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îï[ PES!ð 1(a)"7RSOhGñu5IsKòSóØôaõö÷QsKø[¨8ùú_×ØS¹XASNNZnPc᠂XዴႆήࢍࡇЎࠋʚഏᩓ‫܇‬࢐ࣱ૝ʏჇᆰแˮ¼¹C¿ÀFIóØ[¨8ûüR%ZOýþ7qziEF45ê8óØRÑ³´µA"B8ÿ óØ!aS\"Z[NZnNHOMO᠂XዴԈӓࢍࡇЎࠋ

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h!o,-ê5ziXES 7RåCíÒ

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h!ih!iᩓಊ ஊೞ‫ޖ‬ᩓಊ ஊೞ‫ޖ‬‫׋‬1 (a) ήᩓ‫્܇‬ЈƴǑǔήᩓ‫܇‬ǹȚǯȈȫ(PES)(b) ϋ൉ѕឪƴǑǔ᠂XዴႆήǹȚǯȈȫ(XES)Ʊ
᠂XዴԈӓǹȚǯȈȫ(XAS)

 z78#¥®C9:z4¯aì;zi"$`7R XES P<=å>? X +@>"åæ!FY-XAS"CüQSABZ[sKLMN¯FG
Cê5zDEFG?HI@J!ZnPc, ð 1"8C°± z4¯7SsKLMN8OFI;ÛÜÝÞÝßàáâã878#¥®CKÒ z4¯CLZ¯FIi
᬴ܱXES P< FY-XAS Ò2R"#MN$`8»OPÎå$`QR!UVSOR"8 BL3U 7ShIi
Ò2OüQI ZnPc TR SiO2/Si(111)äO¶UFGPSVWX8\¡¦§C 300 ~ 320 K ¯ 88 K O
YW4¯7 ZnPc 8T¯ZéTCb5[5¶UFIi45ê8óØ8 XES Ò2OPQGR* X +\.OzóØ]^C_`I­S20 !m/min 7Ò2aCbcZOdeFIiኽௐƱᎋ‫ݑ‬
SiO2/Si(111)äO ZnPc C 300 nm f·¸IO¬ i\¡¦§ 300 ~ 320 K 7¶UFI ZnPc
T!RT-ZnPc"7RSFY-XAS Ag=>ÜR
yh[ .i_C¬ ij .!GI"7Rå8¹k=>Ü!E"a\¡¢£Olmno7S
XAS Ag=>Ü8@>pÞ=RZqOrQi

C K-edge FY-XAS!LT"ZnPc(NI)!RT"ZnPc(NI)!RT"ZnPc(GI)Intensity / normalizedóØ8 C K @>O FY-XAS Ag=>ÜCð 2

N K-edge FY-XAS!LT"ZnPc(NI)!RT"ZnPc(NI)!RT"ZnPc(GI)ejSo .!NI"7R E a\¡¢£OsS7S
b8Ag=>ÜOR C 1s Vê "*tu8vw
Ox; zyQ@>pÞ=a5zi#$%&8/z{O5~SC 1s Vê "*tu8vw

280290300

310

390

400

410

420430

Photon Energy / eV‫׋‬2 ZnPcƷኽ୒ᐏ(RT-ZnPc)Ʊ᩼୒ឋᐏ(LT-ZnPc)Ʒ
C KԈӓᇢƓǑƼN KԈӓᇢFY-XASǹȚǯȈȫRS" #XC| z C 2pz tu8}O E asS!no"[¯HO~!°"vw¯[zi484¯VêSRT-ZnPc/SiO2/Si(111)7RS"#R\¡¢£OFGhGÚFGQz4¯a"Vzi45RS\¡¢£a_[ùú_×Ø7qz4¯¯ST aÂ"O Q4¯Vê"#\¡8«¶üar%"#«¶üaZOT¤|O¶ü zI­7qziej%\¡¦§ 88 K
7¶UFI ZnPc ZéT!LT-ZnPc"8¹ºSFY-XAS Ag=>ÜR[ .i_C¬·S
RT-ZnPc 8 NI ¯ GI 8Ag=>ÜCFºu¸Ip[¤¥C¬ i45RS|TX8\¡¦§aÂ"OQ¹ºS"#«¶üOzT8ÌaõöSZéTa¤|·5II­7qziä88[z ZnPc T878#¥®C9:zI­SC K ¯ N K 8
XES ÑCShIiz()!normal emission, NXES"RÏ"¥®U§C zi
ð 3(a)R RT-, LT-ZnPc O z C K#, N K# NXES Ag=>Ü¯TóØ!T20 nm"O z PES Ag=>ÜC

FI7qziNXES Rw¥®U§C z PES¯Q

C¬

aSyh[_R¬F

Intensity / arb. units#$µJÌ8q¯#µJÌOZcå(a) C K", N K" NXES!RT"ZnPc!LT"ZnPc

GQ[Qiej%%&¯cåaeW8()7õöz¡¢JÛÜÝÞOF[Qi48±pÞ=!*"¯¯!$"8;ÛÜÝÞ²R³ 0.8 eV 7%Eg – e2/4"""0r !r: "#´µ"Intensity / arb. units¯!$"C°hIª«Z¬¤¥7S48R%&;

hvi = 410 eV

N K"

hvi = 40 eVPES
thin film-100Energy (vs. EF) / eV

cå!RXES"Ag=>Ü!ð 3(b)"7R%N K# RXES 8©_
LT-ZnPc 7Rª«¬¤¥!aSRT-ZnPc 7R­?Þ®[

C K"

-20

£¤7qS¥¥®OP{z6%&8¦§C¨}z£¤pÞ=!*"¤¥aOFG[hGQzi

hvi = 295 eV(b) N K" RXES!RT"ZnPc!LT"ZnPc*hvi / eV398.1
398.1*Vê¶6z%&#8·¸;ÛÜÝÞ!0.6 ~ 0.8 eV"¯e¹z4¯auVhIiä84¯VêSRT-ZnPc 7KÒFI©_£¤pÞ=8¯RS¥®OP{z"#8Èw%&OzZ©_£¤!RIXS"7
õöI energy loss ¯ energy gain ¯º}ê5zi

380

390

400

402.1
402.1
410

Emission Energy / eV‫׋‬3 (a) ZnPcኽ୒ᐏȷ᩼୒ឋᐏƷNXESǹȚǯȈȫƱᕓᐏƷPESǹȚǯȈȫ (b) ZnPcኽ୒ᐏ
ȷ᩼୒ឋᐏƷN K! RXESǹȚǯȈȫ