JP2013209724A - Ag ALLOY FILM AND METHOD FOR FORMING THE SAME - Google Patents
Ag ALLOY FILM AND METHOD FOR FORMING THE SAME Download PDFInfo
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- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 12
- 229910001245 Sb alloy Inorganic materials 0.000 claims abstract description 64
- 239000013078 crystal Substances 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052787 antimony Inorganic materials 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 166
- 238000005486 sulfidation Methods 0.000 description 22
- 239000012298 atmosphere Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 238000002310 reflectometry Methods 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005211 surface analysis Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000000089 atomic force micrograph Methods 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910017944 Ag—Cu Inorganic materials 0.000 description 3
- 229910002668 Pd-Cu Inorganic materials 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910002696 Ag-Au Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910015363 Au—Sn Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017821 Cu—Ge Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- -1 vacuum Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、Ａｇ合金膜に関するものであり、特に、耐湿性、耐硫化性、耐熱性などの耐性に優れ、かつ、反射率が高く、抵抗率が低いＡｇ合金膜及びその形成方法に関する。 The present invention relates to an Ag alloy film, and more particularly to an Ag alloy film having excellent resistance to moisture, sulfidation, heat resistance, and the like, a high reflectance, and a low resistivity, and a method for forming the same.
有機ＥＬ、光記録ディスク、光学機器用反射ミラーなどにおける反射膜や反射電極では、耐湿性、耐硫化性、耐熱性などの耐性を持った反射率が高く、抵抗率の低いＡｇ合金膜が必要で、これまで、Ｐｄ、Ｃｕ、Ｇｅ、Ｂｉ、Ａｕ、Ｓｎ、希土類元素などを添加したＡｇ合金膜が用いられている。また、そのＡｇ合金膜に熱処理を施したり、酸化物のキャップ層を付けたりすることにより、耐硫化性などの耐性をさらに向上させたＡｇ合金膜が開発されている。また、ＡｇにＢｉ、Ｓｂを添加して、それらの添加元素を表面に濃集させて、凝集性（耐熱性）を向上させたＡｇ合金膜が開発されている。 For reflective films and reflective electrodes in organic EL, optical recording disks, reflective mirrors for optical equipment, etc., an Ag alloy film with high resistance and low resistance such as moisture resistance, sulfidation resistance and heat resistance is required. So far, Ag alloy films to which Pd, Cu, Ge, Bi, Au, Sn, rare earth elements and the like are added have been used. Further, an Ag alloy film having further improved resistance such as sulfidation resistance has been developed by heat-treating the Ag alloy film or attaching an oxide cap layer. Further, an Ag alloy film has been developed in which Bi and Sb are added to Ag, and these additive elements are concentrated on the surface to improve the cohesiveness (heat resistance).
従来から、反射膜の材料には、アルミニウム（Ａｌ）やＡｌを主成分とする合金が、耐熱性に優れているということで多く使用されてきたが、高反射率、低抵抗率が求められるようになって、銀（Ａｇ）が反射材として多用されてきた。純Ａｇによる膜が反射率としては最も高いものであったが、この純Ａｇ膜は、耐候性などに問題があった。そこで、耐候性を向上するものとして、Ａｇ−パラジウム（Ｐｄ）−銅（Ｃｕ）系銀合金が提案された。しかしながら、このＡｇ−Ｐｄ−Ｃｕ系合金による膜は、加熱工程を経ると、表面ラフネスの成長やヒロックの発生が生じ、その結果、その膜の反射率が低下した。さらに、その膜が加熱されることにより、硫化が促進されて、膜の黄色化が起き、その膜の耐硫化性にも問題があった。そこで、より高い耐熱性と耐硫化性を向上したものとして、Ａｇ−Ｐｄ−Ｃｕ系合金にゲルマニウム（Ｇｅ）を含有させたＡｇ−Ｐｄ−Ｃｕ−Ｇｅ系合金により膜を形成することが提案された（例えば、特許文献１を参照）。 Conventionally, aluminum (Al) or an alloy containing Al as a main component has been used as a material for a reflective film because of its excellent heat resistance, but high reflectivity and low resistivity are required. Thus, silver (Ag) has been frequently used as a reflector. The pure Ag film had the highest reflectance, but this pure Ag film had a problem in weather resistance and the like. Therefore, an Ag-palladium (Pd) -copper (Cu) -based silver alloy has been proposed as a means for improving weather resistance. However, when the film of this Ag—Pd—Cu alloy is subjected to a heating step, surface roughness grows and hillocks are generated, and as a result, the reflectivity of the film decreases. Furthermore, when the film is heated, sulfidation is promoted, the film is yellowed, and there is a problem with the sulfidation resistance of the film. Then, as what improved higher heat resistance and sulfidation resistance, it was proposed to form a film with an Ag—Pd—Cu—Ge alloy in which germanium (Ge) is contained in an Ag—Pd—Cu alloy. (For example, see Patent Document 1).
また、Ａｇを主成分として、Ｃｕの他に、金（Ａｕ）、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）などの元素を添加することにより、そのＡｇ基合金による膜において、低電気抵抗性や耐熱性を確保できることも知られている。この様なＡｇ基合金による膜の場合、複数回の高温加熱に対する耐熱性として耐凝集性に優れていることが重要となるが、低電気抵抗率や、真空化での高耐熱性の確保は達成できても、低電気抵抗率を維持したままで、この耐凝集性までは確保できない。そこで、高耐凝集性と低電気抵抗率との両方を兼備した膜として、ビスマス（Ｂｉ）を含有させたＡｇ基合金により形成することが提案されている（例えば、特許文献２を参照）。 In addition, by adding elements such as gold (Au), titanium (Ti), zirconium (Zr), etc. in addition to Cu with Ag as a main component, low electrical resistance and heat resistance can be achieved in the film made of the Ag-based alloy. It is also known that sex can be secured. In the case of such an Ag-based alloy film, it is important to have excellent cohesion resistance as heat resistance against multiple high-temperature heating, but ensuring low electrical resistivity and high heat resistance in a vacuum is important. Even if it can be achieved, this resistance to aggregation cannot be ensured while maintaining a low electrical resistivity. Thus, it has been proposed to form a film having both high agglomeration resistance and low electrical resistivity with an Ag-based alloy containing bismuth (Bi) (see, for example, Patent Document 2).
一方、Ａｇは、一般に、耐環境性に乏しいことも知られている。上述した加熱による凝集が生じることの他に、腐食により黒色に変色して、反射率や透過率を低下させるという問題がある。耐環境性、即ち、耐熱性、耐湿性、耐硫化性を確保し、この膜の反射率や透過率の低下を抑制するため、Ａｇを主成分として、イットリウム（Ｙ）、スカンジウム（Ｓｃ）、ランタノイドからなる希土類元素から選択される少なくとも１種を含有させたＡｇ基合金を用いることが提案されている（例えば、特許文献３を参照）。
また、耐凝集性及び耐硫化性を向上させたＡｇ合金膜も提案されている（例えば、特許文献４を参照）。このＡｇ合金には、Ａｕ、又は、Ａｕ、Ｂｉ、錫（Ｓｎ）の２種以上が含有されており、そのＡｇ合金による薄膜は、１３０〜２００℃の不活性ガス雰囲気で熱処理される。この加熱処理により、耐硫化性を向上させている。
On the other hand, Ag is generally known to have poor environmental resistance. In addition to the above-described aggregation caused by heating, there is a problem that the color changes to black due to corrosion and the reflectance and transmittance are lowered. In order to ensure environmental resistance, that is, heat resistance, moisture resistance, and sulfidation resistance, and to suppress a decrease in reflectance and transmittance of this film, Ag as a main component, yttrium (Y), scandium (Sc), It has been proposed to use an Ag-based alloy containing at least one selected from lanthanoid rare earth elements (see, for example, Patent Document 3).
Further, an Ag alloy film with improved aggregation resistance and sulfidation resistance has also been proposed (see, for example, Patent Document 4). The Ag alloy contains two or more of Au, Au, Bi, and tin (Sn), and the thin film made of the Ag alloy is heat-treated in an inert gas atmosphere at 130 to 200 ° C. This heat treatment improves sulfidation resistance.
また、過酷な耐腐食性試験でも反射率が劣化することがないＡｇ系の膜が提案されている（例えば、特許文献５を参照）。このＡｇ系の膜においては、純Ａｇ膜や、Ａｇ−Ａｕ系、Ａｇ−Ａｕ−Ｓｎ系、Ａｇ−Ｐｄ系、Ａｇ−Ｐｄ−Ｃｕ系の合金膜の表面に、ＩＴＯ、ＺｎＯ、ＩＺＯ、ＳｎＯ２などの酸化物、シリコン（Ｓｉ）、Ａｌ、Ｔｉ及びタンタル（Ｔａ）の酸化物、Ｓｉ、Ａｌ、Ｔｉ及びＴａの窒化物から選ばれた材料による極薄のキャップ層が積層されている。 In addition, an Ag-based film has been proposed in which the reflectance does not deteriorate even in a severe corrosion resistance test (see, for example, Patent Document 5). In this Ag-based film, a pure Ag film or an Ag-Au-based, Ag-Au-Sn-based, Ag-Pd-based, or Ag-Pd-Cu-based alloy film has ITO, ZnO, IZO, SnO on the surface thereof. A very thin cap layer made of a material selected from oxides such as 2 , oxides of silicon (Si), Al, Ti, and tantalum (Ta), and nitrides of Si, Al, Ti, and Ta is laminated.
さらに、Ａｇ合金膜は、時間の経過とともに、Ａｇの凝集が進行してＡｇ合金膜が劣化するという問題があった。これは、Ａｇ合金膜がコーティングされている面を大気中に露出した状態で使用すると、Ａｇ合金膜を覆っている透明膜の欠陥部を中心にＡｇの凝集が生じるためである。この問題に対処するものとして、Ｂｉ及び／又はＳｂの添加量を適切に制御して、Ａｇの表面拡散に起因する結晶粒の成長を効果的に抑制することにより、Ａｇの凝集抑止効果を高めたＡｇ合金膜が提案されている（例えば、特許文献６を参照）。ここでは、Ａｇ合金膜表面が酸素の存在する雰囲気に曝されると、Ａｇ合金膜中のＢｉ及び／又はＳｂがＡｇ合金膜の表面に拡散して濃縮し、Ｂｉ及び／又はＳｂの酸化物層が形成され、この酸化物層が環境との接触を遮断している。これによって、Ａｇ合金膜の劣化を防止している。 Furthermore, the Ag alloy film has a problem that Ag aggregation progresses with time and the Ag alloy film deteriorates. This is because, when the surface coated with the Ag alloy film is used in a state where it is exposed to the atmosphere, Ag agglomeration occurs around the defective portion of the transparent film covering the Ag alloy film. In order to cope with this problem, the addition amount of Bi and / or Sb is appropriately controlled to effectively suppress the growth of crystal grains due to the surface diffusion of Ag, thereby enhancing the Ag aggregation suppressing effect. An Ag alloy film has been proposed (see, for example, Patent Document 6). Here, when the surface of the Ag alloy film is exposed to an atmosphere in which oxygen is present, Bi and / or Sb in the Ag alloy film diffuses and concentrates on the surface of the Ag alloy film, and oxides of Bi and / or Sb. A layer is formed and this oxide layer blocks contact with the environment. This prevents the deterioration of the Ag alloy film.
Ａｇ系膜においては、その膜の反射率は、純Ａｇ膜が最も高いが、この純Ａｇ膜は、耐硫化性、耐湿性、耐熱性などが低い。そのため、上記特許文献１乃至３に示されるように、Ｐｄ、Ｃｕ、Ｇｅ、Ｂｉ、Ａｕ、Ｓｎ、希土類元素などを添加して、それらの膜の耐性、例えば、耐硫化性、耐熱性を改善している。しかしながら、それらの元素を添加することにより、その膜の反射率は、純Ａｇ膜より低下する。 In the Ag-based film, the reflectance of the film is the highest in the pure Ag film, but this pure Ag film has low sulfur resistance, moisture resistance, heat resistance, and the like. Therefore, as shown in the above Patent Documents 1 to 3, Pd, Cu, Ge, Bi, Au, Sn, rare earth elements, etc. are added to improve the resistance of these films, such as sulfidation resistance and heat resistance. doing. However, by adding these elements, the reflectance of the film is lower than that of a pure Ag film.
また、上記特許文献４に示されるように、Ｂｉ、Ａｕ、Ｓｎを添加したＡｇ合金膜を不活性ガス中で熱処理し、或いは、上記特許文献５に示されるように、純Ａｇ膜、又は、Ａｕ、Ｓｎ、Ｐｄ、Ｃｕのうちの一つ以上の元素を添加したＡｇ合金膜の上に、酸化物層などのキャップ層を付けた積層構造とし、その膜を、大気、真空、不活性ガス中で熱処理することにより、反射率の減少を抑制し、耐硫化性をさらに向上させる工夫がなされている。しかしながら、特許文献５に示された組成の膜では、熱処理を行なうと、大きな結晶粒の成長が起こり、結晶性の向上（移動度、伝導率の増加）による反射率の増加の効果を、成長した大きな結晶粒による光の散乱で弱める結果となる。 Further, as shown in Patent Document 4, Ag alloy film added with Bi, Au, and Sn is heat-treated in an inert gas, or as shown in Patent Document 5, a pure Ag film, or A laminated structure in which a cap layer such as an oxide layer is formed on an Ag alloy film to which one or more elements of Au, Sn, Pd, and Cu are added, and the film is formed in the atmosphere, vacuum, or inert gas. By heat-treating inside, the device which suppresses the reduction | decrease in a reflectance and improves a sulfide resistance further is made | formed. However, in the film having the composition shown in Patent Document 5, when heat treatment is performed, growth of large crystal grains occurs, and the effect of increasing reflectivity due to improvement in crystallinity (increasing mobility and conductivity) is obtained. As a result, light is scattered by the large crystal grains.
また、上記特許文献６に示されるように、Ｂｉ、Ｓｂが表面に拡散して濃縮されたＡｇ合金膜により、凝集を抑制する工夫がなされている。しかしながら、このＡｇ合金膜は耐硫化性、耐塩水性などが劣るため、他の膜で表面をコートする必要があり、用途が電磁波防止などに限られ、また、反射率も低下する。しかも、その表面のコートには、手間を要し、コストの増大を招く。 Moreover, as shown in the above-mentioned patent document 6, a device for suppressing aggregation is made by an Ag alloy film in which Bi and Sb are diffused and concentrated on the surface. However, since this Ag alloy film is inferior in sulfidation resistance, salt water resistance, etc., it is necessary to coat the surface with another film, the use is limited to prevention of electromagnetic waves and the like, and the reflectance is also lowered. In addition, the coating on the surface requires labor and increases costs.
以上から、Ａｇ合金膜が用いられる装置の性能をより向上させるためには、膜の耐硫化性、耐熱性、耐塩水性などの耐性を落とさずに、高い反射率を持ったＡｇ合金膜の開発が課題となる。
そこで、本発明は、耐硫化性、耐熱性、耐塩水性などの耐性を落とさずに、高い反射率を持ち、しかも、配線電極膜としても適用可能とする低抵抗率を実現したＡｇ合金膜及びその形成方法を提供することを目的とする。
From the above, in order to further improve the performance of devices using Ag alloy films, development of Ag alloy films with high reflectivity without reducing the resistance to sulfidation, heat resistance, salt water resistance, etc. of the film Is an issue.
Therefore, the present invention provides an Ag alloy film that has high reflectivity without reducing resistance such as sulfidation resistance, heat resistance, salt water resistance, and the like, and that realizes low resistivity that can be applied as a wiring electrode film. An object is to provide a method for forming the same.
本発明者らは、種々の研究により、Ａｇを主成分としてＳｂを含有させたＡｇ合金ターゲットを用いて基板上にスパッタリング成膜したＡｇ―Ｓｂ合金膜を熱処理（アニール）することにより、Ａｇ−Ｓｂ合金膜中の結晶粒が面内方向に成長し、大きな結晶粒を生成できること、さらには、この結晶粒の粒界には、Ｓｂが濃集されることが判明した。この結晶粒が面内方向に大きく成長したＡｇ―Ｓｂ合金膜では、移動度、伝導率の向上と平坦性の維持によって低抵抗率化と高反射率化が実現できるとともに、この熱処理によって結晶粒の表面及び界面に濃集されたＳｂが、酸素（Ｏ）と反応して酸化物となり、この酸化物が、耐硫化性、耐熱性、耐塩水性の向上に大きく寄与するという知見が得られた。 As a result of various studies, the inventors of the present invention heat treated (annealed) an Ag—Sb alloy film formed by sputtering on a substrate using an Ag alloy target containing Ag as a main component and containing Sb. It has been found that the crystal grains in the Sb alloy film grow in the in-plane direction and large crystal grains can be generated, and that Sb is concentrated at the grain boundaries of the crystal grains. In the Ag-Sb alloy film in which the crystal grains are greatly grown in the in-plane direction, low resistivity and high reflectivity can be realized by improving mobility and conductivity and maintaining flatness. It was found that Sb concentrated on the surface and the interface of this material reacts with oxygen (O) to become an oxide, and that this oxide greatly contributes to the improvement of sulfidation resistance, heat resistance and salt water resistance. .
そこで、これらの知見に基づいて、本発明の具体例として、Ｓｂが１．０ａｔ％含まれたＡｇ合金ターゲットを用いて、室温の基板上にスパッタ成膜を行ってＡｇ−Ｓｂ合金膜を成膜した。その後に、成膜したＡｇ−Ｓｂ合金膜に対して、真空雰囲気中で、３００℃の温度で熱処理を行った。 Therefore, based on these findings, as a specific example of the present invention, an Ag—Sb alloy film is formed by performing sputter deposition on a substrate at room temperature using an Ag alloy target containing 1.0 at% Sb. Filmed. After that, the formed Ag—Sb alloy film was heat-treated at a temperature of 300 ° C. in a vacuum atmosphere.
ここで、Ａｇ−Ｓｂ合金がスパッタリングで堆積されたままの状態（以下、as depo.状態と称す）の膜表面について、走査型電子顕微鏡（ＳＥＭ）、原子間力顕微鏡（ＡＦＭ）、オージェ電子分光法（ＡＥＳ）による面分析により得られた画像が図１に示されている。ＳＥＭ、ＡＥＳ、ＡＦＭのいずれの画像においても、as depo.状態においては、Ａｇ−Ｓｂ合金の結晶粒が細かく、表面の凹凸は小さいことが確認された。ＡＦＭ画像にみられるように、そのＡｇ−Ｓｂ合金膜の表面粗さＲａは、０．５９ｎｍであった。このas depo.状態のＡｇ−Ｓｂ合金膜では、その反射率は、純Ａｇ膜の反射率より低いものであった。 Here, a scanning electron microscope (SEM), an atomic force microscope (AFM), Auger electron spectroscopy is performed on the film surface in a state where the Ag—Sb alloy is deposited by sputtering (hereinafter referred to as an as depo. State). An image obtained by surface analysis by the method (AES) is shown in FIG. In any of SEM, AES, and AFM images, it was confirmed that in the as depo. State, the crystal grains of the Ag—Sb alloy were fine and the surface irregularities were small. As can be seen from the AFM image, the surface roughness Ra of the Ag—Sb alloy film was 0.59 nm. In this as depo. Ag-Sb alloy film, the reflectance was lower than that of a pure Ag film.
また、as depo.状態のＡｇ−Ｓｂ合金膜について、耐熱試験（３００℃、１時間、大気中アニール）、耐硫化試験（０．０１ａｔ％のＮａ２Ｓ溶液に１時間浸漬）、耐塩水試験（５ａｔ％のＮａＣｌ溶液に１２時間浸漬）を行ったが、試験後に反射率を測定した結果では、膜の反射率が低下し、耐塩水性、耐硫化性が無いことが確認された。 In addition, as-depo. Ag-Sb alloy film, heat resistance test (300 ° C., 1 hour, annealing in air), sulfur resistance test (immersion in 0.01 at% Na 2 S solution for 1 hour), salt water resistance test (Immersion in a 5 at% NaCl solution for 12 hours) The reflectance was measured after the test, and it was confirmed that the reflectance of the film was reduced and there was no saltwater resistance or sulfidation resistance.
次に、as depo.状態のＡｇ−Ｓｂ合金膜を、真空雰囲気中で、３００℃の熱処理を施したところ、図２に示されるような結果が得られた。図２のＳＥＭ、ＡＥＳ、ＡＦＭの各画像によれば、Ａｇ−Ｓｂ合金膜における結晶粒が、熱処理によって成長し、as depo.状態よりも面内方向に大きくなっていることが確認された。特に、図２のＡＥＳ画像にみられるように、熱処理により、Ａｇ−Ｓｂ合金の結晶粒中のＳｂがその表面及び粒界に濃集していることが観察された。即ち、画像中の濃い部分が結晶粒であり、その結晶粒を取り囲むように存在する淡い部分がＳｂの濃集を表している。この結晶粒の表面では、Ｓｂの多くが、酸化物として存在していることをＸ線光電子分光（ＸＰＳ）により確認した。 Next, the Ag-Sb alloy film in the as depo. State was subjected to a heat treatment at 300 ° C. in a vacuum atmosphere, and the result as shown in FIG. 2 was obtained. According to the images of SEM, AES, and AFM in FIG. 2, it was confirmed that the crystal grains in the Ag—Sb alloy film grew by heat treatment and became larger in the in-plane direction than the as depo. State. In particular, as seen in the AES image of FIG. 2, it was observed that Sb in the crystal grains of the Ag—Sb alloy was concentrated on the surface and grain boundaries by the heat treatment. That is, the dark part in the image is a crystal grain, and the light part existing so as to surround the crystal grain represents the concentration of Sb. It was confirmed by X-ray photoelectron spectroscopy (XPS) that most of Sb was present as an oxide on the surface of the crystal grains.
また、図２のＡＦＭの画像では、熱処理後においても、as depo. 状態よりも凹凸はやや大きくなっているが、ある程度の平坦度を保持していることが観察される。これは、ＳＥＭの画像で見られるように、as depo. 状態のＡｇ−Ｓｂ合金膜に対する熱処理によって、膜を構成する結晶粒はその面内方向に成長しやすい傾向があることを示している。結果として、膜の平坦度は保持されたまま、結晶性が向上することとなる。この平坦性の維持と結晶性の向上による移動度、伝導率の増加によって、熱処理後のＡｇ−Ｓｂ合金膜では、可視域（４００ｎｍ〜７００ｎｍ）の光において、純Ａｇ膜を超える反射率が計測された。また、結晶粒内のＳｂが粒界に濃集することにより、Ｓｂに由来する結晶粒内の欠陥が減少し、結晶性の良い大きな結晶粒が形成されることで、移動度が向上し、膜の抵抗率も低下することが確認された。 In addition, in the AFM image of FIG. 2, it is observed that the unevenness is slightly larger than that in the as depo. State even after the heat treatment, but a certain degree of flatness is maintained. This shows that the crystal grains constituting the film tend to grow in the in-plane direction by heat treatment on the as-depo. Ag-Sb alloy film, as seen in the SEM image. As a result, the crystallinity is improved while the flatness of the film is maintained. Due to the increase in mobility and conductivity by maintaining the flatness and improving the crystallinity, the Ag—Sb alloy film after heat treatment measures the reflectance exceeding the pure Ag film in the light in the visible region (400 nm to 700 nm). It was done. In addition, the concentration of Sb in the crystal grains concentrates at the grain boundary, thereby reducing defects in the crystal grains derived from Sb and forming large crystal grains with good crystallinity, thereby improving mobility. It was confirmed that the resistivity of the film also decreased.
さらに、熱処理後のＡｇ−Ｓｂ合金膜について、上述した試験と同様に、耐熱試験、耐硫化試験、耐塩水試験を行い、試験後に反射率を測定した結果、同様の試験後の純Ａｇ膜よりもかなり高い反射率が得られ、耐熱性、耐塩水性、耐硫化性に優れていることが確認できた。これら耐熱性、耐塩水性、耐硫化性の向上は、Ａｇ−Ｓｂ合金の結晶粒の表面に濃集したＳｂが、成膜中に混入した、或いは、成膜後において膜表面に付着したＯと反応し、その酸化膜が存在することに起因する。この酸化膜が、Ｓと塩水に対するバリア性や耐凝集性の効果を持っていることによる。 Further, as to the Ag—Sb alloy film after the heat treatment, the heat resistance test, the sulfidation resistance test, and the salt water resistance test were performed in the same manner as the above-described test, and the reflectance was measured after the test. As a result, it was confirmed that the film had excellent heat resistance, salt water resistance and sulfidation resistance. These improvements in heat resistance, salt water resistance, and sulfidation resistance are due to the fact that Sb concentrated on the surface of the crystal grains of the Ag-Sb alloy was mixed during the film formation or adhered to the film surface after the film formation. The reaction is caused by the presence of the oxide film. This is because this oxide film has an effect of barrier property against S and salt water and aggregation resistance.
上述した本発明の具体例として、成膜後のas depo.状態のＡｇ−Ｓｂ合金膜に対して、真空雰囲気中で熱処理を施した場合について説明したが、真空雰囲気中で熱処理する代わりに、窒素（Ｎ２）雰囲気中で熱処理を施しても、同様の結果が得られた。また、これらの雰囲気の代わりに、大気中で、３００℃の温度で熱処理を施したところ、図３に示されるように、図２に示された真空雰囲気中で熱処理を施した場合と同様の結果が得られた。 As a specific example of the present invention described above, the case where heat treatment is performed in a vacuum atmosphere on an as-depo. Ag-Sb alloy film after film formation has been described. Similar results were obtained when heat treatment was performed in a nitrogen (N 2 ) atmosphere. Further, instead of these atmospheres, when heat treatment was performed in the atmosphere at a temperature of 300 ° C., as shown in FIG. 3, the same as the case where heat treatment was performed in the vacuum atmosphere shown in FIG. Results were obtained.
図３のＳＥＭ、ＡＥＳ、ＡＦＭの各画像によれば、Ａｇ−Ｓｂ合金膜における結晶粒が、熱処理によって成長し、as depo.状態よりも面内方向に大きくなっていること、図３のＡＥＳ画像にみられるように、画像中の濃い部分が結晶粒であり、その結晶粒を取り囲むように淡い部分が存在するので、熱処理により、Ａｇ−Ｓｂ合金の結晶粒内のＳｂがその表面及び粒界に濃集する様子が観察できる。ここでも、この結晶粒の表面では、濃集したＳｂの多くが、酸化物として存在していることをＸ線光電子分光（ＸＰＳ）により確認した。 According to the SEM, AES, and AFM images in FIG. 3, the crystal grains in the Ag—Sb alloy film grow by heat treatment and are larger in the in-plane direction than the as depo. State, and the AES in FIG. As seen in the image, the dark portion in the image is a crystal grain, and there is a light portion so as to surround the crystal grain, so that the heat treatment causes Sb in the crystal grain of the Ag-Sb alloy to have its surface and grains. You can observe the concentration in the world. Again, it was confirmed by X-ray photoelectron spectroscopy (XPS) that much of the concentrated Sb was present as an oxide on the surface of this crystal grain.
一方、銅（Ｃｕ）や、パラジウム（Ｐｄ）の貴金属元素を添加したＡｇ合金膜は、３００℃程度の温度で熱処理を施すと純Ａｇ膜と同様に結晶粒の成長が起こり、凝集するため、大きな表面凹凸による光の散乱で反射率が低下する。また、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、マンガン（Ｍｎ）、Ｓｂなどの易酸化元素を添加したＡｇ合金膜は、結晶粒の成長、表面粗さＲａの増加が起こるものの、凝集することはない。しかしながら、これらの内、Ａｌ、Ｇａ、Ｍｎについては、３００℃の温度で熱処理を施すと、それらの結晶粒は、面内方向ではなく、面に垂直な方向に成長してしまう。その結果、凹凸が現われ、膜の平坦性を保持できないため、凹凸による光の散乱で反射率が低下する。ところが、Ｓｂに関しては、大気中で、３００℃の温度で熱処理を施しても、面内方向の結晶粒成長が面垂直方向に対して優勢であるため、面内方向に成長した大きな結晶粒を形成することとなって、膜の平坦性を保持でき、高い反射率を得ることができる。 On the other hand, an Ag alloy film to which a noble metal element such as copper (Cu) or palladium (Pd) is added is subjected to heat treatment at a temperature of about 300 ° C., so that crystal grains grow and aggregate in the same manner as a pure Ag film. Reflectance decreases due to light scattering due to large surface irregularities. In addition, Ag alloy films to which easily oxidizable elements such as aluminum (Al), gallium (Ga), manganese (Mn), and Sb are added cause crystal grain growth and increase in surface roughness Ra, but do not aggregate. Absent. However, among these, when Al, Ga, and Mn are heat-treated at a temperature of 300 ° C., their crystal grains grow not in the in-plane direction but in the direction perpendicular to the plane. As a result, irregularities appear and the flatness of the film cannot be maintained, and thus the reflectance is reduced due to light scattering by the irregularities. However, with regard to Sb, even if heat treatment is performed in the atmosphere at a temperature of 300 ° C., since the crystal grain growth in the in-plane direction is dominant over the vertical direction, large crystal grains grown in the in-plane direction are As a result, the flatness of the film can be maintained, and a high reflectance can be obtained.
したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成を採用した。
（１）本発明のＡｇ−Ｓｂ合金膜は、Ａｇを主成分とし、Ｓｂを含有するＡｇ合金において、前記Ｓｂが、Ａｇ合金膜の表面及び結晶粒界に濃集していることを特徴としている。
（２）（１）に記載のＡｇ合金膜において、前記Ｓｂは、０．５〜２．０ａｔ％含有されていることを特徴としている。
（３）本発明のＡｇ−Ｓｂ合金膜の形成方法は、Ａｇを主成分とし、Ｓｂを含有するＡｇ−Ｓｂ合金ターゲットを用いて基板上にスパッタリングしてＡｇ−Ｓｂ合金膜を成膜し、成膜されたＡｇ合金膜を熱処理することを特徴としている。
（４）（３）に記載のＡｇ−Ｓｂ合金膜の形成方法においては、前記熱処理の温度は、１５０〜４５０℃であることを特徴としている。
Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems.
(1) The Ag—Sb alloy film of the present invention is characterized in that, in an Ag alloy containing Ag as a main component and containing Sb, the Sb is concentrated on the surface of the Ag alloy film and the crystal grain boundary. Yes.
(2) The Ag alloy film described in (1) is characterized in that the Sb is contained in an amount of 0.5 to 2.0 at%.
(3) The method for forming an Ag—Sb alloy film of the present invention is a method of forming an Ag—Sb alloy film by sputtering on a substrate using an Ag—Sb alloy target containing Ag as a main component and containing Sb. The Ag alloy film thus formed is heat-treated.
(4) In the method for forming an Ag—Sb alloy film described in (3), the temperature of the heat treatment is 150 to 450 ° C.
ここで、本発明のＡｇ−Ｓｂ合金膜において、Ａｇ−Ｓｂ合金のＳｂの添加濃度を０．５〜２．０ａｔ％とすることが好ましい。その理由は、添加元素の濃度が０．５ａｔ％より少ないと、成膜後の熱処理によって、大きな結晶粒の成長が起こり、反射率が低下する。一方、その濃度が２．０ａｔ％を超えて大きいと、成膜後の熱処理による反射率の向上効果が小さくなる。 Here, in the Ag—Sb alloy film of the present invention, it is preferable that the additive concentration of Sb in the Ag—Sb alloy is 0.5 to 2.0 at%. The reason for this is that if the concentration of the additive element is less than 0.5 at%, large crystal grains grow due to the heat treatment after the film formation, and the reflectance decreases. On the other hand, if the concentration is higher than 2.0 at%, the effect of improving the reflectance by heat treatment after film formation is reduced.
また、Ａｇ−Ｓｂ合金膜の結晶粒の面内方向のサイズが１００ｎｍ以上であることが好ましく、結晶粒の面内方向のサイズが１００ｎｍ未満であると、移動度、伝導率が十分大きくならず、反射率の向上効果が小さくなる。また、膜表面の粗さＲａが２ｎｍ以下であることが好ましい。膜表面の粗さＲａが２ｎｍより大きいと、表面の凹凸が大きくなり、光の散乱が増加し、反射率が低下する。 In addition, the in-plane size of the crystal grains of the Ag—Sb alloy film is preferably 100 nm or more, and if the in-plane size of the crystal grains is less than 100 nm, the mobility and conductivity are not sufficiently increased. As a result, the effect of improving the reflectance is reduced. The film surface roughness Ra is preferably 2 nm or less. When the roughness Ra of the film surface is larger than 2 nm, the unevenness of the surface becomes large, light scattering increases, and the reflectance decreases.
また、１５０℃以下の基板温度でスパッタ成膜を行なったＡｇ−Ｓｂ合金膜を、大気、Ｎ２等の不活性ガス、真空等の雰囲気中で、１５０〜４５０℃の温度で、適度な時間（５ｍｉｎ〜２．０ｈ程度）の熱処理を施すことが好ましい。成膜時の温度を制御して作製する場合、熱処理の温度が１５０℃より低いと、Ａｇ−Ｓｂ合金膜における結晶性があまり向上せず、移動度、伝導率の増加が十分でなく、反射率の向上効果が小さくなる。また、４５０℃より高い温度での熱処理では、Ａｇ−Ｓｂ合金膜において、大きな結晶粒の成長が起こってしまい、膜の反射率が低下する。 Further, an Ag—Sb alloy film formed by sputtering at a substrate temperature of 150 ° C. or lower is subjected to an appropriate time at a temperature of 150 to 450 ° C. in an atmosphere such as air, an inert gas such as N 2, or a vacuum. It is preferable to perform heat treatment (about 5 min to 2.0 h). When manufacturing by controlling the temperature at the time of film formation, if the temperature of the heat treatment is lower than 150 ° C., the crystallinity in the Ag—Sb alloy film is not improved so much, and the mobility and conductivity are not sufficiently increased, and reflection The rate improvement effect is reduced. Further, in the heat treatment at a temperature higher than 450 ° C., large crystal grains grow in the Ag—Sb alloy film, and the reflectance of the film decreases.
なお、成膜後に熱処理を施してＡｇ−Ｓｂ合金膜を作製する場合には、成膜時の温度が１５０℃より大きいと、as depo.状態において既に大きな結晶粒から成る膜となり、熱処理後はさらに大きな結晶粒に成長してしまい、その大きな結晶粒の散乱によって、膜の反射率が低下する。 When an Ag—Sb alloy film is manufactured by performing heat treatment after film formation, if the temperature at the time of film formation is higher than 150 ° C., the film is already made of large crystal grains in the as depo. State. The film grows into larger crystal grains, and the reflectance of the film decreases due to scattering of the large crystal grains.
以上のように、本発明によれば、Ａｇを主成分としてＳｂを含有させたＡｇ−Ｓｂ合金ターゲットを用いて基板上にスパッタリング成膜したＡｇ−Ｓｂ合金膜を熱処理（アニール）することにより、面内方向へ成長した大きい結晶粒を形成できるので、膜の結晶性が向上して移動度、伝導率が増加するのと同時に平坦性が保持され、Ａｇ−Ｓｂ合金膜の反射率が向上する。しかも、結晶粒が面内方向に成長する際、合金中のＳｂが粒界に濃集されるので、耐熱性、耐塩水性、耐硫化性に優れた耐性を持つとともに、膜自体の低抵抗率化も実現できる。そのため、有機ＥＬ、太陽電池用反射膜（Ｓｉ系など）、光記録ディスク、光学機器用反射ミラー、光通信機器用反射膜、熱線反射膜などに用いる配線電極として利用可能となる。 As described above, according to the present invention, by heat-treating (annealing) an Ag—Sb alloy film formed by sputtering on a substrate using an Ag—Sb alloy target containing Ag as a main component and containing Sb, Since large crystal grains grown in the in-plane direction can be formed, the crystallinity of the film is improved, the mobility and conductivity are increased, and at the same time, the flatness is maintained, and the reflectivity of the Ag—Sb alloy film is improved. . Moreover, when the crystal grains grow in the in-plane direction, Sb in the alloy is concentrated at the grain boundaries, so that it has excellent heat resistance, salt water resistance, sulfidation resistance and low resistivity of the film itself. Can also be realized. Therefore, it can be used as a wiring electrode used for an organic EL, a reflective film for a solar cell (such as Si), an optical recording disk, a reflective mirror for an optical device, a reflective film for an optical communication device, a heat ray reflective film, and the like.
つぎに、本発明のＡｇ−Ｓｂ合金膜及びその製造方法について、以下に、真空雰囲気中で熱処理を施す場合と、Ｎ２雰囲気中で熱処理を施す場合と、大気中で熱処理を施す場合とに分けて、実施例及び比較例を示して具体的に説明する。 Next, regarding the Ag—Sb alloy film of the present invention and the method for producing the same, the case where heat treatment is performed in a vacuum atmosphere, the case where heat treatment is performed in an N 2 atmosphere, and the case where heat treatment is performed in the air are described below. It divides and demonstrates concretely, showing an Example and a comparative example.
〔実施例１〜１４〕
実施例１〜１４は、真空雰囲気中で熱処理を施す場合である。Ａｇ−Ｓｂ合金ターゲットを用いて、スパッタ法で、室温でガラス基板上に形成したＡｇ−Ｓｂ合金膜を、真空雰囲気中で、１時間の熱処理を施し、実施例１〜１４のＡｇ−Ｓｂ合金膜を作製した。
[Examples 1 to 14]
Examples 1 to 14 are cases where heat treatment is performed in a vacuum atmosphere. The Ag—Sb alloy film formed on a glass substrate at room temperature by sputtering using an Ag—Sb alloy target was heat-treated in a vacuum atmosphere for 1 hour, and the Ag—Sb alloys of Examples 1 to 14 A membrane was prepared.
そして、各実施例と比較するため、上記実施例と同様にＡｇ−Ｓｂ合金膜（as depo.状態）を成膜し、成膜後に熱処理を施さない場合の比較例１〜５のＡｇ−Ｓｂ合金膜を作製した。
さらに、標準的なＡｇ系の膜として、純Ａｇターゲット、及びＰｄまたはＣｕが１．０ａｔ％含まれたＡｇ−Ｐｄ、Ａｇ−Ｃｕ合金ターゲットを用いて上記実施例と同様の作製方法で純Ａｇ膜又はＡｇ合金膜を作製し、比較例６〜１１の膜とした。
And in order to compare with each Example, the Ag-Sb alloy film (as depo. State) was formed similarly to the said Example, and heat processing is not performed after film-forming. Ag-Sb of Comparative Examples 1-5 An alloy film was prepared.
Further, as a standard Ag-based film, pure Ag target, and Ag—Pd and Ag—Cu alloy target containing 1.0 at% of Pd or Cu are used to produce pure Ag by the same production method as in the above example. A film or an Ag alloy film was produced and used as films of Comparative Examples 6-11.
なお、Ａｇ−Ｓｂ合金膜、Ａｇ−Ｐｄ合金膜、Ａｇ−Ｃｕ合金膜および純Ａｇ膜のスパッタ成膜条件を以下に示す。
（スパッタリング成膜条件）
スパッタリング装置：ＤＣマグネトロンスパッタ装置（アルバック社製 ＣＳ−２００）
磁界強度：１０００Ｇａｕｓｓ（ターゲット直上、垂直成分）
到達真空度：＜５×１０−５Ｐａ
スパッタリングガス：Ａｒ
スパッタリングガス圧：０．５Ｐａ
スパッタリングパワー：ＤＣ２００Ｗ
基板：５０×５０×１ｍｍｔ 無アルカリガラス
膜厚：１００ｎｍ
Note that sputtering conditions for an Ag—Sb alloy film, an Ag—Pd alloy film, an Ag—Cu alloy film, and a pure Ag film are shown below.
(Sputtering film formation conditions)
Sputtering device: DC magnetron sputtering device (ULVAC CS-200)
Magnetic field intensity: 1000 Gauss (directly above the target, vertical component)
Ultimate vacuum: <5 × 10 −5 Pa
Sputtering gas: Ar
Sputtering gas pressure: 0.5 Pa
Sputtering power: DC200W
Substrate: 50 × 50 × 1 mmt Non-alkali glass film thickness: 100 nm
実施例１〜１４のいずれの膜も、結晶粒の面内方向のサイズが１００ｎｍ以上あり、面粗さＲａが２ｎｍ以下であり、結晶粒の粒界に、ＳｂとＯが濃集していることをＳＥＭ、ＡＦＭ、ＡＥＳによる面分析により確認した。また、実施例１〜１４及び比較例１〜１１の膜について、表面の結晶粒内と結晶粒界におけるＳｂとＯの濃度をＡＥＳによる定量分析により求めた。その結果を表１、２に示す。
ここで、表面形状は、ＡＦＭ（セイコーインスッル社製の原子間力顕微鏡、ＳＰＩ４０００）を用いて測定した。ＳＥＭ観察、表面の元素分布及び元素濃度の分析は、ＳＥＭ観察機能が備わったＡＥＳ（アルバック・ファイ社製のオージェ電子分光装置、ＰＨＩ ７００）を用いて測定した。
In any of the films of Examples 1 to 14, the in-plane direction size of the crystal grains is 100 nm or more, the surface roughness Ra is 2 nm or less, and Sb and O are concentrated at the grain boundaries of the crystal grains. This was confirmed by surface analysis using SEM, AFM, and AES. Moreover, about the film | membrane of Examples 1-14 and Comparative Examples 1-11, the density | concentration of Sb and O in the surface crystal grain and a crystal grain boundary was calculated | required by the quantitative analysis by AES. The results are shown in Tables 1 and 2.
Here, the surface shape was measured using AFM (Atomic Force Microscope manufactured by Seiko Instruments Inc., SPI4000). SEM observation, surface element distribution, and analysis of element concentration were measured using AES (Auger Electron Spectrometer manufactured by ULVAC-PHI, PHI 700) equipped with an SEM observation function.
次に、実施例１〜１４、比較例１〜１１の膜について、抵抗率、反射率、耐性試験後の反射率を測定した。反射率は、分光光度計（日立ハイテクノロジーズ社製の分光光度計、Ｕ４１００）を用い、波長が４００〜８００ｎｍの光を用いて測定したが、代表的な波長である４００ｎｍ、５５０ｎｍ、７００ｎｍでの反射率で示した。また、耐性に関して、耐熱試験（３００℃、１時間、大気中アニール）、耐硫化試験（０．０１ａｔ％のＮａ２Ｓ溶液に１時間浸漬）、耐塩水試験（５ａｔ％のＮａＣｌ溶液に１２時間浸漬）を実施した後に、波長が４００〜８００ｎｍの光を用いて、試験後の反射率を測定した。試験後の反射率については、４００〜８００ｎｍの波長範囲での平均反射率で示した。これらの測定結果が、表３，４に示されている。 Next, with respect to the films of Examples 1 to 14 and Comparative Examples 1 to 11, the resistivity, the reflectance, and the reflectance after the resistance test were measured. The reflectance was measured using a spectrophotometer (Hitachi High-Technologies spectrophotometer, U4100) using light having a wavelength of 400 to 800 nm, but the typical wavelengths are 400 nm, 550 nm, and 700 nm. The reflectance is shown. In addition, regarding heat resistance, heat resistance test (300 ° C., 1 hour, annealing in air), sulfidation resistance test (immersion in 0.01 at% Na 2 S solution for 1 hour), salt resistance test (12 hours in 5 at% NaCl solution) After the immersion), the reflectance after the test was measured using light having a wavelength of 400 to 800 nm. About the reflectance after a test, it showed by the average reflectance in the wavelength range of 400-800 nm. These measurement results are shown in Tables 3 and 4.
〔実施例１５〜２８〕
実施例１５〜２８は、Ｎ２雰囲気中で熱処理を施す場合である。これらの実施例では、真空雰囲気をＮ２雰囲気に代えた以外、実施例１〜１４と同様の手順に従って、Ａｇ−Ｓｂ合金膜を作製し、評価した。作製条件と評価の結果を、表５および表６に示す。
[Examples 15 to 28]
Examples 15 to 28 are cases where heat treatment is performed in an N 2 atmosphere. In these examples, an Ag—Sb alloy film was prepared and evaluated according to the same procedure as in Examples 1 to 14 except that the vacuum atmosphere was changed to an N 2 atmosphere. Production conditions and evaluation results are shown in Tables 5 and 6.
〔実施例２９〜４２〕
実施例２９〜４２は、大気雰囲気中で熱処理を施す場合である。これらの実施例では、真空雰囲気を大気雰囲気に代えた以外、実施例１〜１４と同様の手順に従って、Ａｇ−Ｓｂ合金膜を作製し、評価した。作製条件と評価の結果を、表７および表８に示す。
[Examples 29 to 42]
Examples 29 to 42 are cases where heat treatment is performed in an air atmosphere. In these examples, an Ag—Sb alloy film was prepared and evaluated according to the same procedure as in Examples 1 to 14 except that the vacuum atmosphere was changed to an air atmosphere. The production conditions and the results of evaluation are shown in Table 7 and Table 8.
表１〜８に示された結果によれば、実施例の膜は、少なくとも比較例の膜の抵抗率と同等かそれより低く、低抵抗率化を図ることができた。また、反射率に関しても、いずれも４００〜７００ｎｍの波長範囲で、as depo.状態の純Ａｇ膜と同等かそれ以上の反射率が計測され、反射率の向上が見られた。さらに、耐熱試験、耐硫化試験、耐塩水試験を実施したそれぞれの後に測定された実施例の膜の平均反射率は、比較例の膜の平均反射率と同等かそれより高くなっている。このことは、実施例の膜が、熱処理により、耐性が向上したことを示している。 According to the results shown in Tables 1 to 8, the film of the example was at least equal to or lower than the resistivity of the film of the comparative example, and a low resistivity could be achieved. In addition, regarding the reflectance, in the wavelength range of 400 to 700 nm, a reflectance equal to or higher than that of a pure Ag film in an as depo. State was measured, and an improvement in reflectance was observed. Furthermore, the average reflectance of the film of the example measured after each of the heat resistance test, the sulfurization resistance test, and the salt water resistance test is equal to or higher than the average reflectance of the film of the comparative example. This indicates that the film of the example has improved resistance by the heat treatment.
さらに詳細を述べると、Ｓｂの添加濃度が０．５ａｔ％と低いときには、１００℃の温度で熱処理を施した場合でも、そのＡｇ−Ｓｂ合金膜の反射率は、他の実施例と遜色ない結果が得られている。これは、Ｓｂの濃度が低いと、低温でも結晶粒の成長が促進され、抵抗率の低下と反射率の向上とが起こると考えられる。 More specifically, when the additive concentration of Sb is as low as 0.5 at%, even when heat treatment is performed at a temperature of 100 ° C., the reflectance of the Ag—Sb alloy film is comparable to the other examples. Is obtained. This is considered to be because when the Sb concentration is low, the growth of crystal grains is promoted even at a low temperature, and a decrease in resistivity and an increase in reflectance occur.
また、Ｓｂの添加濃度が１．０ａｔ％のとき、２００〜４００℃の温度で熱処理を施した実施例では、耐熱性、耐硫化性、耐塩水性のいずれにおいても良好な結果が得られた。一方、１５０℃以下の温度で熱処理を施した実施例では、結晶粒の成長が十分でなく、抵抗率が低下せず、４５０℃以上の温度で熱処理が施された場合には、大きな結晶粒成長が起こって膜の表面の凹凸が大きくなり反射率が低めであった。 Moreover, in the example which heat-processed at the temperature of 200-400 degreeC when the addition density | concentration of Sb was 1.0 at%, the favorable result was obtained in any of heat resistance, sulfidation resistance, and salt water resistance. On the other hand, in the example in which the heat treatment was performed at a temperature of 150 ° C. or less, the crystal grains did not grow sufficiently, the resistivity did not decrease, and when the heat treatment was performed at a temperature of 450 ° C. or more, large crystal grains As the growth occurred, the irregularities on the surface of the film increased and the reflectivity was low.
さらに、Ｓｂの添加濃度が、２．０ａｔ％と高い場合、５００℃の温度で熱処理した場合でも、そのＡｇ−Ｓｂ合金膜の反射率は、他の実施例と遜色ない結果が得られている。これは、Ｓｂ濃度が高いと、高温の熱処理でも、結晶の成長が抑制され、表面凹凸が大きくならないためと考えられる。一方、１５０℃の熱処理では、Ｓｂの濃度が高く結晶の成長が十分起こらないため、抵抗が下がらず、反射率が低めであった。 Further, when the additive concentration of Sb is as high as 2.0 at%, even when heat treatment is performed at a temperature of 500 ° C., the reflectance of the Ag—Sb alloy film is inferior to other examples. . This is presumably because, when the Sb concentration is high, crystal growth is suppressed even in high-temperature heat treatment, and the surface unevenness does not increase. On the other hand, in the heat treatment at 150 ° C., the concentration of Sb is high and crystal growth does not occur sufficiently, so that the resistance is not lowered and the reflectance is low.
表１〜８に示された結果によれば、実施例の膜では、いずれも表面に２．７ａｔ％以上のＳｂ,Ｏが存在し、ターゲットの最大濃度２．５ａｔ％よりも大きく、表面にＳｂが濃集していることが分かる。さらに、その表面において、結晶粒界の方が結晶粒内よりもＳｂ濃度が０．６ａｔ％以上高く、結晶粒界にＳｂが濃集していることが分かる。 According to the results shown in Tables 1 to 8, in the films of the examples, Sb, O of 2.7 at% or more is present on the surface, and the maximum concentration of the target is larger than 2.5 at%. It can be seen that Sb is concentrated. Further, it can be seen that the Sb concentration is 0.6 at% or more higher in the crystal grain boundary than in the crystal grain on the surface, and Sb is concentrated in the crystal grain boundary.
以上のように、実施例のＡｇ−Ｓｂ合金膜によれば、Ａｇを主成分としてＳｂを含有させたＡｇ−Ｓｂ合金ターゲットを用いて基板上にスパッタリング成膜したＡｇ−Ｓｂ合金膜を熱処理（アニール）することにより、結晶粒の面内方向への成長が促進されて、大きな結晶粒が形成できたので、結晶性が向上して移動度、伝導率が増加するのと同時に膜の平坦性が保持され、熱処理されたＡｇ−Ｓｂ合金膜の反射率が、as depo.状態の純Ａｇ膜、Ａｇ―Ｐｄ、Ａｇ−Ｃｕ及びＡｇ―Ｓｂ合金膜の場合より向上することが確認できた。さらに、結晶粒が面内方向に成長する際、合金結晶粒内のＳｂが粒界に濃集されるので、耐熱性、耐塩水性、耐硫化性に優れた耐性を持つとともに、膜自体の抵抗率を低下させることが確認された。そのため、本発明によるＡｇ−Ｓｂ合金膜は、有機ＥＬ、太陽電池用反射膜（Ｓｉ系など）、光記録ディスク、光学機器用反射ミラー、光通信機器用反射膜、熱線反射膜などに用いる反射膜、液晶やタッチパネルなどに用いる配線電極膜として好適であり、産業上優れたものである。 As described above, according to the Ag—Sb alloy film of the example, the Ag—Sb alloy film formed by sputtering on the substrate using the Ag—Sb alloy target containing Ag as a main component and containing Sb is heat-treated ( Annealing) promoted the growth of crystal grains in the in-plane direction, and formed large crystal grains. As a result, crystallinity was improved and mobility and conductivity were increased. It was confirmed that the reflectance of the Ag—Sb alloy film that was retained and heat-treated was improved as compared with the pure Ag film, Ag—Pd, Ag—Cu, and Ag—Sb alloy film in the as depo. Furthermore, when the crystal grains grow in the in-plane direction, Sb in the alloy crystal grains is concentrated at the grain boundary, so that the film has excellent resistance to heat resistance, salt water resistance, and sulfidation resistance, and the resistance of the film itself. It was confirmed that the rate was lowered. Therefore, the Ag—Sb alloy film according to the present invention is used for organic EL, solar cell reflective films (Si-based, etc.), optical recording disks, optical equipment reflective mirrors, optical communication equipment reflective films, heat ray reflective films, and the like. It is suitable as a wiring electrode film used for a film, a liquid crystal, a touch panel, etc., and is industrially excellent.
Claims (4)
前記Ｓｂが、Ａｇ−Ｓｂ合金膜の表面及び結晶粒界に濃集していることを特徴とするＡｇ−Ｓｂ合金膜。 An Ag—Sb alloy film containing Ag as a main component and containing Sb,
The Ag-Sb alloy film, wherein the Sb is concentrated on the surface of the Ag-Sb alloy film and the crystal grain boundary.
The method of forming an Ag-Sb alloy film according to claim 3, wherein the temperature of the heat treatment is 150 to 450 ° C.
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| JP5920659B2 JP5920659B2 (en) | 2016-05-18 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015151554A (en) * | 2014-02-10 | 2015-08-24 | 三菱マテリアル株式会社 | SPUTTERING TARGET FOR FORMING Ag ALLOY FILM AND Ag ALLOY FILM |
| JP2015178239A (en) * | 2014-03-19 | 2015-10-08 | 三菱マテリアル株式会社 | laminated film |
| KR20220107191A (en) | 2019-12-02 | 2022-08-02 | 미쓰비시 마테리알 가부시키가이샤 | Ag alloy film, Ag alloy sputtering target |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004263290A (en) * | 2002-08-09 | 2004-09-24 | Kobe Steel Ltd | Electromagnetic-shielding ag alloy film, electromagnetic-shielding ag alloy film formed body, and ag alloy sputtering target for depositing electromagnetic-shielding ag alloy film |
| JP2006037169A (en) * | 2004-07-27 | 2006-02-09 | Furuya Kinzoku:Kk | Silver alloy, sputtering target thereof and thin film thereby |
| JP2006284880A (en) * | 2005-03-31 | 2006-10-19 | Kobe Steel Ltd | Light reflecting film and light reflector |
| WO2006132414A1 (en) * | 2005-06-10 | 2006-12-14 | Tanaka Kikinzoku Kogyo K.K. | Silver alloy having excellent reflectivity/transmissivity maintaining characteristics |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004263290A (en) * | 2002-08-09 | 2004-09-24 | Kobe Steel Ltd | Electromagnetic-shielding ag alloy film, electromagnetic-shielding ag alloy film formed body, and ag alloy sputtering target for depositing electromagnetic-shielding ag alloy film |
| JP2006037169A (en) * | 2004-07-27 | 2006-02-09 | Furuya Kinzoku:Kk | Silver alloy, sputtering target thereof and thin film thereby |
| JP2006284880A (en) * | 2005-03-31 | 2006-10-19 | Kobe Steel Ltd | Light reflecting film and light reflector |
| WO2006132414A1 (en) * | 2005-06-10 | 2006-12-14 | Tanaka Kikinzoku Kogyo K.K. | Silver alloy having excellent reflectivity/transmissivity maintaining characteristics |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015151554A (en) * | 2014-02-10 | 2015-08-24 | 三菱マテリアル株式会社 | SPUTTERING TARGET FOR FORMING Ag ALLOY FILM AND Ag ALLOY FILM |
| JP2015178239A (en) * | 2014-03-19 | 2015-10-08 | 三菱マテリアル株式会社 | laminated film |
| KR20220107191A (en) | 2019-12-02 | 2022-08-02 | 미쓰비시 마테리알 가부시키가이샤 | Ag alloy film, Ag alloy sputtering target |
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| JP5920659B2 (en) | 2016-05-18 |
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