JP2009168937A - Copper thin film with superior adhesiveness, and wiring and electrode for liquid crystal display comprising the copper thin film - Google Patents
Copper thin film with superior adhesiveness, and wiring and electrode for liquid crystal display comprising the copper thin film Download PDFInfo
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- JP2009168937A JP2009168937A JP2008004594A JP2008004594A JP2009168937A JP 2009168937 A JP2009168937 A JP 2009168937A JP 2008004594 A JP2008004594 A JP 2008004594A JP 2008004594 A JP2008004594 A JP 2008004594A JP 2009168937 A JP2009168937 A JP 2009168937A
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- 239000010949 copper Substances 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010409 thin film Substances 0.000 title claims abstract description 50
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000005477 sputtering target Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 229910016509 CuF 2 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
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- Non-Insulated Conductors (AREA)
- Liquid Crystal (AREA)
- Physical Vapour Deposition (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
この発明は、ガラス基板表面に対する密着性に優れた銅薄膜に関するものであり、この銅薄膜は液晶表示装置の配線および電極など使用されるものである。 The present invention relates to a copper thin film having excellent adhesion to the surface of a glass substrate, and this copper thin film is used for wiring and electrodes of a liquid crystal display device.
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ガラス基板表面に対する密着性が低いために比較的軽微な振動を受けても剥離し、そのために故障の原因となっていた。これを改善するために、酸素を含有させた銅薄膜が提案されており（特許文献１、２、３参照）、この酸素を含有した銅薄膜はガラス基板表面に対する密着性が高くなることが知られている。
近年、液晶表示装置は益々大型化しており、５０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。しかし、配線は細くなるほど振動などに対して剥離しやすくなり、そのために配線の比抵抗を低く維持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一層優れた銅薄膜が求められている。 In recent years, liquid crystal display devices are becoming larger and larger liquid crystal panels with a size of 50 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. However, the thinner the wiring, the easier it is to peel off against vibrations, etc. Therefore, there is a need for a copper thin film that maintains a low specific resistance of the wiring and that has better adhesion to the glass substrate surface so that the wiring does not peel off. It has been.
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た銅薄膜を開発し、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、純銅（特に純度：９９．９９％以上の無酸素銅）にフッ素：０．０１〜５原子％を含有させた銅薄膜は、従来の純銅薄膜とほぼ同等の比抵抗を有し、さらにガラス基板表面に対する密着性に一層優れていることから、かかる成分組成を有する銅薄膜を液晶表示装置の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。
Accordingly, the present inventors have developed a copper thin film having a low specific resistance and excellent adhesion to the glass substrate surface, and have studied to apply this to a wiring and an electrode in a liquid crystal display device.
As a result, the copper thin film containing fluorine: 0.01 to 5 atomic% in pure copper (especially purity: 99.99% or more oxygen-free copper) has a resistivity substantially equal to that of the conventional pure copper thin film, Furthermore, since the adhesion to the surface of the glass substrate is further excellent, a research result has been obtained that a copper thin film having such a component composition has an excellent effect when used as a wiring and an electrode of a liquid crystal display device. .
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）フッ素：０．０１〜５原子％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密着性に優れた銅薄膜、
（２）前記（１）記載の成分組成を有する銅薄膜からなる密着性に優れた液晶表示装置用配線、
（３）前記（１）記載の成分組成を有する銅薄膜からなる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) Fluorine: a copper thin film having excellent adhesion with a component composition containing 0.01 to 5 atomic%, the balance being Cu and inevitable impurities,
(2) Wiring for a liquid crystal display device having excellent adhesion comprising a copper thin film having the component composition described in (1),
(3) It has the characteristics in the electrode for liquid crystal display devices excellent in the adhesiveness which consists of a copper thin film which has the component composition of said (1) description.
この発明の銅薄膜並びにこの銅薄膜からなる液晶表示装置の配線および電極は、純銅製ターゲットを用い、フッ素を含む不活性ガス中でスパッタリングすることにより成膜することができるが、Ｆ：０．０１〜５原子％、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作製し、このターゲットを用い、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％以上の無酸素銅粉末に銅のフッ化物（例えば、ＣｕＦ２、Ｃｕ（ＯＨ）Ｆなど）からなる粉末を混合し、得られた混合粉末を加圧成型して加圧成型体を作製し、この加圧成型体を不活性ガス雰囲気中、温度：７００〜９５０℃で焼結し、得られた焼結体を所定の寸法に切削することにより得られる。したがって、この発明は、
（４）フッ素：０．０１〜５原子％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スパッタリングターゲット、に特徴を有するものである。
The copper thin film of the present invention and the wiring and electrodes of the liquid crystal display device comprising the copper thin film can be formed by sputtering in an inert gas containing fluorine using a pure copper target. A target having a composition of 01 to 5 atomic%, the balance being Cu and inevitable impurities, is prepared, and this target is used to perform sputtering in an inert gas atmosphere. In this target, first, a powder made of copper fluoride (for example, CuF 2 , Cu (OH) F, etc.) is mixed with oxygen-free copper powder having a purity of 99.99% or more, and the obtained mixed powder is used. A pressure-molded body is produced by pressure molding, the pressure-molded body is sintered in an inert gas atmosphere at a temperature of 700 to 950 ° C., and the obtained sintered body is cut to a predetermined size. Is obtained. Therefore, the present invention
(4) Fluorine: A sputtering target having a component composition containing 0.01 to 5 atom%, with the balance being Cu and inevitable impurities.
次に、この発明の銅薄膜並びにこの銅薄膜からなる液晶表示装置における配線および電極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。この発明の配線および電極を構成する銅薄膜に含まれるフッ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に含まれるＳｉの銅薄膜への拡散を防止する作用を有するので添加するが、フッ素を０．０１原子％未満添加しても所望の効果が得られず、一方、５原子％を越えて添加すると、配線および電極を構成する銅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薄膜に含まれるフッ素：０．０１〜５原子％に定めた。 Next, the reason why the range of the component composition of the wiring and the electrode in the copper thin film of the present invention and the liquid crystal display device comprising the copper thin film is limited as described above will be described. Fluorine contained in the copper thin film constituting the wiring and electrode of the present invention is added because it further improves the adhesion to the glass substrate surface and further prevents the diffusion of Si contained in the underlying glass substrate into the copper thin film. However, the addition of less than 0.01 atomic% of fluorine does not provide the desired effect. On the other hand, the addition of more than 5 atomic% is preferable because the specific resistance of the copper thin film constituting the wiring and electrode is increased. Absent. Therefore, fluorine contained in the copper thin film constituting the wiring and the electrode was set to 0.01 to 5 atomic%.
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、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 and low specific resistance, so that even when used for the wiring and electrodes of liquid crystal display devices with high definition and large size, power consumption is reduced. It has excellent effects such as being able to
実施例１
純度：９９．９９質量％以上の純銅粉末を用意し、さらにＣｕＦ２粉末を用意し、この純銅粉末にＣｕＦ２粉末を表１に示される割合で配合し混合して混合粉末を作製し、得られた混合粉末を金型に充填して成型し、得られた成型体をＡｒガス雰囲気中、温度：９００℃で焼成し、得られた焼成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本発明ターゲット１〜１０および比較ターゲット１〜２を作製した。
Example 1
Purity: A pure copper powder of 99.99% by mass or more is prepared, and further a CuF 2 powder is prepared. The pure copper powder is mixed and mixed with the CuF 2 powder shown in Table 1 to obtain a mixed powder. The obtained mixed powder is filled into a mold and molded. The obtained molded body is fired in an Ar gas atmosphere at a temperature of 900 ° C., and the surface of the obtained fired body is turned to have an outer diameter of 200 mm × Thickness: Inventive targets 1 to 10 and comparative targets 1 to 2 having the component composition shown in Table 1 having a dimension of 5 mm were prepared.
これら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：５００Ｗ、
到達真空度：４×１０−５Ｐａ、
雰囲気ガス組成：Ａｒ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に示される成分組成を有する本発明銅薄膜１〜１０および比較銅薄膜１〜２を形成した。
These backing plate-equipped targets were set so that the distance between the target and the glass substrate (vertical: 50 mm, horizontal: 50 mm, thickness: 1737 made by Corning Inc. having dimensions of 0.7 mm) was 70 mm,
Power supply: DC method,
Sputter power: 500W
Ultimate vacuum: 4 × 10 −5 Pa,
Atmospheric gas composition: Ar gas,
Ar gas pressure: 0.67 Pa,
Glass substrate heating temperature: 150 ° C.
The present invention copper thin films 1 to 10 and comparative copper thin films 1 to 2 having a thickness of 300 nm on the surface of the glass substrate and having the composition shown in Table 2 were formed by sputtering under the conditions described above.
得られた本発明銅薄膜１〜１０および比較銅薄膜１〜２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に示した。 The five specific resistances of the obtained inventive copper thin films 1 to 10 and comparative copper thin films 1 and 2 were measured by a four-probe method, and the average value was determined. The results are shown in Table 2.
さらに、得られた本発明銅薄膜１〜１０および比較銅薄膜１〜２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に示し、ガラス基板に対する密着性を評価した。
従来例１
溶解鋳造して得られた純銅ターゲットを用意し、この純銅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：５００Ｗ、
到達真空度：４×１０−５Ｐａ、
雰囲気ガス組成：Ａｒ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に示される純銅からなる薄膜(以下、従来薄膜１という)を形成した。
さらに、先に用意した純銅ターゲットを用い、雰囲気ガス組成を酸素：２容量％含むＡｒガスとする以外は同じ条件でスパッタリングすることにより表２に示される酸素含有銅からなる薄膜(以下、従来薄膜２という)を形成した。
このようにして得られた従来薄膜１〜２について、実施例１と同様にして比抵抗を測定し、さらにガラス基板に対する密着性を評価し、その結果を表２に示した。
Further, the obtained copper thin films 1 to 10 and the comparative copper thin films 1 to 2 are cut into a grid pattern at intervals of 1 mm according to JIS-K5400, and then peeled off with a 3M Scotch tape. An adhesion test was conducted, and 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 was measured. ) As shown in Table 2, and the adhesion to the glass substrate was evaluated.
Conventional example 1
A pure copper target obtained by melting and casting was prepared, and the distance between the pure copper target and the glass substrate (vertical: 50 mm, horizontal: 50 mm, thickness: 1737 made by Corning Inc. having dimensions of 0.7 mm): 70 mm Set to be
Power supply: DC method,
Sputter power: 500W
Ultimate vacuum: 4 × 10 −5 Pa,
Atmospheric gas composition: Ar gas,
Ar gas pressure: 0.67 Pa,
Glass substrate heating temperature: 150 ° C.
By sputtering under the above conditions, a thin film (hereinafter referred to as the conventional thin film 1) having a thickness of 300 nm and made of pure copper shown in Table 2 was formed on the surface of the glass substrate.
Further, a thin film made of oxygen-containing copper shown in Table 2 (hereinafter referred to as a conventional thin film) is formed by sputtering under the same conditions except that the pure copper target prepared earlier is used and the atmospheric gas composition is Ar gas containing 2% by volume of oxygen. 2).
For the conventional thin films 1 and 2 thus obtained, the specific resistance was measured in the same manner as in Example 1, and the adhesion to the glass substrate was evaluated. The results are shown in Table 2.
Claims (5)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011122241A (en) * | 2009-11-13 | 2011-06-23 | Semiconductor Energy Lab Co Ltd | Method for packaging target material and method for mounting target |
| KR20140085307A (en) * | 2012-12-27 | 2014-07-07 | 제이에스알 가부시끼가이샤 | Composition for forming copper film, method for forming copper film, the copper film, wiring board, and electronic device |
| JP2014143172A (en) * | 2012-12-27 | 2014-08-07 | Jsr Corp | Composition for copper film formation, copper film formation method, copper film, wiring board and electronic apparatus |
| JP2014150048A (en) * | 2013-01-11 | 2014-08-21 | Jsr Corp | Copper film-forming composition, copper film-forming method, copper film, wiring board, and electronic device |
-
2008
- 2008-01-11 JP JP2008004594A patent/JP2009168937A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011122241A (en) * | 2009-11-13 | 2011-06-23 | Semiconductor Energy Lab Co Ltd | Method for packaging target material and method for mounting target |
| US8753491B2 (en) | 2009-11-13 | 2014-06-17 | Semiconductor Energy Laboratory Co., Ltd. | Method for packaging target material and method for mounting target |
| KR20140085307A (en) * | 2012-12-27 | 2014-07-07 | 제이에스알 가부시끼가이샤 | Composition for forming copper film, method for forming copper film, the copper film, wiring board, and electronic device |
| JP2014143172A (en) * | 2012-12-27 | 2014-08-07 | Jsr Corp | Composition for copper film formation, copper film formation method, copper film, wiring board and electronic apparatus |
| KR102021424B1 (en) * | 2012-12-27 | 2019-09-16 | 제이에스알 가부시끼가이샤 | Composition for forming copper film, method for forming copper film, the copper film, wiring board, and electronic device |
| JP2014150048A (en) * | 2013-01-11 | 2014-08-21 | Jsr Corp | Copper film-forming composition, copper film-forming method, copper film, wiring board, and electronic device |
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| A300 | Withdrawal of application because of no request for examination |
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