http://support.spring8.or.jp/Report_JSR/PDF_JSR_31A/2019A1813.pdf

2019A1813

BL46XU࣐ࢢࢿࢺࣟࣥࢫࣃࢵࢱᡂ⭷ࡉࢀࡓ㏱᫂ᑟ㟁⭷୰࡟ṧᏑࡍࡿᡂ⭷ᕼ࢞ࢫࡢ㟁Ꮚ≧ែࡢྠᐃ
Identification of the Electronic State of Deposition Inert Gas Remaining inTransparent Conductive Films Deposited by Magnetron Sputtering㔝ᮏ ῟୍ a, ໭ぢ ᑦஂ b
Junichi Nomoto a, Hisashi Kitami ba⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ㻌 ඛ㐍䝁䞊䝔䜱䞁䜾ᢏ⾡◊✲䝉䞁䝍䞊, b ఫ཭㔜ᶵᲔᕤᴗ䠄ᰴ䠅
aAdvanced Coating Technology Research Center,
National Institute of Advanced Industrial Science and Technology䠄AIST䠅,bSumitomo Heavy Industries, Ltd.,࣐ࢢࢿࢺࣟࣥࢫࣃࢵࢱᡂ⭷ࡉࢀࡓ Al ῧຍ ZnO䠄AZO䠅㏱᫂ᑟ㟁⭷ࡢᴟᛶࡣࠊ⭷୰࡬ࡢ㐣๫ Ar ΰධ࡟ࡼࡗ࡚ࠊZn ᴟᛶ࠿ࡽ O ᴟᛶ࡟ኚ໬ࡍࡿࡇ࡜ࡀ◳ X ⥺ග㟁Ꮚศග䠄HAXPES䠅࡟ࡼࡗ࡚ ᐃࡉࢀࡓ౯㟁Ꮚᖏࢫ࣌ࢡࢺࣝࡼࡾ᫂ࡽ࠿࡜࡞ࡗࡓࠋO ᴟᛶࡣ Zn ᴟᛶ࡜ẚ㍑ࡋ࡚ࠊ࢔ࢡࢭࣉࢱᆺࡢḞ㝗ࡀᑟධࡉࢀࡸࡍࡃࠊࡲࡓ␗ᖖࢢࣞ࢖ࣥᡂ㛗࡟ࡼࡿ⾲㠃ᖹᆠᛶࡢపୗࡸᡂ⭷࣮ࣞࢺࡢపୗ࡞࡝㏱᫂
㟁ᴟᙧᡂ࡟ᑐࡋࠊఱࢀࡶ㈇ࡢຠᯝࢆࡶࡓࡽࡍࠋ⤖ᯝࢆ㏻ࡌ࡚ࠊṧ␃ Ar ࡢపୗࡀ㧗ఏᑟ㏱᫂㟁ᴟ㛤Ⓨ࡟ᴟࡵ࡚㔜せ࡞ࣇ࢓ࢡࢱ࣮࡛࠶ࡿࡇ࡜ࡀ෌ㄆ㆑ࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ㸸 㓟໬ள㖄ࠊ㏱᫂ᑟ㟁⭷ࠊṧ␃࢔ࣝࢦࣥࠊᴟᛶࠊ◳ X ⥺ග㟁Ꮚศග⫼ᬒ࡜◊✲┠ⓗ㸸㧗㏿኱㠃✚ᡂ⭷ྍ⬟࡞┤ὶ࣐ࢢࢿࢺࣟࣥࢫࣃࢵࢱࣜࣥࢢ䠄DC-MS䠅ᡂ⭷ἲࡣࠊ㏱᫂ᑟ㟁ᛶ㓟໬≀ⷧ⭷ࡢሁ✚ᢏ⾡࡜ࡋ࡚᭱ࡶ୍⯡ⓗ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊᙜヱᢏ⾡ࡣ㟁ẼఏᑟࡸᶵᲔⓗᙉᗘࡀᇶᯈࡢ఩⨨࡟ᙉࡃ౫ᏑࡍࡿࠊゎỴࡍ࡭ࡁㄢ㢟ࢆᢪ࠼࡚࠸ࡿࠋ౛࠼ࡤࠊࢱ࣮ࢤࢵࢺࡢ࢚࣮ࣟࢪࣙࣥ㡿ᇦ࡟ᑐྥࡍࡿᇶᯈࡢ఩⨨࡟ᡂ㛗ࡋࡓ⭷ࡢ᢬ᢠ⋡ࡸṧ␃ᛂຊࡀࠊୖグ㡿ᇦ࠿ࡽ㐲ࡃ㞳ࢀࡓ఩⨨࡟ሁ✚ࡋࡓ⭷ࡢࡑࢀࡽ࡜ẚ㍑ࡋ࡚㠀ᖖ࡟㧗࠸ࠋࡇࢀࡽࡢ≉ᛶศᕸࡣᇶᯈࢆᦙ㏦ࡉࡏ࡚ᡂ⭷ࡍࡿࡇ࡜࡟ࡼࡾࠊศᕸࡑࡢࡶࡢࡣᨵၿࡍࡿࡇ࡜ࡀ࡛ࡁࡿࡀࠊᚓࡽࢀࡿ᢬ᢠ⋡ࡢ⤯ᑐ್ࡣ࢚࣮ࣟࢪࣙࣥᑐྥ㒊ࡢ㧗࠸್࡟ᚊ㏿ࡉࢀࡿࠋ㛗ᖺࠊୖグ≉ᛶࡢ✵㛫ศᕸࡢ୙ᆒ୍ᛶࢆỴᐃࡍࡿ୺࡞せᅉࡣࡲࡔ᏶඲࡟ࡣ⌮ゎࡉࢀ࡚࠸࡞࠿ࡗࡓࠋᡃࠎࡣࠊ࢞ࣛࢫᇶᯈୖ࡟ MS ᡂ⭷ࡋࡓ Al ῧຍ ZnO䠄AZO䠅⭷ࡢྛ✀≉ᛶ࡟ᑐࡍࡿࢱ࣮ࢤࢵࢺࡢ࢚࣮ࣟࢪࣙࣥ㡿ᇦࡢᙳ㡪ࢆヲ⣽࡟ㄪ࡭ࡓࠋࡑࡢ⤖ᯝࠊ࢚࣮ࣟࢪࣙࣥᑐྥ㒊࡛ࡢ≉ᛶຎ໬ࡢ୺ᅉࡣࠊࢱ࣮ࢤࢵࢺࢆࢫࣃࢵࢱࣜࣥࢢࡋࡓᚋ࡟཯㊴ࡍࡿᡂ⭷࢞ࢫ࡛࠶ࡿ࢔ࣝࢦࣥ䠄Ar䠅ࡀࠊᑐྥࡍࡿᇶᯈ఩⨨࡟ᡂ㛗ࡋࡓⷧ⭷୰࡟ṧ␃ࡍࡿࡇ࡜࡛࠶ࡿࡇ࡜ࢆⓎぢࡋࡓ [1,2] ࠋᮏㄢ㢟࡛ࡣ AZO ⷧ⭷୰ࡢṧ␃ Ar ࡢ㟁Ꮚ≧ែࡢゎ᫂ཬࡧࠊ⏕ࡌࡿ㟁Ẽ≉ᛶຎ໬ࡢ㟁Ꮚࣂࣥࢻᵓ㐀ࡢほⅬ࠿ࡽࡢゎ᫂ࢆ┠ⓗ࡜ࡋ࡚ࠊࣂࣝࢡᩄឤࢆ≉ᚩ࡜ࡍࡿ◳ X ⥺ග㟁Ꮚศග䠄HAXPES䠅 ᐃཬࡧゎᯒࢆ⾜ࡗࡓࠋᐇ㦂㸸AZO ⷧ⭷ࡣࠊ࢞ࣛࢫᇶᯈ䠄Corning, Eagle-XG䠅ୖ࡟ࠊZnO ࡟ Al2O3 ࢆ 2.0 wt.%ࢆΰྜࡋࡓ෇ᙧ㧗ᐦᗘ↝⤖యࢱ࣮ࢤࢵࢺࢆ⏝࠸ࡿ࣐ࢢࢿࢺࣟࣥࢫࣃࢵࢱ⿦⨨࡟ࡼࡾᡂ⭷ࡋࡓࠋ⭷୰ࡢṧ␃ Ar ࡣࠊᡂ⭷ ᗘࠊᡂ⭷㟁ຊࠊࡑࡋ࡚ᇶᯈ఩⨨ࡢ 3 ࡘࡢᡂ⭷᮲௳ࡢ࣐ࢺࣜࢡࢫ࡟ࡼࡾࠊไᚚࡋࡓࠋ⭷୰ṧ␃Ar 㔞ࡣࠊ㟁Ꮚ⥺࣐࢖ࢡࣟ࢔ࢼࣛ࢖ࢨ䠄EPMA䠅࡟ࡼࡗ࡚ᚓࡽࢀࡿ Ar-KDࣆ࣮ࢡࡢ㠃✚ᙉᗘ࡟ࡼࡾ༙ᐃ㔞໬ࡋࡓࠋ୍౛࡜ࡋ࡚ࠊ
⾲ 1 ࡟␗࡞ࡿ Ar ṧ␃㔞ࡢ AZO ⷧ⭷࠿ࡽᚓࡽࢀࡓ㟁Ẽⓗ≉ᛶ; ᢬ᢠ⋡䠄ȡ䠅ࠊ࢟ࣕࣜ࢔ᐦᗘ䠄N䠅ࠊHall ⛣ືᗘ䠄ȝH䠅ࢆ♧ࡍࠋ⾲ 1 ࠿ࡽ᫂ࡽ࠿࡞ࡼ࠺࡟ࠊAr ṧ␃㔞ࡀከ࠸⭷ࡣᑡ࡞࠸⭷࡜ẚ㍑ࡋ࡚ N ཬࡧ ȝH ࡀⴭࡋࡃపࡃࠊ⤖ᯝ࡜ࡋ࡚ ȡ ࡀ㧗࠸ࠋ
HAXPES ᐃ࡟ࡣࠊ⏘ᴗ฼⏝ࣅ࣮࣒ࣛ࢖ࣥ BL46XU VG ScientaR4000 ࢩࢫࢸ࣒ࢆ฼⏝ࡋࡓࠋᶆ‽ⓗ࡟㐠⏝ࡉࢀ࡚࠸ࡿ࢚ࢿࣝࢠ࣮: 7.94 keV ཬࡧගᏛ⤖ᬗ: Si䠄111䠅 DCM + Si䠄444䠅CC ࡛సࡾฟࡉࢀࡿศゎ⬟⣙ 240 meV ග※ࢆ⏝࠸࡚┿✵୰ᐊ ࡛ࡢ ᐃࢆ⾜ࡗࡓࠋX ⥺ࡢヨᩱ࡬ࡢධᑕゅᗘࡣ䠉㻝㻠㻡䠉
5rࠊග㟁Ꮚྲྀࡾฟࡋゅᗘࡣ 85r࡜ࡋࡓࠋ⾲ 1㸬AZO ⷧ⭷ࡢ㟁Ẽⓗ≉ᛶAr-KD㠃✚ᙉᗘ
[a.u.]

U

NP+>ȍcm][cm-3][cm2/Vs]

18.7

1.45㽢10-2 5.01㽢1019

8.6

10.8

8.81㽢10-4 3.37㽢1020

21.0

Normalized intensity[arbitrary unit]⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸㐣๫࡞ Ar ࡢΰධࡣ AZO ⷧ⭷ࡢᴟᛶࢆ O ᴟᛶ࡬࡜ኚ࠼࡚ࡋࡲ࠺ࡇ࡜ࡀ HAXPES ࡟ࡼࡗ࡚ ᐃࡉࢀࡓ౯㟁Ꮚᖏ䠄VB䠅ࢫ࣌ࢡࢺࣝࡼࡾ᫂ࡽ࠿࡜࡞ࡗࡓࠋᅗ 1 ࡟ HAXPES ᐃ࡟ࡼࡗ࡚ᚓࡽࢀࡓ Arṧ␃㔞ࡀᑡ࡞࠸ࠊከ࠸ AZO ⷧ⭷ࡢ VB ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᅗ 1 ࠿ࡽ᫂ࡽ࠿࡞ࡼ࠺࡟ࠊ୧⪅ࡢ㐪࠸ࡣ⤖ྜ࢚ࢿࣝࢠ࣮⣙ 4.8 eV ࡟࠾ࡅࡿࢧࣈࣆ࣮ࢡࡢ᭷↓࡛࠶ࡾࠊ᫂ⓑ࡛࠶ࡿࠋHAXPES ࡛ほ ࡉࢀࡿᙜヱࣆ࣮ࢡࡢ᭷↓ࡣࠊZnO ⷧ⭷ࡢᴟᛶࡢࣇ࢕࣮ࣥ࢞ࣉࣜࣥࢺ࡜ࡋ࡚▱ࡽࢀ࡚࠾ࡾࠊࢧࣈࣆ࣮ࢡࡀ᭷ࡿሙྜࡣ Zn ᴟᛶࠊᑐࡋ࡚↓࠸ሙྜࡣ O ᴟᛶ࡜ุ᩿ࡉࢀࡿ[3,4]ࠋࡍ࡞ࢃࡕࠊᅗ 1 ࡟♧ࡍ Arṧ␃㔞ࡀᑡ࡞࠸ࠊከ࠸ AZO ⷧ⭷ࡣࡑࢀࡒࢀ Zn ᴟᛶཬࡧ O ᴟᛶ࡜ุ᩿ࡉࢀࡿࠋO ᴟᛶࡣ Zn ᴟᛶ࡜ẚ㍑ࡋ࡚ࠊ࢔ࢡࢭࣉࢱᆺࡢḞ㝗ࡀᑟධࡋࡸࡍ࠸ࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ[5]ࠋࡍ࡞ࢃࡕࠊAr ṧ␃㔞ࡀከ࠸⭷࡛ࡣ Ar ΰධࡢᙳ㡪[1,2]࡜┦ࡲࡗ࡚⾲ 1 ࡟♧ࡋࡓࡼ࠺࡟ N ཬࡧ ȝH ࡢⴭࡋ࠸పୗ࡟క࠺ ȡࡢ኱ᖜ࡞ୖ᪼࡟⮳ࡗࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊO ᴟᛶࡣ␗ᖖࢢࣞ࢖ࣥᡂ㛗࡟ࡼࡿ⾲㠃ᖹᆠᛶࡢపୗ
ࡸࠊᡂ⭷࣮ࣞࢺࡀ Zn ᴟᛶ࡜ẚ㍑ࡋ࡚ప࠸ࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࡀࠊᙜヱ O ᴟᛶ࡜ุ᩿ࡉࢀࡓ Arṧ␃㔞ࡀከ࠸ AZO ⷧ⭷࡟࠾࠸࡚ࡶྠᵝ࡞⤖ᯝࢆ♧ࡋ࡚࠸ࡿࡇ࡜ࡀࠊ㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾࡟ࡼࡿ⾲㠃࣭᩿㠃ᙧ≧ほᐹ࠿ࡽ☜ㄆࡉࢀࡓࠋ
ࡇࢀࡲ࡛࡟ࠊAl ࡸ Ga ࢆప㔞ῧຍࡋࡓ ZnO ⭷࡛ࡣ O ᴟᛶࢆ♧ࡍࡢ࡟ᑐࡋࠊከ㔞ῧຍࡋࡓሙྜ࡛
ࡣ Zn ᴟᛶࢆ♧ࡍࡇ࡜ࡀሗ࿌ࡉࢀ࠸࡚ࡿ[6,7]ࠋᙜヱⷧ⭷ࡣ Al ࡢከ㔞ῧຍ࡟ヱᙜࡍࡿࡓࡵࠊୖグࡋࡓ O ᴟᛶࢆ♧ࡍ⤖ᯝࡣண᝿እ࡛࠶ࡗࡓࠋ࣓࢝ࢽࢬ࣒ࡣᮍゎ࡛᫂ࡣ࠶ࡿࡀࠊ⣔⤫ⓗ࡟ኚ໬ࡉࡏࡓAr ṧ␃㔞࡜ VB ࢫ࣌ࢡࢺࣝ࠿ࡽุ᩿ࡉࢀࡿᴟᛶ࡜ࡢ㛵ಀ࠿ࡽࠊᴟᛶ཯㌿ࡣ㐣๫࡞ Ar ΰධ࡛⏕ࡌࡓ࡜⤖ㄽ௜ࡅ࡚࠸ࡿࠋ

Ar contents
LightlyHeavily

16 14 12 10 8 6 4 2
Binding energy [eV]0ᅗ 1㸬౯㟁Ꮚᖏ䠄VB䠅ࢫ࣌ࢡࢺࣝཧ⪃ᩥ⊩㸸[1] J. Nomoto, et.al., J. Appl. Phys. 124, 065304䠄2018䠅.
[2] J. Nomoto, et.al., ACS Omega 4, 14526䠄2019䠅.
[3] M.W. Allen, et.al., Appl. Phys. Lett. 98, 101906䠄2011䠅.
[4] J.R.Williams, et.al., Appl. Phys. Lett. 100, 051902䠄2012䠅.
[5] H. Makino, H. Shimizu, Appl. Surf. Sci. 439, 839䠄2018䠅.
[6] Y. Adachi, et.al., Thin Solid Films 519, 5875䠄2011䠅.
[7] T. Ogino, et.al., Thin Solid Films 552, 56䠄2014).
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