http://support.spring8.or.jp/Report_JSR/PDF_JSR_31A/2019A1832.pdf

2019A1832BL46XU

HAXPES ᶆ‽໬࡟ྥࡅࡓᨺᑕගࣛ࢘ࣥࢻࣟࣅࣥᐇ㦂
Round Robin Experiments for HAXPES Standardization㝜ᆅ ᏹ a,c, Ᏻ㔝 ⪽ b, 㡲⏣ ⪔ᖹ c, ᰘ⏣ ెᏕ c, ᶓ⁁ ⮧ᬛ d, ୖཎ ᗣ cHiroshi Oji , Satoshi Yasunob, Kohei Sudac, Yoshitaka Shibatac, Mitsutoshi Yokomizod, Yasushi Ueharaca,caྡྂᒇ኱Ꮫ㸪b䠄බ㈈䠅㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮, c䠄බ㈈䠅⛉Ꮫᢏ⾡஺ὶ㈈ᅋ, d䠄ᰴ䠅ࢥ࣋ࣝࢥ⛉◊a
Nagoya University, bJASRI, cAichi Science & Technology Foundation, dKobelco Research Institute. Incගࣅ࣮࣒ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗ࡟࠾࠸࡚ࠊSPring-8 BL46XU ࡜ AichiSR BL6N1 ࡢ୧ࣅ࣮࣒ࣛ࢖࡛ࣥ HAXPES ࣛ࢘ࣥࢻࣟࣅࣥᐇ㦂ࢆᐇ᪋ࡋ࡚࠸ࡿࠋձ⤌ᡂᐃ㔞ࡢࡓࡵࡢྛບ㉳࢚ࢿࣝࢠ࣮࡟࠾ࡅࡿ┦ᑐឤᗘಀᩘࡢࢹ࣮ࢱ࣮࣋ࢫ㛤Ⓨཬࡧղ᭷ຠῶ⾶㛗ࡉࡢᐇ ホ౯ࡢ 2 Ⅼ࡟╔┠ࡋࡓ ᐃࢆ୧᪋タ࡛㐍ࡵ࡚࠾ࡾࠊᮏㄢ㢟࡛⾜ࡗࡓᐇ㦂ࡶࡑࡢ୍⎔࡛࠶ࡿࠋᮏሗ࿌᭩࡛ࡣࠊ௒ᅇᚓࡽࢀࡓࢹ࣮ࢱࢆྵࡵࡓୖグձࠊղ࡟ᑐࡍࡿ㐍ᤖ≧ἣ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ࣮࣮࢟࣡ࢻ㸸 HAXPESࠊ┦ᑐឤᗘಀᩘࠊ᭷ຠῶ⾶㛗ࡉࠊගࣅ࣮࣒ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗ⫼ᬒ࡜◊✲┠ⓗ㸸㏻ᖖࡢᐇ㦂ᐊ⣔ XPS ࡼࡾࡶศᯒ῝ࡉࡀ῝࠸◳ X ⥺ග㟁ᏊศගࡢᏑᅾࡣࠊ᭱㏆࡛ࡣᗈࡃㄆ▱ࡉࢀࡿࡼ࠺࡟࡞ࡗࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊᐃ㔞ホ౯ࡢࡓࡵࡢ┦ᑐឤᗘಀᩘࡢࢹ࣮ࢱ࣮࣋ࢫࡀᏑᅾࡋ࡞࠸ࡇ
࡜ࡸࠊศᯒ῝ࡉ࡟㛵ࡍࡿᐇ ࢹ࣮ࢱࡀ୙㊊ࡋ࡚࠸ࡿࠊ࡜࠸ࡗࡓㄢ㢟ࡀ࠶ࡿࠋࡑࢀࡽࡢゎỴࢆ᭱⤊┠ᶆ࡜ࡋ࡚ࠊගࣅ࣮࣒ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗ࡛ࡣࠊSPring-8 ࡢ BL46XU ཬࡧ AichiSR ࡢ BL6N1 ࡟࠾࠸࡚ࠊບ㉳࢚ࢿࣝࢠ࣮3í10 keV ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ཰㞟ࢆ㐍ࡵ࡚࠸ࡿ[1]ࠋ๓⪅ࡢㄢ㢟࡟ᑐࡋ࡚ࡣࠊ㓟⣲ࢆྵࡴ໬ྜ≀ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ཰㞟ࡋࠊO 1s ࣆ࣮ࢡࢆᇶ‽࡜ࡋࡓྛບ㉳࢚ࢿࣝࢠ࣮࡟࠾ࡅࡿ┦ᑐឤᗘಀᩘࡢࢹ࣮ࢱ࣮࣋ࢫࢆ㛤Ⓨࡍࡿࡇ࡜ࢆ┠ᶆ࡜ࡋࠊࡇࢀࡲ࡛㓟໬≀ࢆ୰ᚰ࡜ࡋࡓ✀ࠎࡢヨᩱࡢ ᐃࢆ⾜ࡗ࡚ࡁࡓࠋᚋ⪅ࡢㄢ㢟࡟ᑐࡋ࡚ࡣࠊྛ✀ヨᩱ࡟࠾ࡅࡿ᭷ຠῶ⾶㛗ࡉࡢᐇ ࢹ࣮ࢱࢆ⵳✚ࡍࡿࡓࡵ࡟ࠊࡇࢀࡲ࡛✀ࠎࡢᇶᯈୖ࡟ⷧ⭷ࢆ〇⭷ࡋࡓヨᩱࢆస〇ࡋࠊࡑࢀࡽࡢヨᩱ࡟࠾ࡅࡿⷧ⭷࡜ᇶᯈ࠿ࡽࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ ᐃࢆ⾜࠸ࠊ᭷ຠῶ⾶㛗ࡉࡢᐇ ࢹ࣮ࢱࢆ⵳✚ࡋ࡚࠸ࡿࠋᮏᐇ㦂ㄢ㢟࡛⾜ࡗࡓᐇ㦂ࡶࠊࡑࢀࡽࡢྲྀࡾ⤌ࡳࡢ୍⎔࡛࠶ࡿࠋᮏሗ࿌᭩࡛ࡣࠊ௒ᅇᚓࡽࢀࡓࢹ࣮ࢱࡢゎᯒ⤖ᯝࢆྵࡵࡓࠊࡇࢀࡽࡢㄢ㢟࡟ᑐࡍࡿྲྀࡾ⤌ࡳ࡟ࡘ࠸࡚ࡢ⌧ᅾࡢ㐍ᤖ≧ἣ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋᐇ㦂㸸ບ㉳ග࢚ࢿࣝࢠ࣮5.95ࠊ7.94 ཬࡧ 9.92 keV ࡢ ᐃࡣ BL46XU ࡛⾜ࡗ࡚࠸ࡿࠋ㟁Ꮚศගჾ࡜ࡋ࡚
ࡣ Scienta Omicron R4000 L1-10kV ࢆ⏝࠸ࠊ㟁Ꮚศගჾࡢタᐃࡣࣃࢫ࢚ࢿࣝࢠ࣮200 eVࠊࢫࣜࢵࢺ
ᙧ≧ࡣ 0.5 mm × 30 mm ࡜ࡋࠊධᑕゅ 10°ࠊග㟁Ꮚ᳨ฟゅᗘ㸦TOA㸧80°࡛ ᐃࡋ࡚࠸ࡿࠋບ㉳ග࢚ࢿࣝࢠ࣮3 keV ࡢ ᐃࡣ AichiSR BL6N1 ࡛⾜ࡗ࡚࠸ࡿ[2,3]ࠋ㟁Ꮚศගჾ࡜ࡋ࡚ࡣ SPECS
Phoibos 150 CCD ࢆ⏝࠸ࠊࣃࢫ࢚ࢿࣝࢠ࣮20 eVࠊࢫࣜࢵࢺᙧ≧ࡣ 7 mm × 25 mm, curvedࠊධᑕゅ55°ࠊTOA 90°ࡢ᮲௳࡛ ᐃࢆᐇ᪋ࡋ࡚࠸ࡿࠋ௒ᅇࡢᐇ㦂࡛ࡣࠊ┦ᑐឤᗘಀᩘࢹ࣮ࢱ࣮࣋ࢫ㛤Ⓨ⏝࡜ࡋ࡚ࠊSiO2䠄300 nm䠅/SiࠊLiFࠊKClࠊGaNࠊ
KTaO3ࠊZnSe㸦௨ୖࠊᯈ≧ヨᩱ㸧ࠊTiO2ࠊVO2ࠊCr2O3ࠊNb2O5ࠊGa2O3ࠊFe2O3ࠊCoOࠊCuOࠊIn2O3ࠊ
SnO2㸦௨ୖࠊ⢊ᮎ㸧ࡢ 16 ヨᩱ࡟ࡘ࠸࡚ࠊບ㉳࢚ࢿࣝࢠ࣮5.95 ཬࡧ 9.92 keV ࡢࢹ࣮ࢱࢆྲྀᚓࡋࡓࠋヨᩱᖏ㟁ࡀᠱᛕࡉࢀࡿ⢊ᮎヨᩱ࡟ࡘ࠸࡚ࡣࠊᑟ㟁ᛶⅣ⣲⢊ᮎ㸦ࢣࢵࢳ࢙ࣥࣈࣛࢵࢡ㸧࡜ΰྜࡋ࣌ࣞࢵࢺ≧࡟ࡋࡓࡶࡢࢆ ᐃ࡟౪ࡋࡓࠋ᭷ຠῶ⾶㛗ࡉࡢᐇ ホ౯⏝࡜ࡋ࡚ࡣࠊMo/InGaZnO4䠄200nm䠅
/Si ᇶᯈ㸦Mo ⭷ཌ㸸0, 2.5, 5, 7.5, 10, 20, 200 nm㸧࡟ࡘ࠸࡚ࠊ7.94 keV ບ㉳ࡢࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸ձ ⤌ᡂᐃ㔞ࡢࡓࡵࡢྛບ㉳࢚ࢿࣝࢠ࣮࡟࠾ࡅࡿ┦ᑐឤᗘಀᩘࡢࢹ࣮ࢱ࣮࣋ࢫ㛤Ⓨ䠉㻝㻢㻟䠉
ᅗ 1 ࡟ບ㉳࢚ࢿࣝࢠ࣮5.95 ཬࡧ 9.92 keV ࡛ྲྀᚓࡋࡓࢣࢵࢳ࢙ࣥࣈࣛࢵࢡࢆΰྜࡋࡓ TiO2 ヨᩱཬࡧ Nb2O5 ヨᩱࡢ Ti 2p ཬࡧ Nb 3d ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋࡑࢀࡒࢀࡢ࣓࢖ࣥࣆ࣮ࢡ䠄Ti㻌2p3/2ࠊNb 3d5/2䠅
ࡢࣆ࣮ࢡ್ࢆぢࡿ࡜ᩥ⊩್[4]ࡢ TiO2䠄Ti 2p3/2: 458.3㹼459.3 eV䠅ཬࡧ Nb2O5䠄Nb 3d5/2: 207.0㹼208.1eV䠅࡜್ࡀ࡯ࡰ୍⮴ࡋ࡚࠾ࡾࠊບ㉳࢚ࢿࣝࢠ࣮࡟౫ࡽࡎᖏ㟁ࡢᙳ㡪ࡀ࡯࡜ࢇ࡝↓ࡃ ᐃࡀ࡛ࡁ࡚࠸ࡿ஦ࡀㄆࡵࡽࢀࡓࠋ௚㓟໬≀⢊ᮎヨᩱ࡟ࡘ࠸࡚ࡶࢣࢵࢳ࢙ࣥࣈࣛࢵࢡࢆΰྜࡉࡏࡿ஦࡛ᖏ㟁ࢆᢚ࠼ࡓ ᐃࡀྍ⬟࡛࠶ࡿ஦ࢆ☜ㄆࡋ࡚࠸ࡿࠋᅗ 1㸬ࢣࢵࢳ࢙ࣥࣈࣛࢵࢡࢆΰྜࡋࡓ TiO2 ヨᩱ䠄Ti 2p䠅ཬࡧ Nb2O5 ⢊ᮎヨᩱ䠄Nb 3d䠅ࡢ
HAXPES ࢫ࣌ࢡࢺࣝ䠄ບ㉳࢚ࢿࣝࢠ࣮㸸5.95 ཬࡧ 9.92 keV䠅
ᅗ 2 ࡟௒ᅇࡢ ᐃ⤖ᯝ࠿ࡽ O 1s ࢆᇶ‽ࣆ࣮ࢡ࡜ࡋ࡚ 1s ㌶㐨ཬࡧ 2p3/2 ㌶㐨ࡢ┦ᑐឤᗘಀᩘࢆồࡵࡓ⤖ᯝ䠄ᐇ ್䠅ࢆ♧ࡍࠋࣆ࣮ࢡ㠃✚ࡢ⟬ฟ᫬ࡢࣂࢵࢡࢢࣛ࢘ࣥࢻࡢ᥎ᐃ࡟ࡣ Shirley ἲࢆ⏝࠸࡚࠸ࡿࠋࡲࡓᅗ 2 ࡟ࡣィ⟬್࡟ࡼࡿ┦ᑐឤᗘಀᩘࡶేࡏ࡚♧ࡍࠋィ⟬್ࡣ Wagner ࡽ[5]ࡢ໬ྜ≀࡟࠾ࡅࡿ┦ᑐឤᗘಀᩘࡢ⪃࠼᪉ࢆᇶ࡟ࠊ௨ୗࡢᘧ䠄1䠅࠿ࡽồࡵࡓࠋ

SSO1s

1dV / d: O § E ·¨¸                                               㻔㻕dV / d: O1sOO1s ¨© EO1s ¸¹ࡇࡇ࡛ S ࡣྛඖ⣲‽఩࡟࠾ࡅࡿ┦ᑐឤᗘಀᩘࠊdV/d:ࡣග࢖࢜ࣥ໬ᚤศ᩿㠃✚ࠊOࡣග㟁Ꮚࡢ㠀ᙎᛶᖹᆒ⮬⏤⾜⛬䠄IMFP䠅ࠊE ࡣྛ㌶㐨ࢫ࣌ࢡࢺࣝࡢ㐠ື࢚ࢿࣝࢠ࣮ࢆ♧ࡋ࡚࠸ࡿࠋdV/d:ࡣග࢖࢜ࣥ໬᩿㠃✚[6]ཬࡧ㠀ᑐ⛠ࣃ࣓࣮ࣛࢱ[7]ࢆ௒ᅇࡢᐇ㦂᮲௳࡟ྜ࠺ࡼ࠺࡟ࢫࢣ࣮ࣜࣥࢢࡋ࡚⟬ฟࡋࠊග㟁Ꮚࡢ IMFP ࡣ TPP-2M ᘧ[8]࠿ࡽồࡵࡓ್ࢆ౑⏝ࡋ࡚࠸ࡿࠋᅗ 2 ࡼࡾࠊྛ‽఩ࠊྛບ㉳࢚ࢿࣝࢠ࣮࡟࠾࠸࡚ᐇ ್ཬࡧィ⟬್࡜ࡶ࡟⤖ྜ࢚ࢿࣝࢠ࣮ࡀቑຍࡍࡿࡢ࡟కࡗ࡚┦ᑐឤᗘಀᩘࡢ್ࡀ኱ࡁࡃ࡞ࡿഴྥࡀㄆࡵࡽࢀࡿࠋࡲࡓᐇ ್࡜ィ⟬್ࡢ್࡟ࡘ࠸࡚ࡣࠊᴫࡡࡼ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࡀࠊ୍㒊ࡢ㡿ᇦ࡛ࡣᕪ␗ࡀㄆࡵࡽࢀࡿࠋ≉࡟ྛບ㉳࢚ࢿࣝࢠ࣮࡜ࡶ 1s ‽఩ࡢ⤖ྜ࢚ࢿࣝࢠ࣮ࡀ㧗࠸㡿ᇦ䠄4㹼8 keV ㏆ഐ䠅࡛ᕪ␗ࡀⴭࡋࡃࠊィ⟬್࡟ẚ࡭࡚ᐇ ್ࡀప࠸஦ࡀศ࠿ࡿࠋࡇࡢせᅉ࡜ࡋ࡚ࠊྠ㡿ᇦࡣ㐠ື࢚ࢿࣝࢠ࣮ࡀప࠸ࡓࡵග㟁Ꮚࡢ IMFP ࡀᑠࡉࡃࠊ⾲㠃ࢥࣥࢱ࣑ࢿ࣮ࢩࣙ
ࣥ➼ࡢᙳ㡪ࢆཷࡅ್࡚ࡀపࡃ࡞ࡗ࡚࠸ࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ௒ᚋࠊࢲ࣓࣮ࢪࡢ↓࠸⾲㠃ࢡ࣮ࣜࢽࣥࢢ➼࡟ࡼࡿ෌ホ౯ࢆ⾜࠺ᚲせࡀ࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋ
㐠ື࢚ࢿࣝࢠ࣮ࡢప࠸㡿ᇦࢆ㝖ࡅࡤࠊ୧ບ㉳࢚ࢿࣝࢠ࣮࡜ࡶ࡟ᐇ ್࡜ィ⟬್ࡣࡼࡃ୍⮴ࡋ࡚࠾ࡾࠊ௒ᅇࡢ⤖ᯝ࠿ࡽ 1s ㌶㐨࡜ 2p3/2 ㌶㐨࡟ࡘ࠸࡚ࡣࠊᘧ䠄1䠅࡜㐺ษ࡞ࣃ࣓࣮ࣛࢱࢆ⤌ࡳྜࢃࡏࡿ
ࡇ࡜࡛ᐇ ್࡟㏆࠸┦ᑐឤᗘಀᩘࢆồࡵࡽࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ
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ᅗ 2㸬1s ㌶㐨ཬࡧ 2p3/2 ㌶㐨ࡢ┦ᑐឤᗘಀᩘࡢᐇ ್࡜ィ⟬್ࡢẚ㍑
䠄ບ㉳࢚ࢿࣝࢠ࣮㸸5.95 ཬࡧ 9.92 keV䠅ղ᭷ຠῶ⾶㛗ࡉࡢᐇ ホ౯᭷ຠῶ⾶㛗ࡉࡢᐇ ホ౯⏝࡟ྲྀᚓࡋࡓ Mo/InGaZnO4䠄200nm䠅/Si ᇶᯈ㸦Mo ⭷ཌ㸸0, 2.5, 5, 7.5, 10,20, 200 nm㸧࡟࠾ࡅࡿ Zn 2p3/2 ཬࡧ Mo 3d ࢫ࣌ࢡࢺࣝࢆᅗ 3 ࡟♧ࡍࠋMo ࡢ⭷ཌࡀཌࡃ࡞ࡿࡢ࡟ᚑ࠸ࠊ
ୗᆅࡢ InGaZnO4 ᒙ࠿ࡽࡢ Zn 2p3/2 ࣆ࣮ࢡࡀῶᙅࡋࠊMo ⭷࠿ࡽࡢ Mo 3d ࣆ࣮ࢡࡀቑຍࡍࡿᵝᏊࡀศ࠿ࡿࠋ⌧ᅾࡢ࡜ࡇࢁ Mo ⭷ཌࡢṇ☜࡞್ࡀᢕᥱ࡛ࡁ࡚࠸࡞࠸ࡓࡵࠊ௒ᚋࠊX ⥺཯ᑕ⋡䠄XRR䠅࡟ࡼࡿ
Mo ⭷ཌࡢホ౯ࢆ⾜࠸ࠊྛ‽఩ࡢࣆ࣮ࢡ㠃✚࠿ࡽ Mo ࡟࠾ࡅࡿ᭷ຠῶ⾶㛗ࡉࡢᐇ ್ࢆồࡵ࡚࠸ࡃࠋ
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ᅗ 3㸬Mo ⭷/InGaZnO4 ࡟࠾ࡅࡿ Zn 2p3/2 ࡜ Mo 3d ࡢ HAXPES ࢫ࣌ࢡࢺࣝࡢ Mo ⭷ཌ౫Ꮡᛶ䠄ບ㉳࢚ࢿࣝࢠ࣮7.94 keV䠅㻌䠉㻝㻢㻡䠉௒ᚋࡢㄢ㢟㸸┦ᑐឤᗘಀᩘ࡜ィ⟬್ࡢഴྥࡣࡼࡃ୍⮴ࡋ࡚࠸ࡿࡶࡢࡢࠊᕪ␗ࡀㄆࡵࡽࢀࡿ㡿ᇦࡶㄆࡵࡽࢀࡓࠋ≉࡟㐠ື࢚ࢿࣝࢠ࣮ࡢప࠸㡿ᇦࡣ⾲㠃ࢥࣥࢱ࣑ࢿ࣮ࢩࣙࣥࡢᙳ㡪ࢆཷࡅ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡾࠊప
㏿ Ar+࢖࢜ࣥ࡟ࡼࡿ⾲㠃ࢡ࣮ࣜࢽࣥࢢ࡞࡝ࢆ᳨ウࡍࡿᚲせࡀ࠶ࡿࠋࡑࡢ௚ࠊᐇ ್ࡢㄗᕪࡢ⟬ฟࡸィ⟬್࡟㐺⏝ࡍࡿྛ✀ࡢࣃ࣓࣮ࣛࢱ࣮䠄⿦⨨㛵ᩘ࡞࡝䠅ࡢጇᙜᛶࡢ᳨ウࡶ⾜ࡗ࡚࠸ࡃᚲせࡀ࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋ᭷ຠῶ⾶㛗ࡉホ౯࡟ࡘ࠸࡚ࡣࠊMo ⭷ཌࡢṇ☜࡞ホ౯࡜ࠊ㓟໬≀࡞࡝௚ᮦᩱ࡛ࡢホ౯ࢆ⾜ࡗ࡚࠸ࡃࠋཧ⪃ᩥ⊩㸸
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[3] 㡲⏣ࡽࠊAichiSR 2019 ᖺᗘබඹ➼฼⏝ᡂᯝሗ࿌᭩ࠊᐇ㦂␒ྕ㸸201902011.
[4] NIST X-ray Photoelectron Spectroscopy Database, NIST Standard Reference Database Number 20,Version 4.1, National Institute of Standards and Technology,䠄2012䠅, doi:10.18434/T4T88K,䠄2019 ᖺ 10
᭶ 6 ᪥㜀ぴ䠅
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