5 Pa or less. The inside of the chamber Pc1 is evacuated (evacuation step of the first step).

次に、各ガスの分圧が夫々所定値以下になると、真空排気されている成膜チャンバＰｃ１内に、その全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるようにアルゴンガスを導入し、スパッタ電源Ｐｓからターゲット２に負の電位を持つ直流電力を２０ｋＷ～３０ｋＷ投入する。すると、成膜チャンバＰｃ１内にプラズマが形成され。プラズマ中で電離したアルゴンガスのイオンによりターゲット２がスパッタリングされる。これにより、ターゲット２から飛散したスパッタ粒子が基材Ｓｗの成膜面（ポリイミドフィルムＰｆ）に付着、堆積して基材Ｓｗ上に第１のチタン層Ｌ１が３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの成膜速度で成膜される（第１工程での成膜工程）。このとき、スパッタ時間を適宜設定して、第１のチタン層Ｌ１は、例えば１０ｎｍ～５０ｎｍの膜厚とされる。 Next, when the partial pressure of each gas becomes equal to or less than a predetermined value, argon gas is introduced into the evacuated deposition chamber Pc1 so that the total pressure is maintained within the range of 0.2 Pa to 0.5 Pa. is introduced, and 20 kW to 30 kW of DC power having a negative potential is applied to the target 2 from the sputtering power source Ps. Then, plasma is formed in the deposition chamber Pc1. The target 2 is sputtered by argon gas ions ionized in the plasma. As a result, the sputtered particles scattered from the target 2 adhere to and accumulate on the film formation surface (polyimide film Pf) of the base material Sw, and the first titanium layer L1 is formed on the base material Sw at a rate of 3 nm/sec to 5 nm/sec. The film is formed at the film speed (film formation step in the first step). At this time, the sputtering time is appropriately set so that the thickness of the first titanium layer L1 is, for example, 10 nm to 50 nm.

第１工程の終了後、基材Ｓｗを成膜チャンバＰｃ２に搬送し、第１工程と同様に真空排気工程を行う。各ガスの分圧が夫々所定値以下になると、真空排気されている成膜チャンバＰｃ２内に、その全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるようにアルゴンガスを導入し、スパッタ電源Ｐｓからアルミニウム製のターゲット２に負の電位を持つ直流電力を３０ｋＷ～４０ｋＷ投入する。すると、成膜チャンバＰｃ２内にプラズマが形成され、ターゲット２から飛散したスパッタ粒子が第１のチタン層Ｌ１の表面に付着、堆積して第１のチタン層Ｌ１上にアルミニウム層Ｌ２が７ｎｍ／ｓｅｃ～１０ｎｍ／ｓｅｃの成膜速度で成膜される（第２工程での成膜工程）。このとき、スパッタ時間を適宜制御して、アルミニウム層Ｌ２は、例えば２００ｎｍ～８００ｎｍの膜厚とされる。 After completion of the first step, the substrate Sw is transported to the film forming chamber Pc2, and an evacuation step is performed in the same manner as in the first step. When the partial pressure of each gas becomes equal to or less than a predetermined value, argon gas is introduced into the evacuated deposition chamber Pc2 so that the total pressure is maintained within the range of 0.2 Pa to 0.5 Pa. , DC power of 30 kW to 40 kW having a negative potential is applied to the target 2 made of aluminum from the sputtering power source Ps. Then, plasma is formed in the deposition chamber Pc2, and the sputtered particles scattered from the target 2 adhere and deposit on the surface of the first titanium layer L1, forming an aluminum layer L2 of 7 nm/sec on the first titanium layer L1. A film is formed at a film formation rate of ~10 nm/sec (film formation step in the second step). At this time, the sputtering time is appropriately controlled so that the thickness of the aluminum layer L2 is, for example, 200 nm to 800 nm.

第２工程の終了後、基材Ｓｗを成膜チャンバＰｃ３に搬送し、第１工程と同様に真空排気工程を行う。各ガスの分圧が夫々所定値以下になると、第１工程と同じスパッタ条件で、アルミ二ウム層Ｌ２の上に第２のチタン層Ｌ３が３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの成膜速度で成膜される（第３工程での成膜工程）。このとき、スパッタ時間を適宜制御して、第２のチタン層Ｌ３の膜厚は、第１のチタン層Ｌ１と同様の膜厚（例えば１０～５０ｎｍ）とされる。 After completion of the second step, the substrate Sw is transported to the film forming chamber Pc3, and an evacuation step is performed in the same manner as in the first step. When the partial pressure of each gas becomes equal to or less than a predetermined value, the second titanium layer L3 is formed on the aluminum layer L2 at a film formation rate of 3 nm/sec to 5 nm/sec under the same sputtering conditions as in the first step. A film is formed (film formation step in the third step). At this time, the film thickness of the second titanium layer L3 is set to the same film thickness (for example, 10 to 50 nm) as the first titanium layer L1 by appropriately controlling the sputtering time.

以上説明したように積層構造体ＬＳを製造すると、各チタン層Ｌ１，Ｌ３の内部に不純物が取り込まれることが可及的に抑制され、結晶粒界Ｃｆに窒化チタンや酸化チタンといったチタン化合物が形成されることが抑制される（図１中、一点鎖線で囲う部分参照）。加えて、各チタン層Ｌ１，Ｌ３を３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内の成膜速度で成膜することで、結晶粒Ｃｇの粒径が従来例のものと比較して大きくなり、しかも、これらの結晶粒Ｃｇがその膜厚方向に不揃いに重なり、その結果として、結晶粒界Ｃｆが膜厚方向に繋がらない結晶構造を有するものにできる（図１参照）。なお、このようなチタン層Ｌ１，Ｌ３のＸ線回折を測定したところ、（００２）面での回折ピークと、（１００）面での回折ピークとが確認され、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２０以上であった。このとき、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下であり、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であった。 When the laminated structure LS is manufactured as described above, the introduction of impurities into the titanium layers L1 and L3 is suppressed as much as possible, and titanium compounds such as titanium nitride and titanium oxide are formed at the grain boundaries Cf. (See the part enclosed by the dashed line in FIG. 1). In addition, by forming the titanium layers L1 and L3 at a film formation rate within the range of 3 nm/sec to 5 nm/sec, the grain size of the crystal grains Cg becomes larger than that of the conventional example, and moreover, , these crystal grains Cg overlap irregularly in the film thickness direction, and as a result, a crystal structure in which the crystal grain boundaries Cf are not connected in the film thickness direction can be obtained (see FIG. 1). When the X-ray diffraction of the titanium layers L1 and L3 was measured, a diffraction peak on the (002) plane and a diffraction peak on the (100) plane were confirmed, and a diffraction peak on the (002) plane was confirmed. The intensity ratio of the diffraction peak on the (100) plane to the peak was 0.20 or more. At this time, the half width of the diffraction peak on the (002) plane was 1.0 deg or less, and the half width of the diffraction peak on the (100) plane was 0.6 deg or less.

次に、上記効果を確認するために、上記スパッタリング装置Ｓｍを用い、以下の実験を行った。 Next, in order to confirm the above effect, the following experiment was conducted using the sputtering apparatus Sm.

発明実験では、基材Ｓｗをガラス基板Ｓｇ上面にポリイミドフィルムＰｆが貼付されたものとし、基材Ｓｗを成膜チャンバＰｃ１のステージ４上に設置した後、質量分析計５により測定される窒素ガスの分圧が１．０×１０－４Ｐａ、酸素ガスの分圧が８．０×１０－５Ｐａ、水蒸気ガスの分圧が５．０×１０－４Ｐａ、水素ガスの分圧が５．０×１０－５Ｐａに達するまで真空排気した（第１工程の真空排気工程）。このとき、真空チャンバＰｃ１内の全圧は７．３×１０－４Ｐａであった。真空排気工程の後、真空チャンバＰｃ１内の全圧が０．３Ｐａに維持されるようにアルゴンガスを流量１２０ｓｃｃｍで真空チャンバＰｃ１内に導入し、これと併せてターゲット２に直流電力を２０～３０ｋＷ投入してチタン製ターゲット２をスパッタリングして、３ｎｍ／ｓｅｃの成膜速度で基材Ｓｗ表面に第１のチタン層Ｌ１を５０ｎｍの膜厚で成膜した（第１工程の成膜工程）。成膜した第１のチタン層Ｌ１のＸ線回折を測定した結果を図４に実線で示す。表１も参照して、回折角（２θ）３８～３９°付近に（００２）面での回折ピークが、回折角３５～３６°付近に（１００）面での回折ピークが夫々確認され、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２５、（００２）面での回折ピークの半値幅は０．５ｄｅｇ、（１００）面での回折ピークの半値幅は０．６ｄｅｇであった。第１工程の後、基材Ｓｗを成膜チャンバＰｃ２に搬送し、第１工程と同様に真空排気工程を行った後、成膜チャンバＰｃ２の全圧が０．３Ｐａに維持されるようにアルゴンガスを流量１２０ｓｃｃｍで成膜チャンバＰｃ２内に導入し、これと併せてアルミニウム製のターゲット２に直流電力を３５～４０ｋＷ投入してターゲット２をスパッタリングして、７ｎｍ／ｓｅｃの成膜速度で第１のチタン層Ｌ１上にアルミニウム層Ｌ２を５００ｎｍの膜厚で成膜した。成膜したアルミニウム層Ｌ２のＸ線回折を測定したところ、回折角（２θ）３８～３９°付近に（１１１）面での回折ピークが確認された。第２工程の後、基材Ｓｗを成膜チャンバＰｃ３に搬送し、第１工程と同様に真空排気工程を行い、その後、第１工程と同じ成膜条件で、３ｎｍ／ｓｅｃの成膜速度でアルミニウム層Ｌ２上に第２のチタン層Ｌ３を５０ｎｍの膜厚で成膜し、これにより、積層構造体ＬＳを得た。成膜した第２のチタン層Ｌ３のＸ線回折を測定したところ、第１のチタン層Ｌ１と同様の回折パターン（図４参照）が得られた。そして、このようにして得られた積層構造体ＬＳの屈曲耐性を確認するため、公知の形状（幅５ｍｍ、長さ２０ｍｍ、厚さ０．０２ｍｍ）を有する試験基材（ポリイミドフィルムＰｆ）をガラス基板Ｓｇ上に形成し、試験基材表面に上述したスパッタ条件で第１のチタン層Ｌ１、アルミニウム層Ｌ２、第２のチタン層Ｌ３を順次積層した後、ガラス基板ＳｇとポリイミドフィルムＰｆとの界面で剥離して得た積層構造体ＬＳに対して、引張試験機（ＯＲＩＥＮＴＥＣ製の「ＳＴＡ－１１５０」）を用いて引張試験（引張速度は０．５ｍｍ／ｍｉｎ）を実施したところ、５％、１０％の伸び量を与えるのに必要な引張荷重を加えても、積層構造体の伸び量は１０％以内（５％、８％）に抑えられることが確認された。また、５％、１０％の伸び量を与える引張荷重を加えたときの抵抗Ｒを抵抗測定器（ＡＤＶＡＮＴＥＳＴ製の「ＡＤ７４６１Ａ」）を用いて夫々測定し、引張荷重を加えないときの抵抗Ｒ０に対する抵抗上昇率（＝（Ｒ－Ｒ０）／Ｒ０）を求めたところ、１０％以内（５％、８％）に抑えることができることが確認された。また、引張試験後の積層構造体ＬＳの表面状態を市販のMicroscopeを用いて観察したところ、クラックが発生していないことが確認された。これらの結果より、本発明実験で得られた積層構造体ＬＳは、従来例のものと比較して強い屈曲耐性を有することが判った。In the invention experiment, the substrate Sw is assumed to be a glass substrate Sg with a polyimide film Pf attached on its upper surface, and after the substrate Sw is placed on the stage 4 of the deposition chamber Pc1, the nitrogen gas measured by the mass spectrometer 5 is 1.0×10 −4 Pa, the partial pressure of oxygen gas is 8.0×10 −5 Pa, the partial pressure of water vapor gas is 5.0×10 −4 Pa, and the partial pressure of hydrogen gas is 5 Evacuation was performed until the pressure reached 0×10 −5 Pa (first step, evacuation step). At this time, the total pressure in the vacuum chamber Pc1 was 7.3×10 −4 Pa. After the evacuation process, argon gas is introduced into the vacuum chamber Pc1 at a flow rate of 120 sccm so that the total pressure in the vacuum chamber Pc1 is maintained at 0.3 Pa, and at the same time, a DC power of 20 to 30 kW is applied to the target 2. Then, the titanium target 2 was sputtered to form a first titanium layer L1 with a film thickness of 50 nm on the surface of the substrate Sw at a film formation rate of 3 nm/sec (first film formation step). The solid line in FIG. 4 shows the result of measuring the X-ray diffraction of the deposited first titanium layer L1. Also referring to Table 1, a diffraction peak on the (002) plane is confirmed near the diffraction angle (2θ) of 38 to 39°, and a diffraction peak on the (100) plane is confirmed near the diffraction angle of 35 to 36°. The intensity ratio of the diffraction peak on the (100) plane to the diffraction peak on the (002) plane is 0.25, the half width of the diffraction peak on the (002) plane is 0.5 deg, and the half width of the diffraction peak on the (100) plane is 0.25. The price range was 0.6deg. After the first step, the substrate Sw is transported to the film forming chamber Pc2, and after performing the evacuation step in the same manner as in the first step, argon is supplied so that the total pressure in the film forming chamber Pc2 is maintained at 0.3 Pa. A gas is introduced into the film formation chamber Pc2 at a flow rate of 120 sccm, and at the same time, DC power of 35 to 40 kW is applied to the target 2 made of aluminum to sputter the target 2, and the first film is formed at a film formation rate of 7 nm/sec. An aluminum layer L2 having a film thickness of 500 nm was formed on the titanium layer L1. When the X-ray diffraction of the deposited aluminum layer L2 was measured, a diffraction peak on the (111) plane was confirmed near the diffraction angle (2θ) of 38 to 39°. After the second step, the substrate Sw is transported to the film forming chamber Pc3, and the evacuation step is performed in the same manner as in the first step. A second titanium layer L3 having a thickness of 50 nm was formed on the aluminum layer L2, thereby obtaining a laminated structure LS. When the X-ray diffraction of the deposited second titanium layer L3 was measured, a diffraction pattern (see FIG. 4) similar to that of the first titanium layer L1 was obtained. Then, in order to confirm the bending resistance of the laminated structure LS thus obtained, a test substrate (polyimide film Pf) having a known shape (width 5 mm, length 20 mm, thickness 0.02 mm) was placed on a glass. After forming on the substrate Sg and successively laminating the first titanium layer L1, the aluminum layer L2, and the second titanium layer L3 on the surface of the test substrate under the sputtering conditions described above, the interface between the glass substrate Sg and the polyimide film Pf A tensile test (tensile speed: 0.5 mm/min) was performed using a tensile tester ("STA-1150" manufactured by ORIENTEC) on the laminated structure LS obtained by peeling in . It was confirmed that the elongation of the laminated structure can be suppressed to within 10% (5%, 8%) even if a tensile load required to give an elongation of 10% is applied. In addition, the resistance R when a tensile load that gives an elongation of 5% and 10% is applied is measured using a resistance measuring instrument ("AD7461A" manufactured by ADVANTEST), and the resistance R0 when no tensile load is applied. When the resistance increase rate (=(R−R0)/R0) was determined, it was confirmed that it could be suppressed within 10% (5%, 8%). Moreover, when the surface state of the laminated structure LS after the tensile test was observed using a commercially available microscope, it was confirmed that no cracks occurred. From these results, it was found that the laminated structure LS obtained in the experiment of the present invention has a higher bending resistance than that of the conventional example.

（表１）

Figure 0007196372000001
(Table 1)
Figure 0007196372000001

次に、上記発明実験に対する比較のため、以下の比較実験を行った。比較実験１では、第１及び第３の各工程の成膜工程での成膜チャンバＰｃ１内の全圧を０．６Ｐａに維持して成膜速度を２ｎｍ／ｓｅｃとした点を除き、上記発明実験と同様の方法で積層構造体ＬＳを得た。上記発明実験と同様の条件で引張試験を実施したところ、積層構造体ＬＳの伸び量が倍以上となることが確認された。また、上記発明実験と同様に抵抗上昇率を求めたところ、３０％、４００％であった。また、上記発明実験と同様に引張試験後の積層構造体ＬＳの表面状態を観察したところ、クラックが発生して白色化していることが確認された。これらの結果より、本比較実験１で得られた積層構造体ＬＳは弱い屈曲耐性を有することが判った。尚、本比較実験１で成膜された第１のチタン層Ｌ１のＸ線回折を測定したところ、図４に破線で示すように、（１００）面での回折ピークは確認されず、（００２）面での回折ピークのみが確認され、その（００２）面での回折ピークの半値幅は０．９ｄｅｇであった。このような回折パターンを有する場合、図５（ａ）に示すように、小さな結晶粒Ｃｇが膜厚方向に整列して結晶粒界Ｃｆがその膜厚方向にのびるように繋がった結晶構造を有すると推察される。 Next, the following comparative experiment was conducted for comparison with the above invention experiment. In Comparative Experiment 1, the above invention was used except that the total pressure in the film formation chamber Pc1 was maintained at 0.6 Pa and the film formation rate was 2 nm/sec in the film formation steps of the first and third steps. A laminated structure LS was obtained in the same manner as in the experiment. When a tensile test was performed under the same conditions as the above invention experiment, it was confirmed that the elongation amount of the laminated structure LS was more than doubled. Further, when the rate of increase in resistance was obtained in the same manner as in the experiment of the invention, it was 30% and 400%. Further, when the surface state of the laminated structure LS after the tensile test was observed in the same manner as in the above invention experiment, it was confirmed that cracks were generated and whitened. From these results, it was found that the laminated structure LS obtained in Comparative Experiment 1 had weak bending resistance. When the X-ray diffraction of the first titanium layer L1 formed in Comparative Experiment 1 was measured, no diffraction peak was observed on the (100) plane, as indicated by the dashed line in FIG. ) plane was confirmed, and the half width of the diffraction peak on the (002) plane was 0.9 deg. In the case of having such a diffraction pattern, as shown in FIG. 5A, it has a crystal structure in which small crystal grains Cg are aligned in the film thickness direction and crystal grain boundaries Cf are connected so as to extend in the film thickness direction. Then it is inferred.

また、比較実験２では、第１及び第３の各工程にて真空排気工程を行わない点（成膜工程のみを行う点）を除き、上記発明実験と同様の方法で積層構造体ＬＳを得た。即ち、真空チャンバＰｃ１内の全圧が所定真空度（２．８×１０－３Ｐａ）に到達すると、不純物ガスの分圧に関わらず、真空チャンバＰｃ１内に希ガスを導入した。このときの不純物ガスの分圧を測定したところ、窒素ガスの分圧が５．０×１０－４Ｐａ、酸素ガスの分圧が２．０×１０－４Ｐａ、水蒸気ガスの分圧が２．０×１０－３Ｐａ、水素ガスの分圧が５．０×１０－５Ｐａであり、水素ガス以外は基準値を下回っていた。上記発明実験と同様の条件で引張試験を実施したところ、積層構造体ＬＳの伸び量は倍以上となることが確認された。また、上記発明実験と同様に抵抗上昇率を求めたところ、比較実験１よりも更に悪い１２０％、６５０％であった。また、上記発明実験と同様に引張試験後の積層構造体ＬＳの表面状態を観察したところ、クラックが発生して白色化していることが確認された。これらの結果より、本比較実験２で得られた積層構造体ＬＳは弱い屈曲耐性を有することが判った。尚、成膜した第１のチタン層Ｌ１のＸ線回折を測定したところ、（００２）面での回折ピークだけでなく（１００）面での回折ピークが観察されたものの、（００２）面での回折ピークに対する（１００）面での回折ピークの強度比は０．２０よりも小さい０．１１であった。また、（１００）面での回折ピークの半値幅は０．６ｄｅｇよりも大きい０．７ｄｅｇであった。このような回折パターンを有する場合、図５（ｂ）に示すように、結晶粒界Ｃｆに窒化チタンや酸化チタンといったチタン化合物Ｉｍが形成されていると推察される。In Comparative Experiment 2, the laminated structure LS was obtained in the same manner as in the Experiment of the Invention except that the first and third steps did not perform the evacuation step (only the film formation step was performed). rice field. That is, when the total pressure in the vacuum chamber Pc1 reached a predetermined degree of vacuum (2.8×10 −3 Pa), the rare gas was introduced into the vacuum chamber Pc1 regardless of the partial pressure of the impurity gas. When the partial pressure of the impurity gas at this time was measured, the partial pressure of the nitrogen gas was 5.0×10 −4 Pa, the partial pressure of the oxygen gas was 2.0×10 −4 Pa, and the partial pressure of the water vapor gas was 2. 0×10 −3 Pa, and the partial pressure of hydrogen gas was 5.0×10 −5 Pa, which were below the standard values except for hydrogen gas. When a tensile test was performed under the same conditions as the above invention experiment, it was confirmed that the elongation amount of the laminated structure LS was more than doubled. Further, when the rate of increase in resistance was obtained in the same manner as in the experiment of the invention, the results were 120% and 650%, which are even worse than those in the comparative experiment 1. Further, when the surface state of the laminated structure LS after the tensile test was observed in the same manner as in the above invention experiment, it was confirmed that cracks were generated and whitened. From these results, it was found that the laminated structure LS obtained in Comparative Experiment 2 had weak bending resistance. When X-ray diffraction of the formed first titanium layer L1 was measured, a diffraction peak was observed not only for the (002) plane but also for the (100) plane. The intensity ratio of the diffraction peak in the (100) plane to the diffraction peak in the (100) plane was 0.11, which is less than 0.20. Also, the half width of the diffraction peak on the (100) plane was 0.7 deg, which is larger than 0.6 deg. In the case of having such a diffraction pattern, as shown in FIG. 5B, it is presumed that a titanium compound Im such as titanium nitride or titanium oxide is formed at the grain boundary Cf.

また、比較実験３では、第１及び第３の各工程の成膜時の成膜チャンバＰｃ１，Ｐｃ３内の全圧を０．６Ｐａに維持して成膜速度を２ｎｍ／ｓｅｃとし、第１及び第３の各工程にて真空排気工程を行わない点（成膜工程のみを行う点）を除き、上記発明実験と同様の方法で積層構造体ＬＳを得た。上記発明実験と同様の条件で引張試験を実施したところ、積層構造体ＬＳの伸び量が倍以上となることが確認された。また、上記発明実験と同様に抵抗上昇率を求めたところ、比較実験２よりも更に悪い３００％、９００％であった。また、上記発明実験と同様に引張試験後の積層構造体ＬＳの表面状態を観察したところ、クラックが発生して白色化していることが確認された。これらの結果より、本比較実験３で得られた積層構造体ＬＳは上記比較実験１，２よりも弱い屈曲耐性を有することが判った。尚、本比較実験３で成膜された第１のチタン層Ｌ１のＸ線回折を測定したところ、（１００）面での回折ピークは確認されず、（００２）面での回折ピークのみが確認され、その（００２）面での回折ピークの半値幅は０．８ｄｅｇであった。このような回折パターンを有する場合、図５（ｃ）に示すように、小さい結晶粒Ｃｇが膜厚方向に整列して結晶粒界Ｃｆがその膜厚方向にのびるように繋がった結晶構造を有し、しかも、その結晶粒界Ｃｆにチタン化合物Ｉｍが形成されていると推測される。 In Comparative Experiment 3, the total pressure in the film forming chambers Pc1 and Pc3 during the film formation in each of the first and third steps was maintained at 0.6 Pa and the film forming rate was set to 2 nm/sec. A laminated structure LS was obtained in the same manner as in the experiment of the invention, except that the evacuation step was not performed in each of the third steps (only the film formation step was performed). When a tensile test was performed under the same conditions as the above invention experiment, it was confirmed that the elongation amount of the laminated structure LS was more than doubled. In addition, when the rate of increase in resistance was obtained in the same manner as in the experiment of the invention, it was 300% and 900%, which is worse than that of the comparative experiment 2. Further, when the surface state of the laminated structure LS after the tensile test was observed in the same manner as in the above invention experiment, it was confirmed that cracks were generated and whitened. From these results, it was found that the laminated structure LS obtained in Comparative Experiment 3 had weaker bending resistance than Comparative Experiments 1 and 2 described above. When the X-ray diffraction of the first titanium layer L1 formed in Comparative Experiment 3 was measured, no diffraction peak on the (100) plane was confirmed, and only a diffraction peak on the (002) plane was confirmed. The half width of the diffraction peak on the (002) plane was 0.8 deg. When having such a diffraction pattern, as shown in FIG. 5(c), it has a crystal structure in which small crystal grains Cg are aligned in the film thickness direction and crystal grain boundaries Cf are connected so as to extend in the film thickness direction. Moreover, it is presumed that the titanium compound Im is formed at the grain boundaries Cf.

以上、本発明の実施形態について説明したが、本発明の技術思想の範囲を逸脱しない限り、種々の変形が可能である。上記実施形態では、積層構造体ＬＳとして第１のチタン層Ｌ１、アルミニウム層Ｌ２、第３のチタン層Ｌ３を積層したものを例に説明したが、第３のチタン層Ｌ３の上に更に窒化チタン層が積層されたものに対しても本発明を適用することができる。 Although the embodiments of the present invention have been described above, various modifications are possible without departing from the scope of the technical idea of the present invention. In the above-described embodiment, the laminated structure LS is described as an example in which the first titanium layer L1, the aluminum layer L2, and the third titanium layer L3 are laminated. The present invention can also be applied to laminated layers.

また、上記実施形態では、成膜チャンバＰｃ１，Ｐｃ２，Ｐｃ３の間で基材Ｓｗをin-situで搬送し、真空雰囲気中で第１のチタン層Ｌ１、アルミニウム層Ｌ２、第２のチタン層Ｌ３を一貫して成膜する場合を例に説明したが、これに限定されず、第１及び第２のチタン層Ｌ１，Ｌ３とアルミニウム層Ｌ２とを異なるスパッタリング装置で実施する場合にも本発明は適用することができる。また、第１のチタン層Ｌ１と第２のチタン層Ｌ３とを同一の成膜チャンバで成膜してもよい。 Further, in the above embodiment, the substrate Sw is transferred in-situ among the film forming chambers Pc1, Pc2, and Pc3, and the first titanium layer L1, the aluminum layer L2, and the second titanium layer L3 are formed in a vacuum atmosphere. However, the present invention is not limited to this, and the present invention can also be applied to the case where the first and second titanium layers L1 and L3 and the aluminum layer L2 are formed by different sputtering apparatuses. can be applied. Also, the first titanium layer L1 and the second titanium layer L3 may be formed in the same film formation chamber.

ＬＳ…積層構造体、Ｌ１…第１のチタン層、Ｌ２…アルミニウム層、Ｌ３…第２のチタン層、Ｓｗ…基材、Ｐｃ１，Ｐｃ２，Ｐｃ３…成膜チャンバ（真空チャンバ）、２…ターゲット。 LS... Laminated structure, L1... First titanium layer, L2... Aluminum layer, L3... Second titanium layer, Sw... Base material, Pc1, Pc2, Pc3... Film formation chamber (vacuum chamber), 2... Target.

Claims (4)

第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体において、
第１及び第２の各チタン層は、Ｘ線回折測定によるミラー指数における（００２）面及び（１００）面に回析ピークを持つ結晶構造を有し、（００２）面での回折ピークの半値幅が１．０ｄｅｇ以下、（１００）面での回折ピークの半値幅が０．６ｄｅｇ以下であることを特徴とする積層構造体。In a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated,
Each of the first and second titanium layers has a crystal structure with diffraction peaks in the (002) plane and the (100) plane in the Miller index measured by X-ray diffraction, and half of the diffraction peak in the (002) plane A laminated structure having a value width of 1.0 deg or less and a diffraction peak half width of 0.6 deg or less on the (100) plane. 前記アルミニウム層は、Ｘ線回折測定によるミラー指数における（１１１）面に回析ピークを持つ結晶構造を有することを特徴とする請求項１記載の積層構造体。 2. The laminated structure according to claim 1, wherein said aluminum layer has a crystal structure having a diffraction peak in the (111) plane in the Miller index measured by X-ray diffraction. 第１のチタン層と、アルミニウム層と、第２のチタン層とを順次積層した積層構造体の製造方法において、
スパッタリング法により、基材上に第１のチタン層を成膜する第１工程と、第１のチタン層の上にアルミニウム層を成膜する第２工程と、アルミニウム層の上に第２のチタン層を成膜する第３工程とを含み、
第１及び第３の各工程は、窒素ガスの分圧が３．０×１０－４Ｐａ以下、酸素ガスの分圧が９．０×１０－５Ｐａ以下、水蒸気ガスの分圧が８．０×１０－４Ｐａ以下、水素ガスの分圧が５．０×１０－５Ｐａ以下に夫々達するまで、チタン製のターゲットと基材とが配置された真空チャンバ内を真空排気する真空排気工程と、真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、チタン製のターゲットに所定電力を投入して３ｎｍ／ｓｅｃ～５ｎｍ／ｓｅｃの範囲内の成膜速度で第１及び第２の各チタン層を成膜する成膜工程と、を更に含むことを特徴とする積層構造体の製造方法。In a method for manufacturing a laminated structure in which a first titanium layer, an aluminum layer, and a second titanium layer are sequentially laminated,
A first step of forming a first titanium layer on a substrate by a sputtering method, a second step of forming an aluminum layer on the first titanium layer, and a second titanium layer on the aluminum layer a third step of depositing a layer;
In each of the first and third steps, the partial pressure of nitrogen gas is 3.0×10 −4 Pa or less, the partial pressure of oxygen gas is 9.0×10 −5 Pa or less, and the partial pressure of steam gas is 8.0×10 −5 Pa or less. Evacuation step of evacuating the vacuum chamber in which the titanium target and the substrate are arranged until the partial pressure of hydrogen gas reaches 0×10 −4 Pa or less and the hydrogen gas partial pressure reaches 5.0×10 −5 Pa or less, respectively. Then, a rare gas is introduced so that the total pressure in the vacuum chamber is maintained within the range of 0.2 Pa to 0.5 Pa, and a predetermined power is applied to the titanium target to achieve 3 nm/sec to 5 nm/sec. and a film forming step of forming the first and second titanium layers at a film forming rate within a range. 前記第２工程は、アルミニウム製のターゲットと基材とが配置された真空チャンバ内の全圧が０．２Ｐａ～０．５Ｐａの範囲内に維持されるように希ガスを導入し、アルミニウム製のターゲットに所定電力を投入して７ｎｍ／ｓｅｃ～１０ｎｍ／ｓｅｃの範囲内の成膜速度でアルミニウム層を成膜する成膜工程を更に含むことを特徴とする請求項３記載の積層構造体の製造方法。 In the second step, a rare gas is introduced so that the total pressure in the vacuum chamber in which the aluminum target and the substrate are arranged is maintained within a range of 0.2 Pa to 0.5 Pa, and the aluminum 4. The manufacturing of the laminated structure according to claim 3, further comprising a film forming step of applying a predetermined power to the target and forming the aluminum layer at a film forming rate within a range of 7 nm/sec to 10 nm/sec. Method.
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