JP4840172B2 - Wiring and electrodes for liquid crystal display devices with no thermal defects and excellent adhesion - Google Patents
Wiring and electrodes for liquid crystal display devices with no thermal defects and excellent adhesion Download PDFInfo
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Description
この発明は、ガラス基板表面およびシリコン基板に対する密着性に優れ、さらにヒロックおよびボイドなどの熱欠陥の発生がない銅合金薄膜からなる液晶表示装置用配線および電極に関するものである。 The present invention relates to a wiring for a liquid crystal display device and an electrode comprising a copper alloy thin film which is excellent in adhesion to the surface of a glass substrate and a silicon substrate and which does not cause thermal defects such as hillocks and voids.
一般に、フラットパネルディスプレイなどの液晶表示装置にはガラス基板表面に格子状に純銅薄膜からなる配線が密着して形成されており、この純銅薄膜からなる格子状配線の交差点にＴＦＴトランジスターが設けられており、このＴＦＴトランジスターのゲート電極にも純銅薄膜が使用されている。これらガラス基板表面に形成された純銅薄膜からなる配線およびＴＦＴトランジスターのゲート電極は液晶表示装置の製造工程においてアモルファスシリコンや窒化珪素等をＰＥＣＶＤ（プラズマ化学蒸着）で成膜する工程で熱履歴を受けることが知られている。さらに、酸素を含有させた銅薄膜は、ガラス基板表面に対する密着性が高くなるものの比抵抗値が高くなるので好ましくないことも知られている（特許文献１参照）。
近年、液晶表示装置は益々大型化しており、３０インチ以上の大型液晶パネルが量産されるようになって来た。そのためにガラス基板表面に形成されている配線が長くなり、さらに液晶表示装置は益々高精細化しているためにガラス基板表面に形成される配線を益々細くすることが求められている。そのために配線の比抵抗を低くするとともに配線が剥離することのないようにガラス基板表面に対する密着性に優れた純銅薄膜で構成されることが必要である。さらに、液晶表示装置の配線および電極はその製造中に熱処理が施されるが、かかる熱処理工程で高温に曝されてもヒロックおよびボイドなどの熱欠陥が発生しない純銅薄膜で構成されることが要求されている。
これら要求に対して、従来の純銅薄膜は比抵抗が極めて低いもののガラス基板表面に対する密着性が悪く、さらに高温に曝されるとヒロックおよびボイドが発生するので好ましくない。また、ガラス基板表面に対する密着性を向上させた従来の酸素を含む銅薄膜は密着性に優れているものの比抵抗が高くなり、さらに高温に曝されるとヒロックおよびボイドなどの熱欠陥が発生するようになるので好ましくない。
In recent years, liquid crystal display devices have become increasingly larger, and large liquid crystal panels of 30 inches or more have been mass-produced. For this reason, the wiring formed on the surface of the glass substrate becomes longer, and the liquid crystal display device is becoming higher in definition, so that the wiring formed on the surface of the glass substrate is required to be thinner. Therefore, it is necessary to reduce the specific resistance of the wiring and to form a pure copper thin film having excellent adhesion to the glass substrate surface so that the wiring does not peel off. Furthermore, the wiring and electrodes of liquid crystal display devices are heat-treated during their manufacture, but are required to be composed of pure copper thin films that do not generate thermal defects such as hillocks and voids even when exposed to high temperatures in such heat treatment processes. Has been.
In response to these requirements, the conventional pure copper thin film has an extremely low specific resistance, but has poor adhesion to the surface of the glass substrate. Further, when exposed to high temperatures, hillocks and voids are generated, which is not preferable. In addition, the conventional oxygen-containing copper thin film with improved adhesion to the glass substrate surface is excellent in adhesion, but has a high specific resistance, and when exposed to high temperatures, thermal defects such as hillocks and voids occur. This is not preferable.
そこで、本発明者等は、比抵抗が低く、しかもガラス基板表面に対する密着性に優れ、さらに高温に曝されてもヒロックおよびボイドなどの熱欠陥の発生が極めて少ない銅合金薄膜を開発し、これを液晶表示装置における配線および電極に適用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、Ａｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０１〜１原子％含有し、さらに酸素：０．１〜２原子％を含有し、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薄膜は、従来の純銅薄膜とほぼ同等の比抵抗を有し、さらに高温に曝されてもヒロックおよびボイドの熱欠陥が発生することが少なく、さらにガラス基板表面に対する密着性に優れていることから、かかる成分組成を有する銅合金薄膜は液晶表示装置用配線および電極として使用した場合に優れた効果を奏する、
（ロ）純銅（特に純度：９９．９９％以上の無酸素銅）に、Ａｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０１〜１原子％含有し、さらに希土類元素の内の１種または２種以上を合計で０．０１〜１原子％を含有し、さらに酸素：０．１〜２原子％を含有し、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薄膜は、従来の純銅薄膜とほぼ同等の比抵抗を有し、さらに高温に曝されてもヒロックおよびボイドの熱欠陥が発生することが少なく、さらにガラス基板表面に対する密着性に優れていることから、かかる成分組成を有する銅合金薄膜は液晶表示装置用配線および電極として使用した場合に優れた効果を奏する、
という研究結果が得られたのである。
Therefore, the present inventors have developed a copper alloy thin film having low specific resistance, excellent adhesion to the glass substrate surface, and extremely low generation of thermal defects such as hillocks and voids even when exposed to high temperatures. Has been studied to apply to the wiring and electrodes in liquid crystal display devices. as a result,
(I) Pure copper (particularly purity: 99.99% or more oxygen-free copper) contains one or more of Ag, Ca, Mg and Zn in a total amount of 0.01 to 1 atomic%, and The copper alloy thin film having a composition containing oxygen: 0.1 to 2 atomic% and the balance consisting of Cu and inevitable impurities has a specific resistance substantially equal to that of a conventional pure copper thin film, and is exposed to a high temperature. Since the thermal defects of hillocks and voids are less likely to occur and the adhesion to the glass substrate surface is excellent, the copper alloy thin film having such a component composition is excellent when used as wiring and electrodes for liquid crystal display devices. Have an effect,
(B) Pure copper (especially purity: 99.99% or more oxygen-free copper) contains one or more of Ag, Ca, Mg and Zn in a total amount of 0.01 to 1 atomic%, One or more of the rare earth elements contain a total of 0.01 to 1 atom%, further contain oxygen: 0.1 to 2 atom%, and the balance is composed of Cu and inevitable impurities. Copper alloy thin film has almost the same specific resistance as that of conventional pure copper thin film, and even when exposed to high temperatures, hillock and void thermal defects are less likely to occur, and it has excellent adhesion to the glass substrate surface. Therefore, a copper alloy thin film having such a component composition has an excellent effect when used as a wiring for a liquid crystal display device and an electrode,
The research result was 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）Ａｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０１〜１原子％含有し、さらに酸素：０．１〜２原子％を含有し、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薄膜からなる熱欠陥発生がなくかつ密着性に優れた液晶表示装置用配線、
（２）Ａｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０１〜１原子％含有し、さらに酸素：０．１〜２原子％を含有し、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薄膜からなる熱欠陥発生がなくかつ密着性に優れた液晶表示装置用電極、
（３）Ａｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０１〜１原子％を含有し、さらに希土類元素の内の１種または２種以上を合計で０．０１〜１原子％を含有し、さらに酸素：０．１〜２原子％を含有し、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薄膜からなる熱欠陥発生がなくかつ密着性に優れた液晶表示装置用配線、
（４）Ａｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０１〜１原子％含有し、さらに希土類元素の内の１種または２種以上を合計で０．０１〜１原子％を含有し、さらに酸素：０．１〜２原子％を含有し、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薄膜からなる熱欠陥発生がなくかつ密着性に優れた液晶表示装置用電極、に特徴を有するものである。
This invention was made based on the above research results,
(1) One or more of Ag, Ca, Mg, and Zn are contained in a total amount of 0.01 to 1 atom%, oxygen is further contained in an amount of 0.1 to 2 atom%, and the balance is Cu and A wiring for a liquid crystal display device free from the occurrence of thermal defects and having excellent adhesion, comprising a copper alloy thin film having a composition comprising inevitable impurities,
(2) One or more of Ag, Ca, Mg and Zn are contained in a total amount of 0.01 to 1 atom%, further oxygen: 0.1 to 2 atom%, the balance being Cu and An electrode for a liquid crystal display device that is free from thermal defects and is excellent in adhesiveness, comprising a copper alloy thin film having a composition comprising inevitable impurities,
(3) One or more of Ag, Ca, Mg and Zn are contained in a total amount of 0.01 to 1 atomic%, and one or more of the rare earth elements are further added in a total amount of 0.001. Containing 01 to 1 atomic%, further containing oxygen: 0.1 to 2 atomic%, the balance being free from the occurrence of thermal defects consisting of a copper alloy thin film having a composition consisting of Cu and inevitable impurities, and excellent adhesion Wiring for liquid crystal display devices,
(4) A total of 0.01 to 1 atomic% of one, two or more of Ag, Ca, Mg and Zn, and 0.01 or more of one or more of the rare earth elements in total. A liquid crystal containing no more than 1 atomic%, further containing oxygen: 0.1 to 2 atomic%, the balance being made of a copper alloy thin film having a composition consisting of Cu and inevitable impurities, and having excellent adhesion The display device electrode has a feature.
この発明の液晶表示装置の配線および電極を構成する銅合金薄膜は、Ａｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０３〜５原子％を含有し、さらに必要に応じて希土類元素の内の１種または２種以上を合計で０．０１〜１原子％を含有し、残部がＣｕおよび不可避不純物からなる組成を有するターゲットを用い、酸素を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形成することができる。そして、このターゲットは、まず純度：９９．９９％以上の無酸素銅を、不活性ガス雰囲気中、高純度グラファイトモールド内で高周波溶解し、得られた純銅溶湯にＡｇ、Ｃａ、ＭｇおよびＺｎの内の１種または２種以上を合計で０．０３〜５原子％を添加して溶解し、さらに必要に応じて希土類元素の内の１種または２種以上を合計で０．０１〜１原子％を添加して溶解し、得られた溶湯を不活性ガス雰囲気中で鋳造し急冷凝固させたのち、さらに熱間圧延し、最後に歪取り焼鈍を施すことにより作製する。このようにして得られたターゲットをバッキングプレートに接合し、酸素を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形成することができる。 The copper alloy thin film constituting the wiring and electrode of the liquid crystal display device of the present invention contains 0.03 to 5 atomic% in total of one or more of Ag, Ca, Mg and Zn, and further necessary In accordance with the above, an inert gas atmosphere containing oxygen using a target having a total content of 0.01 to 1 atomic% of one or more of rare earth elements, with the balance being composed of Cu and inevitable impurities It can be formed by sputtering in. In this target, oxygen-free copper having a purity of 99.99% or higher is firstly melted in a high-purity graphite mold in an inert gas atmosphere, and Ag, Ca, Mg, and Zn are added to the obtained pure copper melt. 1 or 2 or more of them are added and dissolved in a total amount of 0.03 to 5 atom%, and if necessary, one or more of the rare earth elements are added to 0.01 to 1 atoms in total. The molten metal thus obtained is cast in an inert gas atmosphere, rapidly solidified, then hot-rolled, and finally subjected to strain relief annealing. The target thus obtained can be formed by joining to a backing plate and sputtering in an inert gas atmosphere containing oxygen.
この発明の液晶表示装置における配線および電極を構成する銅合金薄膜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）Ａｇ、Ｃａ、ＭｇおよびＺｎ：
配線および電極を構成する銅合金薄膜に含まれるこれら成分は結晶粒を微細化し、液晶表示装置における配線および電極を構成する銅合金薄膜のヒロックおよびボイドなどの熱欠陥の発生を抑制する作用を有するが、その含有量が０．０１原子％未満では所望の効果が得られないので好ましくなく、一方、１原子％を越えて含有するとヒロックが発生するようになるので好ましくない。したがって、この発明の配線および電極を構成する銅合金薄膜に含まれるこれら成分の含有量は０．０１〜１原子％に定めた。
The reason why the range of the component composition of the copper alloy thin film constituting the wiring and electrode in the liquid crystal display device of the present invention is limited as described above will be described.
(A) Ag, Ca, Mg and Zn:
These components contained in the copper alloy thin film constituting the wiring and electrode have the effect of miniaturizing crystal grains and suppressing the occurrence of thermal defects such as hillocks and voids in the copper alloy thin film constituting the wiring and electrode in the liquid crystal display device. However, if the content is less than 0.01 atomic%, the desired effect cannot be obtained, which is not preferable. On the other hand, if the content exceeds 1 atomic%, hillocks are generated, which is not preferable. Therefore, the content of these components contained in the copper alloy thin film constituting the wiring and electrode of the present invention is set to 0.01 to 1 atomic%.
（ｂ）酸素：
この発明の配線および電極を構成する銅合金薄膜に含まれる酸素はガラス基板表面に対する密着性を一層向上させ、さらに下地のガラス基板およびシリコンウエハに含まれるＳｉの銅合金薄膜への拡散を防止する作用を有するが、酸素を０．１原子％未満添加しても所望の効果が得られず、一方、２原子％を越えて添加すると、配線および電極を構成する銅合金薄膜の比抵抗が上昇するので好ましくない。したがって、配線および電極を構成する銅合金薄膜に含まれる酸素０．１〜２原子％に定めた。
(B) Oxygen:
The oxygen contained in the copper alloy thin film constituting the wiring and electrode of the present invention further improves the adhesion to the glass substrate surface, and further prevents the diffusion of Si contained in the underlying glass substrate and silicon wafer into the copper alloy thin film. Although there is an effect, the desired effect cannot be obtained even if oxygen is added in an amount of less than 0.1 atomic%. On the other hand, if it is added in excess of 2 atomic%, the specific resistance of the copper alloy thin film constituting the wiring and electrode is increased. This is not preferable. Therefore, the oxygen content is set to 0.1 to 2 atomic% contained in the copper alloy thin film constituting the wiring and the electrode.
（ｃ）希土類元素：
希土類元素はガラス基板表面に対する密着性を一層向上させるので、必要に応じて添加するが、その含有量が０．０１原子％未満添加しても所望の効果が得られず、一方、１原子％を越えて添加すると、配線および電極を構成する銅合金薄膜の比抵抗が上昇するので好ましくない。したがって、配線および電極を構成する銅合金薄膜に含まれる希土類元素を０．０１〜１原子％に定めた。添加する希土類元素はＰｒ，Ｎｄ，Ｅｕ，Ｇｄ，ＴｂおよびＤｙであることが一層好ましい。
(C) Rare earth elements:
The rare earth element further improves the adhesion to the glass substrate surface, so it is added as necessary, but even if its content is less than 0.01 atomic%, the desired effect cannot be obtained, while 1 atomic%. Addition exceeding the range is not preferable because the specific resistance of the copper alloy thin film constituting the wiring and the electrode increases. Therefore, the rare earth element contained in the copper alloy thin film constituting the wiring and the electrode is set to 0.01 to 1 atomic%. More preferably, the rare earth elements to be added are Pr, Nd, Eu, Gd, Tb and Dy.
この発明の液晶表示装置における配線および電極は、ガラス基板表面に対する密着性に優れ、高温に曝されてもヒロックおよびボイドなどの熱欠陥の発生がなく、さらに比抵抗が低いことから高精細化し大型化した液晶表示装置の配線および電極に使用しても消費電力を少なくすることができるなど優れた効果を奏するものである。 The wiring and electrodes in the liquid crystal display device of the present invention have excellent adhesion to the glass substrate surface, do not generate thermal defects such as hillocks and voids even when exposed to high temperatures, and have a low specific resistance, resulting in high definition and large size. Even if it is used for the wiring and electrodes of the liquid crystal display device, it has excellent effects such as reduced power consumption.
実施例１
純度：９９．９９質量％の無酸素銅を用意し、この無酸素銅をＡｒガス雰囲気中、高純度グラファイトモールド内で高周波溶解し、得られた溶湯にＡｇ、Ｃａ、ＭｇおよびＺｎのうちの１種もしくは２種以上を添加し溶解して表１に示される成分組成を有する溶湯となるように成分調整し、得られた溶湯を冷却されたカーボン鋳型に鋳造し、さらに熱間圧延したのち最終的に歪取り焼鈍し、得られた圧延体の表面を旋盤加工して外径：２００mm×厚さ：５mmの寸法を有し、表１に示される成分組成を有するターゲットＡ〜ｂを作製した。
Example 1
Purity: 99.99 mass% oxygen-free copper was prepared, this oxygen-free copper was melted at high frequency in an Ar gas atmosphere in a high-purity graphite mold, and the resulting molten metal was selected from among Ag, Ca, Mg and Zn. After adding one or two or more types and melting them to adjust the components so as to form a molten metal having the component composition shown in Table 1, the obtained molten metal is cast into a cooled carbon mold and further hot-rolled. Finally, strain relief annealing is performed, and the surface of the obtained rolled body is turned to produce targets A to b having dimensions of outer diameter: 200 mm × thickness: 5 mm and having the composition shown in Table 1. did.
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表１に示されるターゲットＡ〜ｂ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ターゲットＡ〜ｂ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 targets A and b shown in Table 1 are superposed on the oxygen-free copper backing plate, and the targets A and b are made of oxygen-free copper by indium soldering at a temperature of 200 ° C. A target with a backing plate was prepared by bonding to the backing plate.
これらターゲットＡ〜ｂ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（縦：５０ｍｍ、横：５０ｍｍ、厚さ：０．７ｍｍの寸法を有するコーニング社製１７３７）との距離：７０mmとなるようにセットし、
電源：直流方式、
スパッタパワー：６００Ｗ、
到達真空度：４×１０−５Ｐａ、
雰囲気ガス組成：表１に示される酸素を含有したＡｒ混合ガス、
Ａｒガス圧：０．６７Ｐａ、
ガラス基板加熱温度：１５０℃、
の条件でスパッタリングすることによりガラス基板の表面に厚さ：３００ｎｍを有し、表２〜３に示される成分組成を有する本発明銅合金薄膜１〜２１、比較銅合金薄膜１〜６および従来銅合金からなる薄膜(以下、従来銅合金薄膜という)１を形成した。
A target with a backing plate obtained by soldering these targets A to b to an oxygen-free copper backing plate is used as a target and a glass substrate (length: 50 mm, width: 50 mm, thickness: 0.7 mm). Set the distance to 1735): 70mm,
Power supply: DC method,
Sputter power: 600W
Ultimate vacuum: 4 × 10 −5 Pa,
Atmospheric gas composition: Ar mixed gas containing oxygen as shown in Table 1,
Ar gas pressure: 0.67 Pa,
Glass substrate heating temperature: 150 ° C.
The present invention copper alloy thin films 1 to 21, comparative copper alloy thin films 1 to 6 and conventional copper having a thickness of 300 nm on the surface of the glass substrate and having the composition shown in Tables 2 to 3 by sputtering under the conditions of A thin film made of an alloy (hereinafter referred to as a conventional copper alloy thin film) 1 was formed.
得られた本発明銅合金薄膜１〜２１、比較銅合金薄膜１〜６および従来銅合金薄膜１の５点の比抵抗を四探針法により測定し、その平均値を求め、それらの結果を表２〜３に示した。
さらに、得られた本発明銅合金薄膜１〜２１、比較銅合金薄膜１〜６および従来銅合金薄膜１に、ＪＩＳ-Ｋ５４００に準じ、１ｍｍ間隔で碁盤目状に切れ目を入れた後、３Ｍ社製スコッチテープで引き剥がす碁盤目付着試験を実施し、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１００個の碁盤目の内で密着している碁盤目の数を測定し、その結果を（密着数／１００）として表２〜３に示し、ガラス基板に対する密着性を評価した。
さらに、得られた本発明銅合金薄膜１〜２１、比較銅合金薄膜１〜６および従来銅合金薄膜１をそれぞれ赤外線加熱炉に装入し、到達真空度：４×１０−４Ｐａの真空雰囲気中、昇温速度：５℃／ｍｉｎ、最高温度：３５０℃、３０分間保持の熱処理を施したのち真空冷却した。これら熱処理を施し真空冷却した本発明銅合金薄膜１〜２１、比較銅合金薄膜１〜６および従来銅合金薄膜１の表面を１０００倍の光学顕微鏡で５個所の膜表面を観察し、ヒロックボイドの発生の有無を観察し、その結果を表２〜３に示し、さらにＴＥＭで膜の５個所の断面を観察して膜内ボイドの発生の有無を観察し、その結果を表２〜３に示した。
The obtained copper alloy thin films 1 to 21, comparative copper alloy thin films 1 to 6 and the conventional copper alloy thin film 1 were measured for specific resistance at five points by the four-probe method, and the average value was obtained. It showed in Tables 2-3.
Further, after cutting the obtained copper alloy thin films 1 to 21, comparative copper alloy thin films 1 to 6 and the conventional copper alloy thin film 1 according to JIS-K5400 in a grid pattern at intervals of 1 mm, 3M Company A cross-cut adhesion test to be peeled off with a scotch tape made is performed, and the number of cross-cuts that are in close contact with each other within 100 cross-cuts attached to the glass substrate within the 10 mm square in the center of the glass substrate is measured The result was shown to (Table 2-3) as (the number of adhesion | attachment / 100), and the adhesiveness with respect to a glass substrate was evaluated.
Furthermore, the obtained copper alloy thin films 1 to 21, comparative copper alloy thin films 1 to 6 and the conventional copper alloy thin film 1 were respectively charged into an infrared heating furnace, and a vacuum atmosphere of 4 × 10 −4 Pa was reached. Medium, heat-up rate: 5 ° C./min, maximum temperature: 350 ° C., heat treatment for 30 minutes, followed by vacuum cooling. The surface of the copper alloy thin films 1 to 21, the comparative copper alloy thin films 1 to 6 and the conventional copper alloy thin film 1 which have been heat-treated and vacuum-cooled are observed at five locations with a 1000 × optical microscope. The presence or absence of occurrence was observed, the results are shown in Tables 2 to 3, and the cross section of the film was observed with a TEM to observe the presence or absence of voids in the film. The results are shown in Tables 2 to 3 It was.
表１〜３に示される結果から、本発明銅合金薄膜１〜２１と酸素を含む高純度銅からなる従来銅合金薄膜１を比較すると、共にガラス基板に対する密着性に優れかつ比抵抗が極めて小さいものの、従来銅合金薄膜１はヒロックボイドおよび膜内ボイドが発生するのに対し、本発明銅合金薄膜１〜２１はヒロックおよびボイドの発生がないこと、この発明の条件から外れて少ないＡｇ、Ｃａ、Ｍｇ、Ｚｎおよび酸素を含む比較銅合金薄膜１〜６は比抵抗が大きくなり過ぎたり、ヒロックおよびボイドなどが発生するなどして好ましくないとこ、などが分かる。 From the results shown in Tables 1 to 3, when comparing the copper alloy thin films 1 to 21 of the present invention with the conventional copper alloy thin film 1 made of high-purity copper containing oxygen, both have excellent adhesion to the glass substrate and extremely low specific resistance. However, the conventional copper alloy thin film 1 generates hillock voids and in-film voids, whereas the copper alloy thin films 1 to 21 of the present invention do not generate hillocks and voids. It can be seen that the comparative copper alloy thin films 1 to 6 containing Mg, Zn, and oxygen are not preferable because the specific resistance becomes too large, hillocks, voids, and the like are generated.
実施例２
基板としてガラス基板の代わりにシリコン基板（表面に厚さ：２００ｎｍのアモルファスシリコンを成膜した４インチシリコンウエハ）を用いる以外は実施例１と全く同じ条件で本発明銅合金薄膜２２〜４２、比較銅合金薄膜７〜１２および従来銅合金薄膜２の比抵抗を測定し、さらに密着性を評価し、ヒロックボイドの発生の有無を観察し、さらに膜内ボイドの発生の有無を観察し、それらの結果を表４〜５に示した。
Example 2
The copper alloy thin films 22 to 42 of the present invention were compared under the same conditions as in Example 1 except that a silicon substrate (a 4 inch silicon wafer having a thickness of 200 nm of amorphous silicon formed on the surface) was used instead of the glass substrate. The specific resistances of the copper alloy thin films 7 to 12 and the conventional copper alloy thin film 2 are measured, the adhesion is further evaluated, the presence or absence of hillock voids is observed, the presence or absence of voids in the film is further observed, The results are shown in Tables 4-5.
表４〜５から、シリコン基板に形成された本発明銅合金薄膜２２〜４２、比較銅合金薄膜７〜１２および従来銅合金薄膜２は、実施例１とほぼ同じ結果が得られることが分かる。 From Tables 4 to 5, it can be seen that the copper alloy thin films 22 to 42 of the present invention, the comparative copper alloy thin films 7 to 12 and the conventional copper alloy thin film 2 formed on the silicon substrate have almost the same results as in Example 1.
実施例３
純度：９９．９９質量％の無酸素銅を用意し、この無酸素銅をＡｒガス雰囲気中、高純度グラファイトモールド内で高周波溶解し、得られた溶湯にＡｇ、Ｃａ、ＭｇおよびＺｎを添加し溶解し、さらに希土類元素（Ｐｒ，Ｎｄ，Ｅｕ，Ｇｄ，ＴｂおよびＤｙを添加し溶解して表６に示される成分組成を有する溶湯となるように成分調整し、得られた溶湯を冷却されたカーボン鋳型に鋳造し、さらに熱間圧延したのち最終的に歪取り焼鈍し、得られた圧延体の表面を旋盤加工して外径：２００mm×厚さ：５mmの寸法を有し、表１に示される成分組成を有するターゲットｃ〜ｚを作製した。
Example 3
Purity: Prepare 99.99 mass% oxygen-free copper, melt this oxygen-free copper in a high-purity graphite mold in an Ar gas atmosphere, and add Ag, Ca, Mg, and Zn to the resulting molten metal. The components were adjusted so that the molten metal was melted and further added with rare earth elements (Pr, Nd, Eu, Gd, Tb, and Dy and dissolved to have a component composition shown in Table 6, and the resulting molten metal was cooled. After casting into a carbon mold, hot rolling, and finally annealing to remove strain, the surface of the obtained rolled body is turned to have an outer diameter: 200 mm × thickness: 5 mm. Targets cz having the indicated component composition were made.
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表６に示されるターゲットｃ〜ｚ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ターゲットｃ〜ｚ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, the targets cz shown in Table 6 are superimposed on the oxygen-free copper backing plate, and the targets cz are made of oxygen-free copper by soldering indium at a temperature of 200 ° C. A target with a backing plate was prepared by bonding to the backing plate.
これらターゲットｃ〜ｚ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（縦：５０ｍｍ、横：５０ｍｍ、厚さ：０．７ｍｍの寸法を有するコーニング社製１７３７）との距離：７０mmとなるようにセットし、
電源：直流方式、
スパッタパワー：６００Ｗ、
到達真空度：４×１０−５Ｐａ、
雰囲気ガス組成：表１に示される酸素を含有したＡｒ混合ガス、
Ａｒガス圧：０．６７Ｐａ、
ガラス基板加熱温度：１５０℃、
の条件でスパッタリングすることによりガラス基板の表面に厚さ：３００ｎｍを有し、表７〜８に示される成分組成を有する本発明銅合金薄膜４３〜６６を形成した。
A target with a backing plate obtained by soldering these targets c to z to an oxygen-free copper backing plate, a target and a glass substrate (length: 50 mm, width: 50 mm, thickness: 0.7 mm, Corning) Set the distance to 1735): 70mm,
Power supply: DC method,
Sputter power: 600W
Ultimate vacuum: 4 × 10 −5 Pa,
Atmospheric gas composition: Ar mixed gas containing oxygen as shown in Table 1,
Ar gas pressure: 0.67 Pa,
Glass substrate heating temperature: 150 ° C.
The present invention copper alloy thin films 43 to 66 having a thickness of 300 nm on the surface of the glass substrate and the component compositions shown in Tables 7 to 8 were formed by sputtering under the conditions described above.
得られた本発明銅合金薄膜４３〜６６の５点の比抵抗を四探針法により測定し、その平均値を求め、それらの結果を表７〜８に示した。
さらに、得られた本発明銅合金薄膜４３〜６６に、ＪＩＳ-Ｋ５４００に準じ、１ｍｍ間隔で碁盤目状に切れ目を入れた後、３Ｍ社製スコッチテープで引き剥がす碁盤目付着試験を実施し、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１００個の碁盤目の内で密着している碁盤目の数を測定し、その結果を（密着数／１００）として表７〜８に示し、ガラス基板に対する密着性を評価した。
さらに、得られた本発明銅合金薄膜４３〜６６をそれぞれ赤外線加熱炉に装入し、到達真空度：４×１０−４Ｐａの真空雰囲気中、昇温速度：５℃／ｍｉｎ、最高温度：３５０℃、３０分間保持の熱処理を施したのち真空冷却した。これら熱処理を施し真空冷却した本発明銅合金薄膜４３〜６６の表面を１０００倍の光学顕微鏡で５個所の膜表面を観察し、ヒロックボイドの発生の有無を観察し、その結果を表７〜８に示し、さらにＴＥＭで膜の５個所の断面を観察して膜内ボイドの発生の有無を観察し、その結果を表７〜８に示した。
The specific resistances at five points of the obtained copper alloy thin films 43 to 66 of the present invention were measured by the four-probe method, the average value was obtained, and the results are shown in Tables 7 to 8.
Furthermore, according to JIS-K5400, the obtained copper alloy thin films 43 to 66 of the present invention were cut in a grid pattern at intervals of 1 mm, and then a grid adhesion test to be peeled off with a 3M Scotch tape was performed. Tables 7 to 8 were measured by measuring the number of grids in close contact with each other among the 100 grids adhered to the glass substrate within a 10 mm square in the center of the glass substrate, and the results were expressed as (number of adhesions / 100). The adhesion to the glass substrate was evaluated.
Furthermore, the obtained copper alloy thin films 43 to 66 of the present invention were charged into an infrared heating furnace, respectively, in a vacuum atmosphere with a degree of ultimate vacuum of 4 × 10 −4 Pa, a temperature rising rate: 5 ° C./min, and a maximum temperature: A heat treatment was performed at 350 ° C. for 30 minutes, followed by vacuum cooling. The surfaces of the copper alloy thin films 43 to 66 of the present invention that were heat-treated and vacuum-cooled were observed at five locations with a 1000 × optical microscope to observe the presence or absence of hillock voids. The results are shown in Tables 7 to 8 Furthermore, the cross section of five places of the film | membrane was observed with TEM, the presence or absence of the generation | occurrence | production of the void in a film | membrane was observed, and the result was shown to Tables 7-8.
表６〜８に示される本発明銅合金薄膜４３〜６６と表３の酸素を含む銅からなる従来銅合金薄膜１とを比較すると、共にガラス基板に対する密着性に優れかつ比抵抗が極めて小さいものの、従来銅合金薄膜１はヒロックボイドおよび膜内ボイドが発生するのに対し、本発明銅合金薄膜４３〜６６はヒロックおよびボイドの発生がないことが分かる。 When the copper alloy thin films 43 to 66 of the present invention shown in Tables 6 to 8 and the conventional copper alloy thin film 1 made of copper containing oxygen shown in Table 3 are compared, both have excellent adhesion to the glass substrate and extremely low specific resistance. It can be seen that the conventional copper alloy thin film 1 generates hillock voids and in-film voids, whereas the copper alloy thin films 43 to 66 of the present invention do not generate hillocks and voids.
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| JP5269533B2 (en) * | 2008-09-26 | 2013-08-21 | 三菱マテリアル株式会社 | Thin film transistor |
| KR101184240B1 (en) | 2008-10-24 | 2012-09-21 | 가부시키가이샤 알박 | Method for manufacturing thin film transistor and thin film transistor |
| JP5541651B2 (en) * | 2008-10-24 | 2014-07-09 | 三菱マテリアル株式会社 | Sputtering target for wiring film formation for thin film transistors |
| 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 |
| JP5354781B2 (en) * | 2009-03-11 | 2013-11-27 | 三菱マテリアル株式会社 | Thin film transistor having barrier layer as constituent layer and Cu alloy sputtering target used for sputtering film formation of said barrier layer |
| WO2010143609A1 (en) * | 2009-06-12 | 2010-12-16 | 株式会社アルバック | Method for producing electronic device, electronic device, semiconductor device, and transistor |
| JP6394064B2 (en) * | 2013-08-13 | 2018-09-26 | 大同特殊鋼株式会社 | Cu alloy target material, Cu alloy target, Cu alloy film, and touch panel |
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