JP5234483B2 - Wiring base film with excellent adhesion and sputtering target for forming this wiring base film - Google Patents
Wiring base film with excellent adhesion and sputtering target for forming this wiring base film Download PDFInfo
- Publication number
- JP5234483B2 JP5234483B2 JP2007155111A JP2007155111A JP5234483B2 JP 5234483 B2 JP5234483 B2 JP 5234483B2 JP 2007155111 A JP2007155111 A JP 2007155111A JP 2007155111 A JP2007155111 A JP 2007155111A JP 5234483 B2 JP5234483 B2 JP 5234483B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- wiring
- base film
- oxygen
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Physical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Description
この発明は、ガラス基板の表面に対する密着性に優れかつボイドの発生しない銅合金膜からなる配線下地膜およびこの配線下地膜を形成するための銅合金からなるスパッタリングターゲットに関するものであり、この配線下地膜は導電性に優れた配線膜の下に形成して、前記配線膜のガラス基板表面に対する密着性を高めるために使用され、この配線下地膜は、例えば、ＴＦＴトランジスターを用いたフラットパネルディスプレイにおけるガラス基板の上に形成し、この配線下地膜の上に配線膜を形成して配線膜のガラス基板に対する密着性を高めるために使用されるものである。 The present invention relates to a wiring base film made of a copper alloy film that has excellent adhesion to the surface of a glass substrate and does not generate voids, and a sputtering target made of a copper alloy for forming the wiring base film. The ground film is formed under the wiring film having excellent conductivity, and is used to improve the adhesion of the wiring film to the surface of the glass substrate. This wiring base film is used in, for example, a flat panel display using a TFT transistor. It is formed on a glass substrate and used to increase the adhesion of the wiring film to the glass substrate by forming a wiring film on the wiring base film.
アクティブマトリックス方式で駆動するＴＦＴトランジスターを用いたフラットパネルディスプレイとして、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ、無機ＥＬディスプレイなどが知られている。これらＴＦＴトランジスターを用いたフラットパネルディスプレイにはガラス基板表面に格子状に純銅配線膜が密着形成されている。
この従来のＴＦＴトランジスターを用いたフラットパネルディスプレイにおいてガラス基板表面に形成される純銅配線膜は、純銅膜自体がガラス基板に対する密着性が悪いので、通常は、図１の断面概略拡大説明図に示されるように、ガラス基板１の表面に酸素：１〜６モル％を含有する酸素含有銅下地膜２を形成し、この酸素含有銅下地膜２の上に導電性に優れた純銅膜３を形成して二重構造配線膜４を形成し、この酸素含有銅下地膜２および純銅膜３からなる二重構造配線膜４の純銅膜３の上にゲート絶縁膜（ＳｉＮｘ膜）５を形成し、このゲート絶縁膜（ＳｉＮｘ膜）５の上にアモルファスＳｉ膜７を形成している（特許文献１、２参照）。そして、ガラス基板１の表面に対する酸素含有銅下地膜２の密着性は酸素が多く含まれているほど向上することも知られている。
The pure copper wiring film formed on the glass substrate surface in this conventional flat panel display using TFT transistors usually has a poor adhesion to the glass substrate. As shown, an oxygen-containing copper base film 2 containing oxygen: 1 to 6 mol% is formed on the surface of the glass substrate 1, and a pure copper film 3 having excellent conductivity is formed on the oxygen-containing copper base film 2. A double structure wiring film 4 is formed, and a gate insulating film (SiNx film) 5 is formed on the pure copper film 3 of the double structure wiring film 4 composed of the oxygen-containing copper base film 2 and the pure copper film 3. An amorphous Si film 7 is formed on the gate insulating film (SiNx film) 5 (see Patent Documents 1 and 2). It is also known that the adhesion of the oxygen-containing copper base film 2 to the surface of the glass substrate 1 improves as the oxygen content increases.
前記ゲート絶縁膜（ＳｉＮｘ膜）５は、ＳｉＨ４、ＮＨ３およびＮ２からなる水素を含む混合ガス中で３００℃前後に加熱された雰囲気中で化学蒸着することにより形成されることから、前記ゲート絶縁膜（ＳｉＮｘ膜）５の形成に際して水素（Ｈ＋）が純銅膜３を通過して酸素含有銅下地膜５に到達し、そこで酸素含有銅下地膜５の酸素と結合して水となり酸素含有銅下地膜５に大きなボイド６が発生させ、ガラス基板１の表面に対する酸素含有銅下地膜２の密着性を低下させることがあるので好ましくない。
さらに前記ゲート絶縁膜（ＳｉＮｘ膜）５は水素を含む混合ガス中で化学蒸着することにより形成されることからゲート絶縁膜（ＳｉＮｘ膜）５に水素が不可避不純物として含まれることは避けられず、フラットパネルディスプレイのアモルファスＳｉ膜７のＣＶＤ成膜（成膜温度は２５０℃程度である）に際してゲート絶縁膜（ＳｉＮｘ膜）５に含まれる水素（Ｈ＋）が純銅膜３を通過して酸素含有銅下地膜５に到達し、そこで酸素含有銅下地膜の酸素と結合して水となり酸素含有銅下地膜５に大きなボイド６が発生するので好ましくない。
The gate insulating film (SiNx film) 5 is formed by chemical vapor deposition in an atmosphere heated to around 300 ° C. in a mixed gas containing hydrogen consisting of SiH 4 , NH 3 and N 2. When forming the gate insulating film (SiNx film) 5, hydrogen (H + ) passes through the pure copper film 3 and reaches the oxygen-containing copper base film 5, where it combines with oxygen in the oxygen-containing copper base film 5 to form water and oxygen It is not preferable because a large void 6 is generated in the containing copper base film 5 and the adhesion of the oxygen-containing copper base film 2 to the surface of the glass substrate 1 may be lowered.
Furthermore, since the gate insulating film (SiNx film) 5 is formed by chemical vapor deposition in a mixed gas containing hydrogen, it is inevitable that hydrogen is included in the gate insulating film (SiNx film) 5 as an inevitable impurity. Hydrogen (H + ) contained in the gate insulating film (SiNx film) 5 passes through the pure copper film 3 and contains oxygen during CVD film formation (film formation temperature is about 250 ° C.) of the amorphous Si film 7 of the flat panel display. Since it reaches the copper base film 5 and combines with oxygen in the oxygen-containing copper base film to form water, a large void 6 is generated in the oxygen-containing copper base film 5, which is not preferable.
そこで、本発明者等は、大きなボイドが発生することがなくさらに一層密着性に優れた酸素含有下地膜を開発すべく研究を行った。その結果、
（イ）純銅（特に純度：９９．９９％以上の無酸素銅）に、酸素を６モル％越え〜２０モル％含有し、さらにＭｏ、Ｍｎ、Ｃａ、Ｚｎ、Ｎｉ、Ｔｉ、Ａｌ、ＭｇおよびＦｅのうちの１種または２種以上を合計で０．２〜５モル％を含有した成分組成を有する銅合金からなる下地膜は、従来の酸素含有銅下地膜に比べて酸素が多く含有しているのでガラス基板に対する密着性が一層優れるようになり、さらにＭｏ、Ｍｎ、Ｃａ、Ｚｎ、Ｎｉ、Ｔｉ、Ａｌ、ＭｇおよびＦｅのうちの１種または２種以上を合計で０．２〜５モル％を含有することにより、ゲート絶縁膜（ＳｉＮｘ膜）形成に際して発生する水素（Ｈ＋）が前記銅合金からなる下地膜に拡散侵入したり、さらにゲート絶縁膜（ＳｉＮｘ膜）に含まれる水素（Ｈ＋）がアモルファスＳｉ膜７のＣＶＤ成膜（成膜温度は２５０℃程度である）に際して前記銅合金からなる下地膜に拡散侵入することがあっても、銅合金からなる下地膜にＭｏ、Ｍｎ、Ｃａ、Ｚｎ、Ｎｉ、Ｔｉ、Ａｌ、ＭｇおよびＦｅのうちの１種または２種以上を合計で０．２〜５モル％が含有しているので大きなボイドの発生がなくなることから、この銅合金からなる下地膜の上に純銅膜などの導電性に優れた膜を形成して得られる二重構造配線膜は密着性に優れたものとなり、ＴＦＴトランジスターを用いたフラットパネルディスプレイの配線膜として一層優れた効果を奏するものとなる、
（ロ）前記銅合金からなる下地膜は、酸素：６越え〜２０モル％含有し、さらにＭｏ、Ｍｎ、Ｃａ、Ｚｎ、Ｎｉ、Ｔｉ、Ａｌ、ＭｇおよびＦｅのうちの１種または２種以上を合計で０．２〜５モル％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有する前記銅合金からなる下地膜と同じ成分組成を有するターゲットを用いてスパッタリングすることにより形成することができる、などの研究結果が得られたのである。
Accordingly, the present inventors have conducted research to develop an oxygen-containing base film that is superior in adhesion without generating large voids. as a result,
(B) Pure copper (particularly purity: 99.99% or more oxygen-free copper) contains oxygen in an amount exceeding 6 mol% to 20 mol%, and Mo, Mn, Ca, Zn, Ni, Ti, Al, Mg, and A base film made of a copper alloy having a component composition containing a total of 0.2 to 5 mol% of one or more of Fe contains a larger amount of oxygen than a conventional oxygen-containing copper base film. Therefore, the adhesion to the glass substrate is further improved, and one or more of Mo, Mn, Ca, Zn, Ni, Ti, Al, Mg, and Fe are added in a total amount of 0.2-5. By containing mol%, hydrogen (H + ) generated during the formation of the gate insulating film (SiNx film) diffuses and penetrates into the base film made of the copper alloy, or hydrogen contained in the gate insulating film (SiNx film). (H + ) is amorphous S Even if the i-film 7 is CVD-deposited (deposition temperature is about 250 ° C.), the base film made of copper alloy may diffuse into the base film made of copper alloy, but Mo, Mn, Ca, Zn , Ni, Ti, Al, Mg, and Fe are contained in one or more kinds in a total amount of 0.2 to 5 mol%, so that no large voids are generated. The double-layer wiring film obtained by forming a film with excellent conductivity such as a pure copper film on the ground film has excellent adhesion, and is more effective as a wiring film for flat panel displays using TFT transistors. Will be played,
(B) The base film made of the copper alloy contains oxygen: more than 6 to 20 mol%, and one or more of Mo, Mn, Ca, Zn, Ni, Ti, Al, Mg and Fe Is formed by sputtering using a target having the same component composition as the base film made of the copper alloy having a component composition of Cu and unavoidable impurities. The research results were obtained.
この発明は、上記の研究結果に基づいてなされたものであって、
（１）酸素：６越え〜２０モル％を含有し、さらに、Ｍｎ、ＺｎおよびＦｅのうちの１種を、或いは、ＭｎとＣａ、Ｎｉ、Ａｌのうちの１種との合計を０．２〜５モル％含有し、残部がＣｕおよび不可避不純物からなる組成を有する銅合金膜からなる配線下地膜、
（２）酸素：６越え〜２０モル％を含有し、さらに、Ｍｎ、ＺｎおよびＦｅのうちの１種を、或いは、ＭｎとＣａ、Ｎｉ、Ａｌのうちの１種との合計を０．２〜５モル％含有し、残部がＣｕおよび不可避不純物からなる組成を有する銅合金からなる前記（１）記載の密着性に優れた配線下地膜を形成するためのスパッタリングターゲット、に特徴を有するものである。
This invention was made based on the above research results,
(1) Oxygen: 6 exceeds contained 20 mol%, in further, Mn, and one of Zn and Fe, or, Mn and Ca, Ni, the sum of one of Al 0. a 2-5 mole% containing, wiring base film made of a copper alloy film having the balance consisting of Cu and unavoidable impurities,
(2) Oxygen: 6 exceeds contained 20 mol%, in further, Mn, and one of Zn and Fe, or, Mn and Ca, Ni, the sum of one of Al 0. a 2-5 mole% containing the balance characterized by the sputtering target for forming a wiring base film having excellent adhesiveness to the (1) described consisting of a copper alloy having a composition consisting of Cu and unavoidable impurities Is.
この発明の密着性に優れた銅合金からなる配線下地膜は、この銅合金からなる配線下地膜と同じ成分組成を有するターゲットを用い、スパッタリングすることにより形成することができる。そして、このターゲットは、無酸素銅粉末、Ｍｏ粉末、Ｍｎ粉末、Ｃｕ−Ｃａ合金粉末、Ｚｎ粉末、Ｎｉ粉末、Ｔｉ粉末、Ａｌ粉末、Ｃｕ−Ｍｇ合金粉末、Ｆｅ粉末およびＣｕＯ粉末を原料粉末として用意し、これら原料粉末を酸素：６越え〜２０モル％を含有し、さらに、Ｍｎ、ＺｎおよびＦｅのうちの１種を、或いは、ＭｎとＣａ、Ｎｉ、Ａｌのうちの１種との合計を０．２〜５モル％含有し、残部がＣｕおよび不可避不純物からなる組成を有するように配合し、ボールミルで混合して混合粉末を作製し、この混合粉末をホットプレスし、得られたホットプレス体を機械加工することにより作製することができる。 The wiring base film made of a copper alloy having excellent adhesion of the present invention can be formed by sputtering using a target having the same component composition as that of the wiring base film made of this copper alloy. And this target uses oxygen-free copper powder, Mo powder, Mn powder, Cu-Ca alloy powder, Zn powder, Ni powder, Ti powder, Al powder, Cu-Mg alloy powder, Fe powder and CuO powder as raw material powders. prepared, these raw material powders oxygen: 6 exceeds contained 20 mol%, in further, Mn, and one of Zn and Fe, or, Mn and Ca, Ni, and one of Al total has 0.2 to 5 mole% containing, formulated to have the balance consisting of Cu and inevitable impurities, were mixed by a ball mill to prepare a mixed powder, the mixed powder was hot pressed, obtained The hot-pressed body can be manufactured by machining.
さらに、この発明の密着性に優れた銅合金からなる配線下地膜は、無酸素銅粉末、Ｍｏ粉末、Ｍｎ粉末、Ｃｕ−Ｃａ合金粉末、Ｚｎ粉末、Ｎｉ粉末、Ｔｉ粉末、Ａｌ粉末、Ｃｕ−Ｍｇ合金粉末およびＦｅ粉末を用意し、これら原料粉末をに、Ｍｎ、ＺｎおよびＦｅのうちの１種を、或いは、ＭｎとＣａ、Ｎｉ、Ａｌのうちの１種との合計を０．２〜５モル％含有し、残部がＣｕおよび不可避不純物からなる組成を有するように配合し、ボールミルで混合して混合粉末を作製し、この混合粉末をホットプレスし、得られたホットプレス体を機械加工することにより実質的に酸素を含まない銅合金製ターゲットを作製し、このターゲットを用い、酸素：３〜２５体積％含む不活性ガス雰囲気中でスパッタリングすることにより成膜することもできる。 Furthermore, the wiring base film made of the copper alloy having excellent adhesion according to the present invention includes oxygen-free copper powder, Mo powder, Mn powder, Cu—Ca alloy powder, Zn powder, Ni powder, Ti powder, Al powder, Cu— Mg alloy powder and Fe powder are prepared, and one of Mn, Zn and Fe, or the total of Mn and one of Ca, Ni and Al is 0.2 to a 5 mole% containing, formulated to have the balance consisting of Cu and inevitable impurities, were mixed by a ball mill to prepare a mixed powder, the mixed powder was hot pressed, the machine and the resulting hot pressed body A copper alloy target substantially free of oxygen can be produced by processing, and this target can be used to form a film by sputtering in an inert gas atmosphere containing 3 to 25% by volume of oxygen. .
この発明の密着性に優れた配線下地膜、およびこの配線下地膜を成膜するためのターゲットの成分組成の範囲を前述のごとく限定した理由を説明する。
（ａ）配線下地膜の成分組成：
この発明の銅合金からなる配線下地膜に含まれる酸素は６モル％を越えて含有させることにより密着強度を一層向上させることができるが２０モル％を越えて含有すると電気抵抗があまりにも上昇し過ぎ、さらに配線下地膜に含まれる酸素により大きなボイドが発生するようになるので好ましくない。したがって、配線下地膜に含まれる酸素を６モル％越え〜２０モル％に定めた。
さらに、この発明の銅合金からなる配線下地膜に含まれるＭｏ、Ｍｎ、Ｃａ、Ｚｎ、Ｎｉ、Ｔｉ、Ａｌ、ＭｇおよびＦｅはゲート絶縁膜（ＳｉＮｘ膜）形成に際して発生する水素が銅合金下地膜に拡散侵入しても大きなボイドの発生を阻止する作用を有するので添加するが、その含有量が０．２モル％未満添加してもボイドの発生を抑制することができず、一方、５モル％を越えて添加すると、銅合金下地膜の電気抵抗が上昇するので好ましくない。したがって、Ｍｎ、ＺｎおよびＦｅのうちの１種を、或いは、ＭｎとＣａ、Ｎｉ、Ａｌのうちの１種との合計を０．２〜５モル％に定めた。
The reason why the wiring underlayer excellent in adhesiveness of the present invention and the range of the component composition of the target for forming the wiring underlayer are limited as described above.
(A) Component composition of wiring base film:
The adhesion strength can be further improved by containing more than 6 mol% of oxygen contained in the wiring underlayer made of the copper alloy of the present invention. However, if it exceeds 20 mol%, the electrical resistance increases too much. Further, it is not preferable because a large void is generated due to oxygen contained in the wiring base film. Therefore, the oxygen contained in the wiring base film is determined to be over 6 mol% to 20 mol%.
Further, Mo, Mn, Ca, Zn, Ni, Ti, Al, Mg, and Fe contained in the wiring base film made of the copper alloy of the present invention are hydrogen generated during the formation of the gate insulating film (SiNx film). Even if it diffuses and penetrates into the layer, it is added because it has the action of preventing the generation of large voids. However, even if the content is less than 0.2 mol%, the generation of voids cannot be suppressed. If the addition exceeds 50%, the electrical resistance of the copper alloy underlayer increases, which is not preferable. Therefore, the total of one of Mn, Zn, and Fe, or the total of Mn and one of Ca, Ni, and Al is set to 0.2 to 5 mol % .
（ｂ）ターゲットの成分組成：
この発明の銅合金からなる配線下地膜を成膜するためのターゲットに含まれる酸素を６越え〜２０モル％に限定したのは、ターゲットに含まれる酸素が６モル％以下ではスパッタリングすることにより形成される銅合金膜に含まれる酸素が６モル％以下となって所望の効果が得られなくなるので好ましくなく、一方、ターゲットに含まれる酸素が２０モル％を越えて含まれるようになると、スパッタリングして得られた膜の密着性は向上するものの電気抵抗が大幅に上昇するので好ましくないからである。
さらに、この発明の銅合金からなる配線下地膜を成膜するためのターゲットに含まれるＭｎ、ＺｎおよびＦｅのうちの１種を、或いは、ＭｎとＣａ、Ｎｉ、Ａｌのうちの１種との合計を０．２〜５モル％に限定したのは、これら成分のうちの１種または２種以上を合計で０．２モル％より少なく添加したターゲットは、これを用いてスパッタリングしてもＭｎ、Ｃａ、Ｚｎ、Ｎｉ、Ｔｉ、ＡｌおよびＦｅのうちの１種または２種以上を合計で０．２モル％未満含有する銅合金膜が形成されて十分なボイドの発生を抑制することができないので好ましくないからであり、一方、５モル％を越えて添加したターゲットを使用してスパッタリングすると、成膜される銅合金膜に含まれるこれら成分の含有量が５モル％を越えるようになり、電気抵抗が上昇するので好ましくないことによるものである。
(B) Target component composition:
The reason why the oxygen contained in the target for forming the wiring base film made of the copper alloy of the present invention is limited to more than 6 to 20 mol% is that the oxygen contained in the target is formed by sputtering when the oxygen contained in the target is 6 mol% or less. When the oxygen contained in the target exceeds 6 mol% and the desired effect cannot be obtained, it is not preferable. On the other hand, when the oxygen contained in the target exceeds 20 mol%, sputtering is performed. This is because although the adhesion of the film obtained in this way is improved, the electrical resistance is greatly increased, which is not preferable.
Further, one of Mn, Zn and Fe contained in the target for forming the wiring underlayer made of the copper alloy of the present invention , or one of Mn and one of Ca, Ni and Al. The total was limited to 0.2 to 5 mol % because the target added with one or more of these components in less than 0.2 mol% in total was Mn , Ca, Zn, Ni, Ti, Al, and one or more of Fe and a copper alloy film containing less than 0.2 mol% in total are formed, and generation of sufficient voids cannot be suppressed On the other hand, when sputtering using a target added in excess of 5 mol%, the content of these components contained in the copper alloy film to be formed exceeds 5 mol%, Electrical resistance Since increased is by undesirable.
この発明の配線下地膜はガラス基板に対する密着性を一層優れており、さらに、ゲート絶縁膜（例えば、ＳｉＮｘ膜）の成膜に際してまたはアモルファスＳｉのＣＶＤ成膜時の水素の拡散浸透によるボイドの発生がなく、この発明の配線下地膜の上に導電性に優れた銅または銅合金からなる膜を形成して作製した二重構造配線膜は、これをＴＦＴトランジスターを用いたフラットパネルディスプレイにおける配線膜などに用いると、ＴＦＴトランジスターを用いたフラットパネルディスプレイが激しい振動を受けるなど過酷な環境下で長期間おかれても配線が剥離することがなく、したがって、故障することがないＴＦＴトランジスターを用いたフラットパネルディスプレイを提供することができるという優れた効果を奏するものである。 The wiring underlayer of the present invention is further excellent in adhesion to a glass substrate, and further, voids are generated due to diffusion and penetration of hydrogen during the formation of a gate insulating film (for example, SiNx film) or during CVD of amorphous Si. The double structure wiring film produced by forming a film made of copper or copper alloy having excellent conductivity on the wiring base film of the present invention is a wiring film in a flat panel display using a TFT transistor. When a flat panel display using a TFT transistor is subjected to severe vibration, the wiring does not peel off even if it is placed for a long time in a harsh environment, and therefore a TFT transistor that does not break down is used. The present invention provides an excellent effect that a flat panel display can be provided.
純度：９９．９９質量％の純Ｃｕ粉末（平均粒径：７０μｍ）、Ｍｏ粉末（平均粒径：５μｍ）、Ｍｎ粉末（平均粒径：７５μｍ）、表１〜４に示されるＣｕ−Ｃａ合金粉末（平均粒径：１２０μｍ）、Ｚｎ粉末（平均粒径：７５μｍ）、Ｎｉ粉末（平均粒径：４０μｍ）、Ｔｉ粉末（平均粒径：３０μｍ）、Ａｌ粉末（平均粒径：３０μｍ）、表１〜４に示されるＣｕ−Ｍｇ合金粉末（平均粒径：１２０μｍ）、Ｆｅ粉末（平均粒径：５μｍ）およびＣｕＯ粉末（平均粒径：５μｍ）を用意し、これら原料粉末を表１〜４に示される配合割合で配合し、ボールミルで１６時間乾式混合して混合粉末を作製し、この混合粉末を温度：５００℃、圧力：２．５Ｔｏｎ／ｃｍ２に保持することによりホットプレスし、得られたホットプレス体を機械加工して直径：１５４ｍｍ、厚さ：５ｍｍの寸法を有し表１〜４に示される成分組成を有する本発明銅合金スパッタリングターゲット（以下、本発明ターゲットという）１〜１３、比較銅合金スパッタリングターゲット（以下、比較ターゲットという）１〜３３および酸素含有銅からなるスパッタリングターゲット（以下、従来ターゲットという）１を作製した。
得られた本発明ターゲット１〜１３、比較ターゲット１〜３３および従来ターゲット１の任意の三箇所からターゲット材を各１ｇ程度切り取り、ＩＣＰ法によりその金属組成を測定し、その平均値を求め、その結果を表１〜４に示した。また、酸素含有量は赤外線吸収法により測定し、その結果を表１〜４に示した。
Purity: 99.99 mass% pure Cu powder (average particle size: 70 μm), Mo powder (average particle size: 5 μm), Mn powder (average particle size: 75 μm), Cu—Ca alloys shown in Tables 1 to 4 Powder (average particle size: 120 μm), Zn powder (average particle size: 75 μm), Ni powder (average particle size: 40 μm), Ti powder (average particle size: 30 μm), Al powder (average particle size: 30 μm), table 1 to 4, Cu—Mg alloy powder (average particle size: 120 μm), Fe powder (average particle size: 5 μm) and CuO powder (average particle size: 5 μm) are prepared. The mixture is blended at a blending ratio shown in the following, and dry mixed with a ball mill for 16 hours to produce a mixed powder. This mixed powder is hot-pressed by holding at a temperature of 500 ° C. and a pressure of 2.5 Ton / cm 2. Machined hot press body Te diameter: 154 mm, thickness: 5mm present invention copper alloy sputtering target having a component composition shown in a table 1-4 dimensions of (hereinafter referred to as the present invention target) 1 to 13, Comparative copper alloy sputtering target (hereinafter Sputtering target (hereinafter referred to as a conventional target) 1 made of 1 to 33 and oxygen-containing copper was prepared.
About 1 g each of the target material is cut out from any three locations of the obtained present invention targets 1 to 13 , comparative targets 1 to 33 and the conventional target 1, the metal composition is measured by ICP method, the average value is obtained, The results are shown in Tables 1-4. Moreover, oxygen content was measured by the infrared absorption method, and the result was shown to Tables 1-4.
さらに、無酸素銅製バッキングプレートを用意し、この無酸素銅製バッキングプレートに前記本発明ターゲット１〜１３、比較ターゲット１〜３３および従来ターゲット１を重ね合わせ、温度：２００℃でインジウムはんだ付けすることにより本発明ターゲット１〜１３、比較ターゲット１〜３３および従来ターゲット１を無酸素銅製バッキングプレートに接合してバッキングプレート付きターゲットを作製した。 Furthermore, an oxygen-free copper backing plate is prepared, and the present invention targets 1 to 13 , the comparative targets 1 to 33 and the conventional target 1 are superposed on the oxygen-free copper backing plate, and indium soldered at a temperature of 200 ° C. Invention targets 1-13 , comparative targets 1-33, and conventional target 1 were joined to an oxygen-free copper backing plate to produce a target with a backing plate.
さらに、ガラス基板（縦：５０ｍｍ、横：５０ｍｍ、厚さ：０．７ｍｍの寸法を有するコーニング社製１７３７のガラス基板）を用意した。
本発明ターゲット１〜１３、比較ターゲット１〜３３および従来ターゲット１を無酸素銅製バッキングプレートにはんだ付けして得られたバッキングプレート付きターゲットを、ターゲットとガラス基板との距離が７０mmとなるようにスパッタリング装置にセットし、
電源：直流方式、
スパッタパワー：６００Ｗ、
到達真空度：５×１０−５Ｐａ、
雰囲気ガス組成：Ａｒ、
Ａｒガス圧：０．５Ｐａ、
ガラス基板加熱：なし、
の条件で１分間程度成膜し、ガラス基板の表面に、厚さ：３００ｎｍを有し、表５〜８に示される成分組成を有する本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１を形成した。
Furthermore, a glass substrate (1737 glass substrate manufactured by Corning Inc. having dimensions of 50 mm in length, 50 mm in width, and 0.7 mm in thickness) was prepared.
Sputtering a target with a backing plate obtained by soldering the inventive targets 1 to 13 , comparative targets 1 to 33 and the conventional target 1 to an oxygen-free copper backing plate so that the distance between the target and the glass substrate is 70 mm. Set in the device,
Power supply: DC method,
Sputter power: 600W
Ultimate vacuum: 5 × 10 −5 Pa,
Atmospheric gas composition: Ar,
Ar gas pressure: 0.5 Pa,
Glass substrate heating: None,
The present invention wiring underlayers 1 to 13 and comparative wiring underlayers 1 to 1 having a thickness of 300 nm on the surface of the glass substrate and the composition shown in Tables 5 to 8 are formed on the surface of the glass substrate. 33 and the conventional wiring base film 1 were formed.
得られた本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１をそれぞれＥＰＭＡの波長分散型の分光器ＷＤＳ（Ｗａｖｅｌｅｎｇｈｔ Ｄｉｓｐｅｒｓｉｖｅ Ｘ−ｒａｙ Ｓｐｅｃｔｒｏｍｅｔｅｒ）によって成分組成を測定し、その結果を表５〜８に示した。 Component compositions of the obtained wiring underlayers 1 to 13 of the present invention, comparative wiring underlayers 1 to 33 and the conventional wiring underlayer 1 were measured using an EPMA wavelength dispersion type spectrometer WDS (Wavelength Dispersive X-ray Spectrometer). The results are shown in Tables 5-8.
さらに得られた本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１をそれぞれ２×１０−４Ｐａの真空雰囲気中、温度：３５０℃、３０分間保持する熱処理を行なった後、下記の測定および試験を行い、その結果を表５〜８に示した。
抵抗値測定：
前記熱処理を行なった本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１をそれぞれ四探針法により抵抗値を測定し、その結果を表５〜８に示した。
碁盤目付着試験：
ＪＩＳ-Ｋ５４００に準じ、１ｍｍ間隔で縦横１１本ずつカッターで１ｍｍ間隔の切り込みを入れ、本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１に１００個の升目膜を作り、３Ｍ社製スコッチテープを密着させたのち一気に引き剥がし、ガラス基板中央部の１０ｍｍ角内でガラス基板に付着していた升目膜に剥離が生じた升目膜の数を測定し、その結果を表５〜８に示すことによりガラス基板に対する本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１の密着性を評価した。なお、一部しか剥がれていない升目について、面積の半分以上剥がれたものは「剥がれ」と数え、剥がれた部分が面積の半分以下の場合は「剥がれなし」として数えた。
Furthermore, the obtained wiring underlayers 1 to 13 of the present invention, the comparative wiring underlayers 1 to 33 and the conventional wiring underlayer 1 are each subjected to heat treatment for holding in a vacuum atmosphere of 2 × 10 −4 Pa at a temperature of 350 ° C. for 30 minutes. Then, the following measurements and tests were performed, and the results are shown in Tables 5-8.
Resistance measurement:
The resistance values of the wiring underlayers 1 to 13 of the present invention, the comparative wiring underlayers 1 to 33 and the conventional wiring underlayer 1 subjected to the heat treatment were measured by the four-probe method, and the results are shown in Tables 5-8. .
Cross-cut adhesion test:
According to JIS-K5400, an incision of 1mm intervals by a cutter by vertical and horizontal 11 present at 1mm intervals, the present invention wiring base film 1 to 13, Comparative wiring base film 1 to 33 and 100 square film with conventional wiring base film 1 After the 3M company scotch tape was made in close contact, it was peeled off at once, and the number of cell membranes that peeled off the cell membrane attached to the glass substrate within the 10 mm square at the center of the glass substrate was measured. Tables 5 to 8 evaluated the adhesion of the present wiring substrate films 1 to 13 , the comparative wiring substrate films 1 to 33 and the conventional wiring substrate film 1 to the glass substrate. In addition, regarding the cells that were peeled off only partially, those that peeled more than half of the area were counted as “peeling”, and when the peeled part was less than half of the area, they were counted as “no peeling”.
さらに、先に作製したガラス基板の表面に成膜した厚さ：３００ｎｍを有する本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１の上にさらにＳｉＨ４、ＮＨ３およびＮ２からなる水素を含む混合ガス雰囲気中、温度：３００℃保持の条件のＰＥＣＶＤ法により厚さ：３００ｎｍを有するゲート絶縁膜（ＳｉＮｘ膜）を形成し、このガラス基板の表面に形成した本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１およびこれら下地膜の上にそれぞれ成膜したゲート絶縁膜（ＳｉＮｘ膜）からなる積層膜の断面をＴＥＭを用いて観察し、本発明配線下地膜１〜１３、比較配線下地膜１〜３３および従来配線下地膜１の長さ２０μｍの範囲内に発生した直径：２０ｎｍ以上の大きなボイドの有無を確認し、その結果をその結果を表５〜８に示した。 Further, on the surface of the previously produced glass substrate, SiH 4 , NH is further formed on the wiring base films 1 to 13 of the present invention having a thickness of 300 nm, the comparative wiring base films 1 to 33 and the conventional wiring base film 1. A gate insulating film (SiNx film) having a thickness of 300 nm was formed by PECVD under a temperature of 300 ° C. in a mixed gas atmosphere containing hydrogen containing 3 and N 2, and formed on the surface of this glass substrate. TEM is used for the cross section of the laminated film composed of the wiring underlayers 1 to 13 of the present invention, the comparative wiring underlayers 1 to 33, the conventional wiring underlayer 1 and the gate insulating film (SiNx film) formed on each of these underlayers. observing Te, the present invention wiring underlayer 1-13, the diameter has occurred within the comparison wiring underlayer 1-33 and length 20μm conventional wiring base film 1: 20 nm or more large voids Whether to confirm, and the results The results are shown in Table 5-8.
表１〜８に示される結果から、本発明配線下地膜１〜１３は酸素を含む銅からなる従来配線下地膜１に比べてガラス基板に対する密着性に一層優れていること、この発明の条件から外れて酸素、Ｍｏ、Ｍｎ、Ｃａ、Ｚｎ、Ｎｉ、Ｔｉ、Ａｌ、ＭｇおよびＦｅを含む比較配線下地膜１〜３３は比抵抗が大きくなり過ぎたり、密着性が低下したり、大きなボイドが発生するなど好ましくないことなどが分かる。
From the results shown in Tables 1 to 8, the wiring underlayers 1 to 13 of the present invention are more excellent in adhesion to the glass substrate than the conventional wiring underlayer 1 made of copper containing oxygen, from the conditions of the present invention. The comparative wiring base films 1-33 containing oxygen, Mo, Mn, Ca, Zn, Ni, Ti, Al, Mg, and Fe are excessively high in specific resistance, adhesion is deteriorated, and large voids are generated. It is understood that it is not preferable, for example.
１：ガラス基板、２：酸素含有銅下地膜、３：純銅膜、４：二重構造配線膜４、５：ゲート絶縁膜（ＳｉＮｘ膜）、６：ボイド、７：アモルファスＳｉ膜 1: glass substrate, 2: oxygen-containing copper base film, 3: pure copper film, 4: double structure wiring film 4, 5: gate insulating film (SiNx film), 6: void, 7: amorphous Si film
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007155111A JP5234483B2 (en) | 2007-06-12 | 2007-06-12 | Wiring base film with excellent adhesion and sputtering target for forming this wiring base film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007155111A JP5234483B2 (en) | 2007-06-12 | 2007-06-12 | Wiring base film with excellent adhesion and sputtering target for forming this wiring base film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013068744A Division JP5674064B2 (en) | 2013-03-28 | 2013-03-28 | Manufacturing method of wiring base film with excellent adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008311283A JP2008311283A (en) | 2008-12-25 |
| JP5234483B2 true JP5234483B2 (en) | 2013-07-10 |
Family
ID=40238666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007155111A Expired - Fee Related JP5234483B2 (en) | 2007-06-12 | 2007-06-12 | Wiring base film with excellent adhesion and sputtering target for forming this wiring base film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5234483B2 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4936560B2 (en) * | 2008-03-11 | 2012-05-23 | 三菱マテリアル株式会社 | Method for forming copper alloy composite film having excellent adhesion and Ca-containing copper alloy target used in this film forming method |
| JP2009280834A (en) * | 2008-05-19 | 2009-12-03 | Ulvac Japan Ltd | Target, wiring film forming method, and manufacturing method of thin film transistor |
| JP5269533B2 (en) * | 2008-09-26 | 2013-08-21 | 三菱マテリアル株式会社 | Thin film transistor |
| JP5360959B2 (en) | 2008-10-24 | 2013-12-04 | 三菱マテリアル株式会社 | Thin film transistor having high adhesion strength between barrier film, drain electrode film and source electrode film |
| JP2010165955A (en) * | 2009-01-16 | 2010-07-29 | Kobe Steel Ltd | Cu ALLOY FILM, AND DISPLAY DEVICE |
| KR20110105806A (en) * | 2009-01-16 | 2011-09-27 | 가부시키가이샤 고베 세이코쇼 | Cu alloy film and display device |
| JP5622079B2 (en) * | 2009-03-27 | 2014-11-12 | 日立金属株式会社 | Sputtering target |
| CN102804341A (en) * | 2009-06-12 | 2012-11-28 | 株式会社爱发科 | Method for producing electronic device, electronic device, semiconductor device, and transistor |
| JP4970621B2 (en) | 2009-08-28 | 2012-07-11 | 株式会社アルバック | Wiring layer, semiconductor device, liquid crystal display device |
| KR20140091734A (en) | 2011-09-14 | 2014-07-22 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | High-purity copper-manganese-alloy sputtering target |
| SG10201607223SA (en) | 2011-09-14 | 2016-10-28 | Jx Nippon Mining & Metals Corp | High-purity copper-manganese-alloy sputtering target |
| CN104066868B (en) | 2012-01-23 | 2016-09-28 | 吉坤日矿日石金属株式会社 | High-purity copper-manganese-alloy sputtering target |
| JP5979034B2 (en) | 2013-02-14 | 2016-08-24 | 三菱マテリアル株式会社 | Sputtering target for protective film formation |
| WO2014136673A1 (en) | 2013-03-07 | 2014-09-12 | Jx日鉱日石金属株式会社 | Copper alloy sputtering target |
| KR102094841B1 (en) | 2013-05-16 | 2020-03-31 | 삼성디스플레이 주식회사 | Display apparatus and method of manufacturing the same |
| JP6369750B2 (en) | 2013-09-10 | 2018-08-08 | 日立金属株式会社 | LAMINATED WIRING FILM, MANUFACTURING METHOD THEREOF, AND NI ALLOY SPUTTERING TARGET MATERIAL |
| JP5757318B2 (en) | 2013-11-06 | 2015-07-29 | 三菱マテリアル株式会社 | Protective film forming sputtering target and laminated wiring film |
| JP6860990B2 (en) * | 2016-07-27 | 2021-04-21 | デクセリアルズ株式会社 | Mn-Zn-O-based sputtering target and its manufacturing method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6464338A (en) * | 1987-09-04 | 1989-03-10 | Hitachi Ltd | Wiring for semiconductor device |
| JPH0525612A (en) * | 1991-07-22 | 1993-02-02 | Komatsu Ltd | Formation of metallic thin film |
| JPH0826889A (en) * | 1994-07-15 | 1996-01-30 | Fujitsu Ltd | Formation of metallic film and metallic film for wiring |
| JP2005158887A (en) * | 2003-11-21 | 2005-06-16 | Dept Corp | Circuit board and its production process |
| CN101529566B (en) * | 2006-12-28 | 2011-11-16 | 株式会社爱发科 | Method for forming wiring film, transistor, and electronic device |
-
2007
- 2007-06-12 JP JP2007155111A patent/JP5234483B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008311283A (en) | 2008-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5234483B2 (en) | Wiring base film with excellent adhesion and sputtering target for forming this wiring base film | |
| JP5541651B2 (en) | Sputtering target for wiring film formation for thin film transistors | |
| JP5420328B2 (en) | Sputtering target for forming wiring films for flat panel displays | |
| JP5339830B2 (en) | Thin film transistor wiring film having excellent adhesion and sputtering target for forming this wiring film | |
| JP4840172B2 (en) | Wiring and electrodes for liquid crystal display devices with no thermal defects and excellent adhesion | |
| CN102165596B (en) | Thin-film transistor and intermediate of thin-film transistor | |
| TW201232739A (en) | Wiring structure and display device | |
| CN102349157B (en) | Thin film transistor having a barrier layer as a constituting layer and cu-alloy sputtering target used for sputter film formation of the barrier layer | |
| JP2009010089A (en) | Wiring base film with good adhesiveness, and double-structure wiring film with good adhesiveness including the same | |
| JP2010248619A (en) | Method for producing oxygen-containing copper alloy film | |
| JP2004076080A (en) | Thin film for wiring and sputtering target | |
| Chu et al. | Thermal stability of Cu (W) and Cu (Mo) films for advanced barrierless Cu metallization: Effects of annealing time | |
| JP4936560B2 (en) | Method for forming copper alloy composite film having excellent adhesion and Ca-containing copper alloy target used in this film forming method | |
| JP5674064B2 (en) | Manufacturing method of wiring base film with excellent adhesion | |
| JP2008124450A (en) | Target, film forming method, thin film transistor, panel with thin film transistor, manufacturing method for thin film transistor, and manufacturing method for panel with thin film transistor | |
| JP2004076079A (en) | Thin film for wiring and sputtering target | |
| JP5099504B2 (en) | Wiring and electrodes for liquid crystal display devices with excellent adhesion | |
| JP2008277685A (en) | Interconnection film and electrode film for flat panel display using thin film transistor (tft) superior in adhesiveness, and sputtering target for forming them | |
| JP5008146B2 (en) | Copper alloy composite film with excellent adhesion | |
| JP2010248627A (en) | Sputtering target | |
| JP2008112989A (en) | Target, film forming method, thin film transistor, panel with thin film transistor, and manufacturing method for thin film transistor | |
| US20090035173A1 (en) | Electrically Conductive Material | |
| JP2008057031A (en) | Wiring and electrode electrode for liquid crystal display free from generation of heat defect and sputtering target for forming them | |
| JP5077695B2 (en) | Sputtering target for forming wiring film for flat panel display | |
| JP5377914B2 (en) | Thin film transistor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100330 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120726 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120803 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120926 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130304 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130317 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160405 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |