JP4714477B2 - Ag alloy film and manufacturing method thereof - Google Patents
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- 229910001316 Ag alloy Inorganic materials 0.000 title claims description 122
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000010408 film Substances 0.000 claims description 182
- 239000010409 thin film Substances 0.000 claims description 96
- 239000007789 gas Substances 0.000 claims description 59
- 238000004544 sputter deposition Methods 0.000 claims description 58
- 229910045601 alloy Inorganic materials 0.000 claims description 42
- 239000000956 alloy Substances 0.000 claims description 42
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052737 gold Inorganic materials 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 24
- 229910052718 tin Inorganic materials 0.000 claims description 22
- 238000005530 etching Methods 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 18
- 238000002310 reflectometry Methods 0.000 description 14
- 239000002356 single layer Substances 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、Ａｇを主成分とする合金膜(以下、「Ａｇ合金膜」と称す)の成膜プロセスに関し、特に二層からなるＡｇ合金膜、Ａｇ合金反射膜、Ａｇ合金電極膜及びそれらの製造方法に関する。 The present invention relates to a film forming process of an alloy film containing Ag as a main component (hereinafter referred to as “Ag alloy film”), and in particular, a two-layer Ag alloy film, an Ag alloy reflective film, an Ag alloy electrode film, and their It relates to a manufacturing method.
近年、ＬＣＤ等の表示装置の反射膜や電極膜として、Ａｌ合金に代わりＡｇ膜、Ａｇ合金膜が検討されている。このＡｇ合金膜とは、例えば、Ａｇを主体として微量の他の金属(例えば、Ａｕ、Ｃｕ、Ｓｉ、Ｎｄ、Ｐｔ、Ｐｄ、Ａｌ、Ｓｎ、Ｉｎ等)を一種類以上添加して合金化した組成を有するターゲットを用いて形成した膜のことであり、多数市販されている。 In recent years, Ag films and Ag alloy films have been studied as reflective films and electrode films for display devices such as LCDs instead of Al alloys. This Ag alloy film is alloyed by adding one or more kinds of other metals (for example, Au, Cu, Si, Nd, Pt, Pd, Al, Sn, In, etc.) mainly composed of Ag. It is a film formed using a target having a composition, and many are commercially available.
このようなＡｇ合金膜等は、高い反射特性と高い導電特性とを持つので、各種の表示素子、特に液晶表示素子(ＬＣＤ)用反射膜や配線膜に用いられている。近年、携帯電話その他のモバイル製品向けのＬＣＤにおいては、より高精細と同時に、より省電力（充電毎にバッテリーがより長時間使えること）であることが求められている。高精細の要求に対しては、ＬＣＤを構成する電極パターンを１０μｍ程度まで細くすると、抵抗が増して応答速度は遅くなるという問題がある。そこで、より低抵抗特性を持つＡｇやＡｇ合金からなる配線膜の開発が望まれている。また、省電力の要求に対しては、ＬＣＤを反射透過型にする方式を採用する場合、Ａｌ膜より高い反射特性を持つＡｇ膜やＡｇ合金膜の開発が望まれている。 Such an Ag alloy film or the like has high reflection characteristics and high conductivity characteristics, and is therefore used for various display elements, particularly for liquid crystal display element (LCD) reflection films and wiring films. In recent years, LCDs for mobile phones and other mobile products are required to have higher definition and at the same time more power saving (a battery can be used for a longer period of time for each charge). In response to the demand for high definition, when the electrode pattern constituting the LCD is thinned to about 10 μm, there is a problem that the resistance increases and the response speed becomes slow. Therefore, development of a wiring film made of Ag or an Ag alloy having lower resistance characteristics is desired. Further, in response to the demand for power saving, when adopting a system in which the LCD is made to be a reflection / transmission type, it is desired to develop an Ag film or an Ag alloy film having higher reflection characteristics than the Al film.
また、Ａｇを主成分としてこれにＡｕとＳｎ等とを添加してなるＡｇ合金膜が知られている(例えば、特許文献１参照)。さらに、本出願人は、Ａｇ合金(Ａｇ/Ａｕ/Ｓｎ)膜製造の際に、反応ガスとしてＡｒに酸素ガスや酸素含有ガスを添加したガスを用いてスパッタリングすると、基板に対して高い密着性を有する単層のＡｇ合金膜を得ることができることを提案している(特許文献２参照)。
ところで、Ａｇ合金膜は、その低抵抗特性から電極として有用である。ＬＣＤの構成には、一般に二種類ある。すなわち、反射膜上にカラーフィルターを形成し、さらにその上に電極膜＋液晶配向膜＋液晶層＋電極膜を順次形成するか、或いは反射膜上に電極膜＋液晶配向膜＋液晶層＋電極膜を順次形成し、さらにその上部にカラーフィルターを貼り付け形成することにより構成される。電極膜としては、現在、例えばＣｒ膜等が用いられている。有用なＡｇ合金膜が開発されれば、ＬＣＤ用の反射膜だけでなく、電極をも兼ねることができるので、Ｃｒ膜は不要となり、ＬＣＤの低コスト化が可能となる。 Incidentally, the Ag alloy film is useful as an electrode because of its low resistance characteristics. There are generally two types of LCD configurations. That is, a color filter is formed on the reflective film, and an electrode film + liquid crystal alignment film + liquid crystal layer + electrode film is sequentially formed thereon, or an electrode film + liquid crystal alignment film + liquid crystal layer + electrode on the reflective film. A film is formed in sequence, and a color filter is attached to the upper part of the film. Currently, for example, a Cr film or the like is used as the electrode film. If a useful Ag alloy film is developed, it can serve not only as a reflective film for LCD but also as an electrode, so that a Cr film becomes unnecessary, and the cost of LCD can be reduced.
しかるに、反射膜用途のみに用いる場合は、パターニングサイズは数１０μｍであればよいのに対して、反射電極用途に用いる場合には、数μｍであることが必要となる。パターニングサイズが細かくなれば、膜の基板に対する密着性が充分でなければ、パターン形成後の洗浄工程で剥がれてしまったり、パターンエッジが欠けるといった問題を生じる。 However, the patterning size may be several tens of μm when used only for a reflective film, whereas it needs to be several μm when used for a reflective electrode. If the patterning size becomes fine, if the adhesion of the film to the substrate is not sufficient, problems such as peeling off in the cleaning step after pattern formation and chipping of the pattern edge occur.
また、上記特許文献２(特開２００４−１９７１１７号公報)に示すように、ＡｇにＡｕとＳｎとを添加してなる単層のＡｇ合金膜の場合に、反応ガスとしてＡｒに酸素ガス又は酸素含有ガスを添加したガスを使用すると、高い密着性を得ることができる。この場合、さらに高い密着性を得るためには、Ｓｎ含有量及び酸素ガス又は酸素元素含有ガスの添加量を増加させればよいものの、含有量や添加量を増加させると、ＬＣＤ用の反射膜として必要な高反射率を保つことが困難になるという問題がある。 Further, as shown in Patent Document 2 (Japanese Patent Application Laid-Open No. 2004-197117), in the case of a single layer Ag alloy film formed by adding Au and Sn to Ag, oxygen gas or oxygen is added to Ar as a reaction gas. High adhesion can be obtained by using a gas to which a contained gas is added. In this case, in order to obtain higher adhesion, it is only necessary to increase the Sn content and the addition amount of oxygen gas or oxygen element-containing gas. However, if the content or addition amount is increased, the reflective film for LCD There is a problem that it becomes difficult to maintain the necessary high reflectivity.
Ｓｎ含有量の増加以外に密着性を得る方法として、下地としてＴｉＯ２等の膜を用い、この膜上にＡｇ合金膜を形成する方法も提案されているが、ＬＣＤ作製に必要な材料及び工程が増えるためコストアップとなってしまう。 As a method for obtaining adhesion other than the increase in Sn content, a method of using a film of TiO 2 or the like as a base and forming an Ag alloy film on the film has been proposed. Will increase the cost.
以上のことから、従来の技術では、高い反射率を維持しつつ、電極膜に必要な密着性を確保することは困難であった。 From the above, it has been difficult for the conventional technology to secure the necessary adhesion to the electrode film while maintaining a high reflectance.
本発明の課題は、上記従来技術の問題点を解決することにあり、反射率を損なうことなく、低抵抗で、より高い密着性を有するＡｇ合金膜パターンを得ることができるＡｇ合金膜(例えば、Ａｇ合金反射膜、Ａｇ合金電極膜)及びその製造方法を提供することにある。 An object of the present invention is to solve the above-described problems of the prior art, and an Ag alloy film (for example, an Ag alloy film pattern having a high resistance and a low resistance can be obtained without impairing the reflectance (for example, , Ag alloy reflective film, Ag alloy electrode film) and a method for producing the same.
本発明のＡｇ合金膜の製造方法は、スパッタリングガスと添加ガスとしての酸素含有ガスを用いたスパッタ成膜により第一の薄膜を形成する工程と、スパッタ成膜により前記第一の薄膜上に前記第一の薄膜に比べて反射率が高くかつ低抵抗である第二の薄膜を形成する工程と、前記第一及び第二の薄膜をエッチングする工程とを有するＡｇ合金膜の製造方法であって、前記第一の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ及び０．５〜１０．０ｗｔ％のＳｎを含む第一のＡｇ合金ターゲットを用い、前記第二の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ及び２．０ｗｔ％以下のＳｎを含み、前記第一のＡｇ合金ターゲットとはＳｎ含有量が異なる第二のＡｇ合金ターゲットを用いることにより、前記第一の薄膜中のＳｎ含有量が、前記第二の薄膜中のＳｎ含有量より多くなるようにすることを特徴とする。第一のＡｇ合金ターゲットのＡｕ添加量が０．１ｗｔ％未満であると、得られるＡｇ合金膜の耐熱性及び耐食性に寄与せず、また、４．０ｗｔ％を超えると、後工程でのエッチング中にエッチング残渣が生じるという問題がある。第一のＡｇ合金ターゲットのＳｎ添加量が０．５ｗｔ％未満であると、得られるＡｇ合金膜の基板に対する良好な密着性が得られず、１０．０ｗｔ％を超えると、得られるＡｇ合金膜の抵抗値が高くなり、電極膜として使用できない。第二のＡｇ合金ターゲットのＡｕの添加量が０．１ｗｔ％未満であると、得られるＡｇ合金膜の耐熱性及び耐食性に寄与せず、また、４．０ｗｔ％を超えると、後工程でのエッチング中にエッチング残渣が生じるという問題がある。第二のＡｇ合金ターゲットのＳｎ添加量が２．０ｗｔ％を超えると、得られるＡｇ合金膜の反射率が低くなり、反射膜として使用できない。第一及び第二の薄膜中のＳｎ含有量をこのような関係にすることにより、得られたＡｇ合金膜の基板に対する密着性や反射率等の特性が単層の場合と比べて改良される。 Production of an Ag alloy film of the present invention includes the steps of forming a first film by sputtering film formation using an oxygen-containing gas as additive gas and the sputtering gas, the said first thin film by sputtering A method for producing an Ag alloy film, comprising: a step of forming a second thin film having a higher reflectance and a lower resistance than the first thin film; and a step of etching the first and second thin films. In the step of forming the first thin film, the first Ag containing 0.1 to 4.0 wt% Au and 0.5 to 10.0 wt% Sn on the basis of the alloy as a main component and all the alloy components. In the step of forming the second thin film using the alloy target, the alloy contains Ag as a main component, 0.1 to 4.0 wt% Au and 2.0 wt% or less Sn on the basis of the total component of the alloy, One Ag alloy target contains Sn It is by using different second Ag alloy target, the Sn content of the first thin film, characterized in that set to be more than the Sn content of the second thin film. If the amount of Au added to the first Ag alloy target is less than 0.1 wt%, it will not contribute to the heat resistance and corrosion resistance of the resulting Ag alloy film, and if it exceeds 4.0 wt%, it will be etched in a later step. There is a problem that an etching residue is generated therein. When the Sn addition amount of the first Ag alloy target is less than 0.5 wt%, good adhesion to the substrate of the obtained Ag alloy film cannot be obtained, and when it exceeds 10.0 wt%, the obtained Ag alloy film is obtained. The resistance value becomes high and cannot be used as an electrode film. If the added amount of Au in the second Ag alloy target is less than 0.1 wt%, it will not contribute to the heat resistance and corrosion resistance of the resulting Ag alloy film, and if it exceeds 4.0 wt%, There is a problem that an etching residue is generated during etching. If the amount of Sn added to the second Ag alloy target exceeds 2.0 wt%, the resulting Ag alloy film has a low reflectance and cannot be used as a reflecting film. By setting the Sn content in the first and second thin films in such a relationship, the properties of the obtained Ag alloy film such as adhesion to the substrate and reflectivity are improved as compared with the case of a single layer. .
また、本発明のＡｇ合金反射膜の製造方法は、スパッタリングガスと添加ガスとしての酸素含有ガスを用いたスパッタ成膜により第一の薄膜を形成する工程と、スパッタ成膜により前記第一の薄膜上に前記第一の薄膜に比べて反射率が高くかつ低抵抗である第二の薄膜を形成する工程と、前記第一及び第二の薄膜をエッチングする工程とを有するＡｇ合金反射膜の製造方法であって、前記第一の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ及び０．５〜１０．０ｗｔ％のＳｎを含む第一のＡｇ合金ターゲットを用い、前記第二の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ、Ｐｄ、Ｎｄ及びＣｕから選ばれた少なくとも１種を含み、Ｓｎを含まない第二のＡｇ合金ターゲットを用いることを特徴とする。第一のＡｇ合金ターゲットのＡｕ添加量が０．１ｗｔ％未満であると、得られるＡｇ合金膜の耐熱性及び耐食性に寄与せず、また、４．０ｗｔ％を超えると、後工程でのエッチング中にエッチング残渣が生じるという問題がある。第一のＡｇ合金ターゲットのＳｎ添加量が０．５ｗｔ％未満であると、得られるＡｇ合金膜の基板に対する良好な密着性が得られず、１０．０ｗｔ％を超えると、得られるＡｇ合金膜の抵抗値が高くなり、電極膜として使用できない。第二の薄膜にＳｎが含まれていなくても、この合金組成によれば、得られた二層からなるＡｇ合金膜の基板に対する密着性や反射率特性は単層の場合と比べて改良される。 The method for producing an Ag alloy reflective film of the present invention includes a step of forming a first thin film by sputtering film formation using a sputtering gas and an oxygen-containing gas as an additive gas, and the first thin film film by sputtering film formation. Production of an Ag alloy reflective film comprising a step of forming a second thin film having a higher reflectance and a lower resistance than the first thin film, and a step of etching the first and second thin films. In the method of forming the first thin film, Ag as a main component and 0.1 to 4.0 wt% of Au and 0.5 to 10.0 wt% of Sn are included on the basis of the total component of the alloy. In the step of forming the second thin film using the first Ag alloy target, Ag as a main component and 0.1 to 4.0 wt% of Au, Pd, Nd, and Cu are selected on the basis of all alloy components. Including at least one kind of Sn Characterized by using the Manai second Ag alloy target. If the amount of Au added to the first Ag alloy target is less than 0.1 wt%, it will not contribute to the heat resistance and corrosion resistance of the resulting Ag alloy film, and if it exceeds 4.0 wt%, it will be etched in a later step. There is a problem that an etching residue is generated therein. When the Sn addition amount of the first Ag alloy target is less than 0.5 wt%, good adhesion to the substrate of the obtained Ag alloy film cannot be obtained, and when it exceeds 10.0 wt%, the obtained Ag alloy film is obtained. The resistance value becomes high and cannot be used as an electrode film. Even if Sn is not contained in the second thin film, according to this alloy composition, the adhesion and reflectance characteristics of the obtained Ag alloy film composed of two layers to the substrate are improved as compared with the case of a single layer. The
本発明において、第一の薄膜の膜厚は、一般に５０Å以上、好ましくは５０〜５００Å、より好ましくは１００〜５００Å、最も好ましくは２００Å前後であることを特徴とする。５０Å未満であると、形成される膜は基板に対する密着層として機能しなくなる。上限は、目的とする反射率特性に応じて適宜選択すればよい。 In the present invention, the thickness of the first thin film is generally 50 mm or more, preferably 50 to 500 mm, more preferably 100 to 500 mm, and most preferably about 200 mm. If it is less than 50 mm, the formed film does not function as an adhesion layer for the substrate. What is necessary is just to select an upper limit suitably according to the target reflectance characteristic.
本発明において、第一及び第二の薄膜のそれぞれを、主成分としてのＡｇに対してＡｕ及びＳｎを異なる量で含む前記第一及び第二のＡｇ合金ターゲットを用いて形成した後に、第一及び第二の薄膜を同じエッチング液でパターン加工することを特徴とする。 In the present invention, after forming each of the first and second thin films using the first and second Ag alloy targets containing Au and Sn in different amounts with respect to Ag as a main component, And patterning the second thin film with the same etching solution.
本発明において、第一の薄膜を形成する工程では、スパッタリングガスとしての不活性ガスと添加ガスとしての酸素含有ガスとを用い、第二の薄膜を形成する工程では、スパッタリングガスとしての不活性ガスのみ又は不活性ガスと酸素含有ガスとを用いることを特徴とする。この不活性ガスとしては、例えば、ヘリウム、ネオン、アルゴン、クリプトン、キセノン等の希ガスを用いることができる。 In the present invention, in the step of forming a first thin film, it has use an oxygen-containing gas as additive gas and inert gas as the sputtering gas, in the step of forming a second thin film, as the sputtering gas characterized in that there use the only or an inert gas and an oxygen-containing gas an inert gas. As the inert gas, for example, it may be used helium, neon, argon, krypton, a rare gas scan such xenon.
本発明において、前記第一の薄膜を形成する工程では、酸素含有ガスを、酸素含有ガスの分圧が、６．６５Ｅ−０３〜２．８７Ｅ−０２Ｐａとなるように添加することが望ましい。６．６５Ｅ−０３Ｐａ未満であると、基板へのＡｇ合金膜(例えば、第一の薄膜)の密着性の向上にあまり寄与せず、２．８７Ｅ−０２Ｐａを超えると、反射率の劣化や高抵抗化の弊害が著しくなる。 In the present invention, in the forming the first thin film, the oxygen-containing gas, the partial pressure of the oxygen-containing gas, Rukoto be added so that the 6.65E-03~2.87E-02Pa is desirable. If it is less than 6.65E-03 Pa, it will not contribute much to the improvement of the adhesion of the Ag alloy film (for example, the first thin film) to the substrate. The harmful effect of resistance becomes significant.
また、本発明のＡｇ合金膜(Ａｇ合金反射膜やＡｇ合金電極膜)は、主成分としてのＡｇと合金全成分基準で一般に０．１〜４．０ｗｔ％、好ましくは０．５〜２．０ｗｔ％のＡｕ及び一般に０．５〜１０．０ｗｔ％、好ましくは１．０〜１０．０ｗｔ％、より好ましくは１．５〜９．０ｗｔ％のＳｎを含む合金からなり、基板表面に酸素含有雰囲気下で形成された第一の薄膜と、主成分としてのＡｇと合金全成分基準で一般に０．１〜４．０ｗｔ％、好ましくは０．５〜２．０ｗｔ％のＡｕ及び一般に２．０ｗｔ％以下、好ましくは１．５ｗｔ％以下のＳｎを含む合金からなり、第一の薄膜上に形成された第二の薄膜と、を有し、第一の薄膜中のＳｎ含有量が、第二の薄膜中のＳｎ含有量より多いことを特徴とする。 The Ag alloy film of the present invention (Ag alloy reflective film or Ag alloy electrode film) is generally 0.1 to 4.0 wt%, preferably 0.5 to 2. 0 wt% of Au and generally 0.5~10.0wt%, preferably 1.0~10.0wt%, more preferably Ri Do an alloy containing 1.5～9.0Wt% of Sn, oxygen on the surface of the substrate 2 a first thin film formed under an atmosphere containing generally 0.1～4.0Wt% of Ag and alloys all components criteria as the main component, preferably Au and general 0.5~2.0wt%. 0 wt% or less, preferably Ri Do an alloy containing 1.5 wt% or less of Sn, and a second thin film formed on the first thin film has a, and Sn content of the first thin film, More than the Sn content in the second thin film.
また、本発明のＡｇ合金膜(Ａｇ合金反射膜又はＡｇ合金電極膜)は、主成分としてのＡｇと合金全成分基準で一般に０．１〜４．０ｗｔ％、好ましくは０．５〜２．０ｗｔ％のＡｕ及び一般に０．５〜１０．０ｗｔ％、好ましくは１．０〜１０．０ｗｔ％、より好ましくは１．５〜９．０ｗｔ％のＳｎを含む合金からなり、基板表面に酸素含有雰囲気下で形成された第一の薄膜と、主成分としてのＡｇと合金全成分基準で一般に０．１〜４．０ｗｔ％、好ましくは０．５〜２．０ｗｔ％のＡｕ、Ｐｄ、Ｎｄ及びＣｕから選ばれた少なくとも１種を含み、Ｓｎを含まない合金からなり、第一の薄膜上に形成された第二の薄膜と、を有することを特徴とする。 The Ag alloy film (Ag alloy reflective film or Ag alloy electrode film) of the present invention is generally 0.1 to 4.0 wt%, preferably 0.5 to 2. 0 wt% of Au and generally 0.5~10.0wt%, preferably 1.0~10.0wt%, more preferably Ri Do an alloy containing 1.5～9.0Wt% of Sn, oxygen on the surface of the substrate a first thin film formed under an atmosphere containing generally 0.1～4.0Wt% of Ag and alloys all components criteria as the main component, preferably 0.5～2.0Wt% of Au, Pd, Nd and at least one selected from Cu, Ri do alloy that does not contain Sn, and having a second thin film formed on the first thin film, the.
本発明のＡｇ合金膜の製造方法によれば、スパッタ成膜により形成される第二の薄膜は、スパッタ成膜により形成される第一の薄膜に比べて反射率が高くかつ低抵抗であり、また、第一の薄膜の基板への密着性は極めて優れているという効果を奏する。 According to the method for producing an Ag alloy film of the present invention, the second thin film formed by sputtering film formation has a higher reflectance and lower resistance than the first thin film formed by sputtering film formation, In addition, the first thin film has an excellent adhesion to the substrate.
そのため、本発明のＡｇ合金膜は、例えば、ＬＣＤや有機ＥＬ等の発光素子のような各種表示素子用の反射膜や各種素子用の配線膜(電極膜)や、その他にランプや装飾品等の一般材料用としても有用であるという効果を奏する。 Therefore, the Ag alloy film of the present invention is, for example, a reflective film for various display elements such as a light emitting element such as an LCD or an organic EL, a wiring film (electrode film) for various elements, a lamp, a decorative article, etc. It is also useful as a general material.
本発明に係わるＡｇ合金膜の製造方法の実施の形態によれば、目的とするＡｇ合金膜は、Ａｇを主成分としてＡｕ及びＳｎを含有するＡｇ合金からなる二層膜であって、第一の薄膜中のＳｎ含有量が第二の薄膜中の場合より高くなるように、Ｓｎ含有量が異なる組成を有するＡｇ合金ターゲットを用いてスパッタ成膜することにより製造される。このターゲットは、各合金成分を配合・溶融・焼結する通常の合金ターゲット作製方法により製造できる。 According to the embodiment of the method for producing an Ag alloy film according to the present invention, the target Ag alloy film is a two-layer film made of an Ag alloy containing Ag and Au as a main component. This is manufactured by sputtering film formation using an Ag alloy target having a composition with a different Sn content so that the Sn content in the thin film is higher than that in the second thin film. This target can be manufactured by a normal alloy target manufacturing method in which each alloy component is blended, melted, and sintered.
本発明によれば、Ａｇ合金膜はまた、Ａｇを主成分としてＡｕ及びＳｎを含有するＡｇ合金からなる二層膜であって、第一の薄膜が、Ａｇを主成分としてＡｕ及び密着性に充分な量のＳｎを含有するＡｇ合金からなる膜となるように、そして第二の薄膜が、Ａｇを主成分としてＡｕ及びＳｎ又はＡｕのみを含有するＡｇ合金からなる膜であって、第一の薄膜よりも反射率が高く、低抵抗である膜となるように製造される。 According to the present invention, the Ag alloy film is also a two-layer film made of an Ag alloy containing Au and Sn containing Ag as a main component, and the first thin film is made Au and adhesive with Ag as a main component. The film is made of an Ag alloy containing a sufficient amount of Sn, and the second thin film is a film made of an Ag alloy containing Au as a main component and containing only Au and Sn or Au. It is manufactured so as to be a film having higher reflectivity and lower resistance than the above thin film.
本発明で用いる第一の薄膜形成用のＡｇ合金ターゲットはＳｎ成分を含有しているので、酸素含有ガスを添加したガスでスパッタすると、成膜中にＳｎと酸素との反応によりＳｎＯ２が生じ、このＳｎＯ２が基板とのバインダとなって、基板(例えば、ガラス、シリコンの他にプラスチックフィルム等からなる基板)へのＡｇ合金膜(第一の薄膜)の密着性が向上するものと考えられる。より高い密着性を得るためには、ＳｎＯ２生成量の増加、すなわちＳｎ含有量及び酸素含有ガスの添加量を適宜増加させれば達成される。この場合、酸素含有ガスの添加量は、本発明の目的を達成するためには、前記したように、酸素含有ガスの分圧で、６．６５Ｅ−０３〜２．８７Ｅ−０２Ｐａであることが望ましい。 Since the Ag alloy target for forming the first thin film used in the present invention contains a Sn component, SnO 2 is generated by the reaction of Sn and oxygen during the film formation when sputtered with a gas to which an oxygen-containing gas is added. The SnO 2 serves as a binder with the substrate, which improves the adhesion of the Ag alloy film (first thin film) to the substrate (for example, a substrate made of plastic film in addition to glass or silicon). It is done. In order to obtain higher adhesion, it is achieved by increasing the amount of SnO 2 production, that is, by appropriately increasing the amount of Sn and the amount of oxygen-containing gas added. In this case, in order to achieve the object of the present invention, the amount of oxygen-containing gas added is, as described above, 6.65E-03 to 2.87E-02Pa as the partial pressure of the oxygen-containing gas. desirable.
しかし、Ａｇ合金膜中のＳｎ含有量や酸素含有ガス添加量の増加の程度によっては、反射率の劣化や高抵抗化の弊害が著しくなる。そこで、より高い密着性と反射率という相反する二つの特性を同時に満たすためには、上記したように、多層化、すなわち密着性に寄与する膜と反射率に寄与する膜とを組み合わせることにより達成可能となる。 However, depending on the degree of increase of the Sn content and the oxygen-containing gas addition amount in the Ag alloy film, the adverse effect of the deterioration of the reflectivity and the increase in resistance becomes significant. Therefore, in order to satisfy the two conflicting properties of higher adhesion and reflectance at the same time, as described above, it is achieved by multilayering, that is, by combining a film that contributes to adhesion and a film that contributes to reflectance. It becomes possible.
また、密着性に寄与する膜と反射率に寄与する膜とは、若干の組成は異なるものの、Ａｇを主成分とするＡｇ合金膜からなるため、同一のエッチング液を用いることができ、一回のエッチングプロセスで加工可能となる。エッチング液としては、特に制限はなく、Ａｇ合金膜をエッチングする際に通常用いられる液であればよい。例えば、リン酸：硝酸：水＝３８：５：５７(重量％)に硝酸銀を０．１重量％加えたエッチング液を用い、室温（２３℃）で基板を静止状態にしてエッチングを行うことができる。 In addition, the film contributing to adhesion and the film contributing to reflectivity are slightly different in composition, but are composed of an Ag alloy film containing Ag as a main component, so the same etching solution can be used once. It becomes possible to process by this etching process. There is no restriction | limiting in particular as etching liquid, What is necessary is just a liquid normally used when etching an Ag alloy film. For example, etching can be performed by using an etchant obtained by adding 0.1 wt% of silver nitrate to phosphoric acid: nitric acid: water = 38: 5: 57 (wt%) at room temperature (23 ° C.). it can.
一般に、膜の抵抗は膜全体の特性によるため、抵抗の高い第一の薄膜の厚みを薄くすることにより、膜の低抵抗化が達成可能となる。 In general, since the resistance of the film depends on the characteristics of the entire film, the resistance of the film can be reduced by reducing the thickness of the first thin film having high resistance.
膜の厚み方向で異なるＳｎ含有量を持つ二層のＡｇ合金膜は、Ｓｎ含有量の異なるＡｇ合金ターゲットを用いて、或いはＳｎを含むターゲットとＳｎを含まないターゲットとを用いて積層成膜することにより作製できる。反射率に寄与する膜である第二の薄膜は、第一の薄膜よりも反射率が高く、低抵抗であれば、その組成に制限はない。また、第二の薄膜がＳｎを含まないものである場合は、ＡｕやＰｄやＮｄやＣｕ等から選ばれた少なくとも１種が含まれていてもよい。この場合も、第二の薄膜が高い反射率と低抵抗を有すれば、第一の薄膜と積層することにより、高い密着性、高い反射率、及び低抵抗を有するＡｇ合金膜を得ることができる。 Two-layer Ag alloy films having different Sn contents in the thickness direction of the film are stacked using Ag alloy targets having different Sn contents, or using a target containing Sn and a target not containing Sn. Can be produced. The second thin film, which is a film that contributes to the reflectivity, has a higher reflectivity than the first thin film and has a low resistance, so that the composition is not limited. Further, when the second thin film does not contain Sn, at least one selected from Au, Pd, Nd, Cu, and the like may be included. Also in this case, if the second thin film has high reflectance and low resistance, an Ag alloy film having high adhesion, high reflectance, and low resistance can be obtained by laminating with the first thin film. it can.
本発明によれば、Ｓｎ含有量の多い第一の薄膜を形成するときには、この薄膜の基板に対する密着性の点から酸素含有ガスを添加し、第二の薄膜を形成するときには、酸素含有ガスを添加してもしなくてもよい。その結果、高反射率、低抵抗の密着性に優れた二層からなるＡｇ合金膜の製造が可能となる。酸素含有ガスを添加すると反射率が若干低くなる可能性があるが、第二の薄膜の反射率が第一の薄膜よりも高ければ、第二の薄膜を形成するときに酸素含有ガスを添加してスパッタ成膜してもよい。 According to the present invention, when forming the first thin film having a high Sn content, an oxygen-containing gas is added from the viewpoint of adhesion of the thin film to the substrate, and when forming the second thin film, the oxygen-containing gas is added. It may or may not be added. As a result, it is possible to produce a two-layered Ag alloy film with high reflectivity and low resistance and excellent adhesion. When oxygen-containing gas is added, the reflectivity may be slightly lower, but if the second thin film has a higher reflectivity than the first thin film, the oxygen-containing gas is added when forming the second thin film. Sputter deposition may be performed.
スパッタ成膜の際に用いる酸素含有ガスとしては、酸素を含んでいて、その酸素がスパッタ時にＳｎと反応できるものであれば特に制限はなく、例えば、Ｏ２、Ｈ２Ｏ、Ｈ２＋Ｏ２等の中から選ばれた少なくとも１種のガスを使用できる。 The oxygen-containing gas used for sputtering film formation is not particularly limited as long as it contains oxygen and can react with Sn at the time of sputtering. For example, O 2 , H 2 O, H 2 + O 2 At least one gas selected from among these can be used.
なお、本発明のスパッタリング工程で使用するスパッタリング装置は、特に制限はなく、公知のインライン式、バッチ式、枚葉式等のスパッタリング装置を使用できる。例えば、スパッタ室を有し、このスパッタ室が真空排気系に接続できる構成になっているスパッタ装置を使用できる。スパッタ室内部には、磁気回路を有したカソード電極が配置され、カソード電極の上にはターゲットを取付けることができ、このターゲットに電源からＤＣバイアスを印加できるように構成されていればよい。本発明では、このターゲットとして、目的とするＡｇ合金膜の組成に応じて適宜選択した所定の割合の合金組成で構成されたものを使用する。また、スパッタ室には、ガス導入系が接続され、スパッタ室にＡｒ等の不活性ガスの他にＯ２、Ｈ２Ｏ、Ｈ２＋Ｏ２等の酸素含有ガスの導入が可能になるように構成されている。スパッタ室の隣には真空排気系を有した仕込み室が設けられ、基板をスパッタ室へ搬送できる構造になっているものが好都合である。 In addition, the sputtering apparatus used in the sputtering process of the present invention is not particularly limited, and a known in-line type, batch type, single-wafer type sputtering apparatus or the like can be used. For example, it is possible to use a sputtering apparatus that has a sputtering chamber and is configured such that the sputtering chamber can be connected to a vacuum exhaust system. A cathode electrode having a magnetic circuit is disposed inside the sputtering chamber, and a target can be mounted on the cathode electrode, and a DC bias can be applied to the target from a power source. In the present invention, a target composed of an alloy composition of a predetermined ratio appropriately selected according to the composition of the target Ag alloy film is used as the target. In addition, a gas introduction system is connected to the sputtering chamber so that an oxygen-containing gas such as O 2 , H 2 O, and H 2 + O 2 can be introduced into the sputtering chamber in addition to an inert gas such as Ar. It is configured. It is advantageous that a preparation chamber having an evacuation system is provided next to the sputtering chamber so that the substrate can be transferred to the sputtering chamber.
以下、実施例に基づき本発明を詳細に説明する。以下の実施例中で示す各合金成分の割合（ｗｔ％）は、合金成分の全量基準である。 Hereinafter, the present invention will be described in detail based on examples. The ratio (wt%) of each alloy component shown in the following examples is based on the total amount of alloy components.
本実施例では、二層からなるＡｇ合金膜製造の際の最適プロセス条件を決めるために、上記公知のスパッタリング装置を用いて単層膜を作製した。すなわち、基板との密着性に寄与する第一の層であるＡｇ合金膜のＳｎ含有量の最適値及び酸素添加量の最適値を検討すると共に、反射率に寄与する第二の層であるＡｇ合金膜のＳｎ含有量の最適値を検討した。 In this example, a single-layer film was produced using the above-described known sputtering apparatus in order to determine the optimum process conditions for producing a two-layer Ag alloy film. That is, the optimum value of the Sn content and the optimum value of the oxygen addition amount of the Ag alloy film, which is the first layer that contributes to the adhesion to the substrate, are examined, and the second layer, Ag, that contributes to the reflectance. The optimum value of the Sn content of the alloy film was examined.
第一のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で１．７ｗｔ％のＡｕ及び２．０ｗｔ％のＳｎを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲット、第二のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で１．０ｗｔ％のＡｕ及び１．５ｗｔ％のＳｎを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲット、第三のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で０．５ｗｔ％のＡｕ及び０．５ｗｔ％のＳｎを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲットをスパッタ室内にセットして、公知のスパッタリング法でそれぞれの単層膜を作製した。また、第四のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ基準で０．５ｗｔ％のＡｕを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲットをスパッタ室内にセットして、公知のスパッタリング法で単層膜を作製した。さらに、第五のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で１．７ｗｔ％のＡｕ及び９．０ｗｔ％のＳｎを添加し、上記したようにして作製したＡｇ合金ターゲットを用いて単層膜を作製した。 As a first target, an Ag alloy target having a composition in which Ag is a main component, 1.7 wt% Au and 2.0 wt% Sn are added to this based on Ag + Au + Sn, and alloyed by a normal alloy target manufacturing method. As a second target, an Ag alloy having a composition in which Ag is a main component, 1.0 wt% Au and 1.5 wt% Sn are added to this and Ag + Au + Sn, and alloyed by a normal alloy target manufacturing method. As a target and a third target, Ag having a composition in which Ag is a main component, 0.5 wt% Au and 0.5 wt% Sn are added to this and Ag + Au + Sn, and alloyed by a normal alloy target manufacturing method. An alloy target was set in the sputtering chamber, and each single-layer film was produced by a known sputtering method. As the fourth target, an Ag alloy target having a composition in which Ag is the main component, 0.5 wt% of Au is added to the Ag + Au standard, and alloyed by a normal alloy target manufacturing method is set in the sputtering chamber. Then, a single layer film was produced by a known sputtering method. Furthermore, as a fifth target, Ag is the main component, 1.7 wt% Au and 9.0 wt% Sn are added to this with Ag + Au + Sn as a reference, and the Ag alloy target manufactured as described above is used as a single target. A layer film was prepared.
スパッタ室にＡｒガス２００ｓｃｃｍ、酸素ガスをＯ２分圧で表１に示した量導入し、ＤＣパワー５００Ｗ(パワー密度１Ｗ／ｃｍ２)を各ターゲットに投入した。スパッタ圧力は０．６６７Ｐａ程度であった。仕込み室から、洗浄したガラス基板(コーニング１７３７)を保持した基板搬送トレイを２０ｃｍ／ｍｉｎの搬送速度でスパッタ室へ移送し、１３０℃で通過成膜を行った。トレイがターゲットを通過した時点で、放電を終了し、トレイを仕込み室へ戻した。基板上に表１に示す膜厚のＡｇ合金膜(サンプルＮｏ．１〜１５)が作製された。 Ar gas was introduced into the sputtering chamber at 200 sccm and oxygen gas was introduced in the amounts shown in Table 1 in O 2 partial pressure, and DC power of 500 W (power density of 1 W / cm 2 ) was introduced into each target. The sputtering pressure was about 0.667 Pa. From the preparation chamber, the substrate transfer tray holding the cleaned glass substrate (Corning 1737) was transferred to the sputtering chamber at a transfer rate of 20 cm / min, and film formation was performed at 130 ° C. When the tray passed the target, the discharge was terminated and the tray was returned to the preparation chamber. Ag alloy films (sample Nos. 1 to 15) having the thicknesses shown in Table 1 were produced on the substrate.
それぞれのプロセス条件で作製した単層膜の特性として、反射率、シート抵抗値、密着性を評価した。その結果を表１に示す。 As the characteristics of the single layer film produced under each process condition, the reflectance, sheet resistance value, and adhesion were evaluated. The results are shown in Table 1.
反射率は、Ａｌ基板をリファレンスとし、可視光領域(波長４００ｎｍ、４８０ｎｍ、５５０ｎｍ)で分光光度計を用いて測定した。 The reflectance was measured using a spectrophotometer in the visible light region (wavelength 400 nm, 480 nm, 550 nm) with an Al substrate as a reference.
密着性は、ベタ膜への粘着テープ(３Ｍ社製、型番６１０−１ＰＫ)による剥離テストにより評価すると共に、より優位性を評価することができるテストとして、２０μｍのパターンを公知の条件下でウエットエッチングにより作製し、それに対する上記粘着テープによる剥離テストも実施した。後者の剥離テストでは、クロスカット法に従って、５ｍｍ×５ｍｍの２５マスの膜のけがき及びパターニング後の２０μｍパターンに対するテープ剥離テストにて評価した。その結果を、○(パターン欠け・剥がれなし)、△(パターン欠けあり)、×(パターン剥がれあり)として表１に示す。 Adhesion is evaluated by a peel test using an adhesive tape (made by 3M, Model No. 610-1PK) to a solid film, and a 20 μm pattern is wetted under known conditions as a test that can evaluate more superiority. It produced by the etching and the peeling test with the said adhesive tape with respect to it was also implemented. In the latter peeling test, evaluation was made by a tape peeling test on a 25 mm film scribing of 5 mm × 5 mm and a 20 μm pattern after patterning according to a cross-cut method. The results are shown in Table 1 as ◯ (no pattern chipping / peeling), Δ (pattern missing), × (pattern peeling).
なお、上記エッチングは、リン酸：硝酸：水＝３８：５：５７(重量％)に硝酸銀を０．１重量％加えたエッチング液を用い、室温(２３℃)で基板を静止状態にして行った。 Note that the etching is performed by using an etching solution obtained by adding 0.1% by weight of silver nitrate to phosphoric acid: nitric acid: water = 38: 5: 57 (% by weight) and keeping the substrate stationary at room temperature (23 ° C.). It was.
表１から明らかなように、密着性に寄与する第一の薄膜として用いる場合のＡｇ合金膜中のＳｎ含有量は、一般に０．５〜１０．０ｗｔ％、好ましくは１．０〜１０．０ｗｔ％、より好ましくは１．５〜９．０ｗｔ％である。また、Ｏ２添加量は、酸素分圧で６．６５Ｅ−０３〜２．８７Ｅ−０２Ｐａ程度必要であることが分かる。 As is apparent from Table 1, the Sn content in the Ag alloy film when used as the first thin film contributing to adhesion is generally 0.5 to 10.0 wt%, preferably 1.0 to 10.0 wt%. %, More preferably 1.5 to 9.0 wt%. Also, O 2 amount of addition, it is understood the oxygen partial pressure is needed about 6.65E-03~2.87E-02Pa at.
また、反射率に寄与する第二の薄膜として用いる場合のＡｇ合金膜中のＳｎ含有量は、一般に２．０ｗｔ％以下、好ましくは１．５ｗｔ％以下であればよく、この場合、Ｏ２ガスを添加しないで成膜すれば、より高い反射率を有する膜を得ることが可能であることが分かる。なお、表１中、サンプルＮｏ．２のようにＳｎが含まれていないターゲットを用いてスパッタリングして得られたＡｇ薄膜の場合には、密着性は良くないが、反射率が高いので、第二の薄膜として使用することが可能である。 Further, the Sn content in the Ag alloy film when used as the second thin film contributing to the reflectance is generally 2.0 wt% or less, preferably 1.5 wt% or less. In this case, the O 2 gas It can be seen that a film having higher reflectivity can be obtained if the film is formed without adding. In Table 1, sample No. In the case of an Ag thin film obtained by sputtering using a target that does not contain Sn, such as 2, the adhesion is not good, but the reflectance is high, so it can be used as a second thin film. It is.
第一のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で１．７ｗｔ％のＡｕ及び２．０ｗｔ％のＳｎを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲット、第二のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で１．０ｗｔ％のＡｕ及び１．５ｗｔ％のＳｎを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲット、第三のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で０．５ｗｔ％のＡｕ及び０．５ｗｔ％のＳｎを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲットをスパッタ室内にセットして、公知のスパッタリング法で二層膜を作製した。また、第四のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ基準で０．５ｗｔ％のＡｕを添加し、通常の合金ターゲット作製方法により合金化した組成を有するＡｇ合金ターゲット、さらに、第五のターゲットとして、Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で１．７ｗｔ％のＡｕ及び９．０ｗｔ％のＳｎを添加し、上記したようにして作製したＡｇ合金ターゲットをスパッタ室内にセットして、公知のスパッタリング法で二層膜を作製した。 As a first target, an Ag alloy target having a composition in which Ag is a main component, 1.7 wt% Au and 2.0 wt% Sn are added to this based on Ag + Au + Sn, and alloyed by a normal alloy target manufacturing method. As a second target, an Ag alloy having a composition in which Ag is a main component, 1.0 wt% Au and 1.5 wt% Sn are added to this and Ag + Au + Sn, and alloyed by a normal alloy target manufacturing method. As a target and a third target, Ag having a composition in which Ag is a main component, 0.5 wt% Au and 0.5 wt% Sn are added to this and Ag + Au + Sn, and alloyed by a normal alloy target manufacturing method. An alloy target was set in the sputtering chamber, and a two-layer film was produced by a known sputtering method. Further, as a fourth target, an Ag alloy target having a composition in which Ag is a main component, 0.5 wt% of Au is added to the Ag + Au standard, and alloyed by a normal alloy target manufacturing method, As a target, Ag is a main component, 1.7 wt% Au and 9.0 wt% Sn are added to this based on Ag + Au + Sn, and the Ag alloy target prepared as described above is set in the sputtering chamber, A two-layer film was produced by a known sputtering method.
上記Ａｇ合金ターゲットのうち、第一のＡｇ合金ターゲット、第二のＡｇ合金ターゲット又は第五のＡｇ合金ターゲットを用い、スパッタリングガスとしてのＡｒガスと添加ガスとしてのＯ２ガスとを用いてスパッタ成膜し、密着性を有する第一の薄膜(一層目)を作製し、次いでこの上に、第三又は第四のＡｇ合金ターゲットを用い、スパッタリングガスとしてのＡｒガスのみを用いてスパッタ成膜し、第二の薄膜(二層目)を作製した。 Of the above Ag alloy targets, the first Ag alloy target, the second Ag alloy target, or the fifth Ag alloy target is used, and sputtering is performed using Ar gas as the sputtering gas and O 2 gas as the additive gas. A first thin film (first layer) having an adhesive property is formed, and then a sputtering film is formed thereon using a third or fourth Ag alloy target and using only Ar gas as a sputtering gas. A second thin film (second layer) was prepared.
一層目の膜は、実施例１で求めたＯ２添加量の最適値の６．６５Ｅ−０３Ｐａ、１．３３Ｅ−０２Ｐａ、２．８７Ｅ−０２Ｐａでスパッタ成膜し、その膜厚が２００〜５００Åとなるようにした。また、二層目の膜については、一層目及び二層目の膜を組み合わせた場合に、合計厚みが１５００Åとなるような膜厚とした。 The first film was formed by sputtering at the optimum values of O 2 addition amount obtained in Example 1, 6.65E-03Pa, 1.33E-02Pa, 2.87E-02Pa, and the film thickness was 200 to 500 mm. It was made to become. The second layer film was formed to have a total thickness of 1500 mm when the first and second layer films were combined.
かくして得られた二層からなるＡｇ合金膜をサンプルＮｏ．１６〜２０、２２及び２３として表２に示す。また、得られた二層膜の膜特性として、実施例１と同様な方法で反射率、シート抵抗値、密着性を評価し、その結果を表２に示す。 The two-layered Ag alloy film thus obtained was sample No. It is shown in Table 2 as 16-20, 22 and 23. Further, as the film characteristics of the obtained two-layer film, the reflectance, sheet resistance value, and adhesion were evaluated in the same manner as in Example 1, and the results are shown in Table 2.
表２から明らかなように、いずれのＡｇ合金二層膜も、密着性は良好であった。また、反射率は、一層目の膜厚が５００Åである場合、極僅か低かったが、いずれのＡｇ合金二層膜も、実施例１においてＯ２添加なしで作製した単層薄膜に近い高反射率を示していることが明らかである。さらに、サンプルＮｏ．２０から明らかなように、二層目の膜にＳｎが含まれていなくとも、密着性がよく、高反射率かつ低抵抗のＡｇ合金膜が得られることが分かる。 As is clear from Table 2, the adhesiveness of all the Ag alloy bilayer films was good. Moreover, the reflectance was extremely low when the film thickness of the first layer was 500 mm, but any of the Ag alloy bilayer films was highly reflective similar to the single layer thin film prepared in Example 1 without addition of O 2. It is clear that the rate is shown. Furthermore, sample no. As can be seen from FIG. 20, even if Sn is not contained in the second layer film, it can be seen that an Ag alloy film having good adhesion and high reflectance and low resistance can be obtained.
また、一層目の膜厚が２００Åあれば、一層目の膜厚が５００Åである二層膜の場合よりも抵抗値は低く、かつ密着性も維持できている。よって、密着性に寄与する一層目の膜厚は、一般に５０Å以上、好ましくは５０〜５００Å、より好ましくは１００〜５００Å、最も好ましくは２００Å前後であればよいことが分かる。 Further, when the thickness of the first layer is 200 mm, the resistance value is lower and the adhesion can be maintained than in the case of the two-layer film having the thickness of the first layer of 500 mm. Therefore, it can be seen that the thickness of the first layer contributing to adhesion is generally 50 mm or more, preferably 50 to 500 mm, more preferably 100 to 500 mm, and most preferably about 200 mm.
Ａｇを主成分とし、これにＡｇ＋Ａｕ＋Ｓｎ基準で１．７ｗｔ％のＡｕ及び２．０ｗｔ％のＳｎを添加して合金化した組成を有する上記第一のＡｇ合金ターゲット、そしてＡｇを主成分とし、これに１．０ｗｔ％のＰｄ及び０．９ｗｔ％のＣｕを添加して合金化した組成を有する第六のＡｇ合金ターゲットをスパッタ室内にセットして、公知のスパッタリング法により、以下の条件で二層膜を作製した。 The first Ag alloy target having a composition in which Ag is a main component and 1.7 wt% Au and 2.0 wt% Sn are added and alloyed thereto based on Ag + Au + Sn, and Ag is the main component. A sixth Ag alloy target having a composition alloyed by adding 1.0 wt% Pd and 0.9 wt% Cu to a sputtering chamber is set in a sputtering chamber, and two layers are formed by a known sputtering method under the following conditions: A membrane was prepared.
表２のサンプルＮｏ．２１に示すように、一層目の薄膜は、Ｓｎ含有量２．０ｗｔ％の第一のＡｇ合金ターゲットを用い、スパッタリングガスとしてのＡｒガスと添加ガスとしての酸素ガス(Ｏ２添加量を酸素分圧で１．３３Ｅ−０２Ｐａ)とを用いてスパッタ成膜して作製し、その膜厚が２００Åとなるようにした。次に、二層目の薄膜は、Ａｇを主成分とし、これにＰｄ及びＣｕを添加してなる第六のＡｇ合金ターゲットを用い、スパッタリングガスとしてのＡｒガスのみを用いてスパッタ成膜して作製した。二層目の膜厚は、一層目及び二層目の膜を組み合わせた場合に、合計膜厚が１５００Åとなるようにした。 Sample No. in Table 2 As shown in FIG. 21, the first thin film uses a first Ag alloy target having an Sn content of 2.0 wt%, and Ar gas as a sputtering gas and oxygen gas (O 2 addition amount as an additive gas) Sputter film formation was performed using a pressure of 1.33E-02 Pa), and the film thickness was set to 200 mm. Next, the second thin film is formed by sputtering using only the Ar gas as the sputtering gas, using a sixth Ag alloy target composed mainly of Ag and adding Pd and Cu thereto. Produced. The film thickness of the second layer was such that the total film thickness was 1500 mm when the first and second layers were combined.
得られた二層膜の特性として、実施例１と同様な方法で反射率、シート抵抗値、密着性を評価した。その結果、表２のサンプルＮｏ．２１から明らかなように、高反射率、低抵抗であり、密着性が良好であることが分かった。 As the characteristics of the obtained two-layer film, the reflectance, sheet resistance value, and adhesion were evaluated in the same manner as in Example 1. As a result, sample No. As can be seen from FIG. 21, it was found that the film had high reflectivity, low resistance, and good adhesion.
上記実施例１〜３から明らかなように、反射率に寄与する膜である第二の薄膜は、第一の薄膜よりも反射率が高くかつ低抵抗であれば、その膜組成にＳｎが含まれていなくとも、また、Ａｇ、Ｓｎの代わりに他の金属が含まれていてもよいことが分かる。 As is clear from Examples 1 to 3, if the second thin film, which is a film that contributes to reflectivity, has higher reflectivity and lower resistance than the first thin film, Sn is included in the film composition. Even if not, it is understood that other metals may be contained in place of Ag and Sn.
本発明によれば、反射率を損なうことなく、低抵抗で、より高い密着性を有するＡｇ合金膜パターンを得ることができるＡｇ合金膜(例えば、Ａｇ合金反射膜、Ａｇ合金電極膜)を提供できるので、本発明のＡｇ合金膜及びその製造方法は、ＬＣＤや有機ＥＬ等の発光素子のような各種表示素子用の反射膜や各種素子用の配線膜(電極膜)等の分野や、その他にランプや装飾品等の一般材料用の分野にも適用可能である。 According to the present invention, there is provided an Ag alloy film (for example, an Ag alloy reflective film, an Ag alloy electrode film) capable of obtaining an Ag alloy film pattern having a low resistance and higher adhesion without impairing the reflectance. Therefore, the Ag alloy film of the present invention and the manufacturing method thereof can be applied to fields such as reflective films for various display elements such as light emitting elements such as LCD and organic EL, and wiring films (electrode films) for various elements. It can also be applied to the field of general materials such as lamps and ornaments.
Claims (8)
前記第一の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ及び０．５〜１０．０ｗｔ％のＳｎを含む第一のＡｇ合金ターゲットを用い、前記第二の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ及び２．０ｗｔ％以下のＳｎを含み、前記第一のＡｇ合金ターゲットとはＳｎ含有量が異なる第二のＡｇ合金ターゲットを用いることにより、前記第一の薄膜中のＳｎ含有量が、前記第二の薄膜中のＳｎ含有量より多くなるようにすることを特徴とするＡｇ合金膜の製造方法。 A step of forming a first thin film by sputtering film formation using a sputtering gas and an oxygen-containing gas as an additive gas, and a reflectance higher than that of the first thin film on the first thin film film by sputtering film formation. And the manufacturing method of Ag alloy film which has the process of forming the 2nd thin film which is low resistance, and the process of etching said 1st and 2nd thin film,
In the step of forming the first thin film, a first Ag alloy containing 0.1 to 4.0 wt% Au and 0.5 to 10.0 wt% Sn on the basis of Ag as a main component and all the alloy components The step of forming the second thin film using the target includes Ag as a main component, 0.1 to 4.0 wt% Au and 2.0 wt% or less Sn based on the total alloy component, By using a second Ag alloy target having a Sn content different from that of the Ag alloy target, the Sn content in the first thin film is made larger than the Sn content in the second thin film. A method for producing an Ag alloy film, comprising:
前記第一の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ及び０．５〜１０．０ｗｔ％のＳｎを含む第一のＡｇ合金ターゲットを用い、前記第二の薄膜を形成する工程では、主成分としてのＡｇと合金全成分基準で０．１〜４．０ｗｔ％のＡｕ、Ｐｄ、Ｎｄ及びＣｕから選ばれた少なくとも１種を含み、Ｓｎを含まない第二のＡｇ合金ターゲットを用いることを特徴とするＡｇ合金反射膜の製造方法。 A step of forming a first thin film by sputtering film formation using a sputtering gas and an oxygen-containing gas as an additive gas, and a reflectance higher than that of the first thin film on the first thin film film by sputtering film formation. And the manufacturing method of Ag alloy reflective film which has the process of forming the 2nd thin film which is low resistance, and the process of etching said 1st and 2nd thin film,
In the step of forming the first thin film, a first Ag alloy containing 0.1 to 4.0 wt% Au and 0.5 to 10.0 wt% Sn on the basis of Ag as a main component and all the alloy components In the step of forming the second thin film using the target, at least one selected from 0.1 to 4.0 wt% of Au, Pd, Nd, and Cu on the basis of the alloy as a main component and all the alloy components is used. A method for producing an Ag alloy reflective film comprising using a second Ag alloy target that contains Sn and does not contain Sn.
該第一の薄膜中のＳｎ含有量が、該第二の薄膜中のＳｎ含有量より多いことを特徴とするＡｇ合金反射膜又は電極膜であるＡｇ合金膜。 Ri Do in Ag and alloys all components criteria as the main component from 0.1～4.0Wt% of Au and 0.5～10.0Wt% of an alloy containing Sn, which is formed in an oxygen-containing atmosphere on the substrate surface a first thin film, Ri Do alloy containing 0.1～4.0Wt% Au and 2.0 wt% or less of Sn in Ag alloy all components criteria as the main component, formed on said first thin film has a second thin films, a
An Ag alloy film which is an Ag alloy reflective film or an electrode film, wherein the Sn content in the first thin film is higher than the Sn content in the second thin film.
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| WO2008035617A1 (en) * | 2006-09-21 | 2008-03-27 | Kabushiki Kaisha Kobe Seiko Sho | Ag ALLOY THIN FILM, AND Ag ALLOY SPUTTERING TARGET FOR FORMATION OF THE Ag ALLOY THIN FILM |
| JP4176136B2 (en) * | 2006-09-21 | 2008-11-05 | 株式会社神戸製鋼所 | Ag alloy thin film |
| JPWO2009154137A1 (en) | 2008-06-17 | 2011-12-01 | 株式会社アルバック | Solar cell and method for manufacturing the same |
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| JP2020090708A (en) * | 2018-12-05 | 2020-06-11 | 三菱マテリアル株式会社 | Metal film and sputtering target |
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| JP2003170524A (en) * | 2001-12-10 | 2003-06-17 | Ulvac Japan Ltd | LAMINATE HAVING Ag-BASED FILM AND METHOD FOR FORMING Ag-BASED FILM |
| JP2004197117A (en) * | 2002-12-16 | 2004-07-15 | Ulvac Japan Ltd | Ag-ALLOY REFLECTIVE FILM, SPUTTERING TARGET AND METHOD FOR MANUFACTURING Ag-ALLOY THIN FILM |
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| JP2003170524A (en) * | 2001-12-10 | 2003-06-17 | Ulvac Japan Ltd | LAMINATE HAVING Ag-BASED FILM AND METHOD FOR FORMING Ag-BASED FILM |
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