2014s2&001 eck …pf › outline › pf-s › pfsympo33 › 14s2-001web.pdf · 2016-05-27 ·...

1
lxFS±LD+cxw+ gE#+jªH+CK+w¨c Structural sciences for the understanding of the origin of physical properties and optimization of functions in the organic molecular assemblies. > < E ¥w¨Td 1 2 [5]b5O5¬5<95w2hn5Yt5;Z5C¤[5p952033;Z5\[R§5¬95rIR¬5}«5¤^ rRC5³|5V^5rRcu595K5n5zZ5[ ¢´lGm® ~k 4 )~&k 7+lxofiJi5M,*M²S¦*Aw¨QHO*"M!EOE"M#0$0+i*MWw¨ s5v°q?:B~5B ~7¶M5²P:)F* Mw¨Q£)F+*N&57+c²y@Xc5c5¡²c5M,#0L+=_¯cxwOgL*"M Uµ3R8PS6 BL#8A, , BL#8B, BL#3A, BL#4C, BL#7C (~a+©e{ 水素結合系有機反強誘電体の電場誘起構造相転移 BL#8A,8B 2014S2&001 BL# 8A, 8B, 7C O 1. S. Horiuchi, K. Kobayashi, R. Kumai, N. Minami, F. Kagawa and Y. Tokura, "Quantumferroelectricityin chargeFtra n sfe r c o mp l e x c ry sta l s", Na tu re Co mmu n ., 6, 7469:1F7 (2015). 2. Akira Ueda, Akari Hatakeyama, Masaya Enomoto, Reiji Kumai, Youich i Murakami, and Ha ts u mi Mo ri , "Mo d u l a ti o n of Mo l e c u l ar πFEl e c tro n Sy ste m i n a Pu re l y Org a n i c Co n d uc to r th at Sh o ws Hy d ro g e nFBo n d FDy n a mi c s FBa s ed Swi tc h i ng o f Co n d u cti vi ty a nd Ma g n e ti sm", Ch e m. Eu r. J ., 21, 15020–15028 (2015). 3. Yuki Noda, ToshikazuYamada, Kensuke Kobayashi , Re i j i Ku ma i , Sa ch i o Ho ri u ch i , Fu mi ta ka Ka g a wa , a n d Ta tsu o Ha s e ga wa , "Fe wFVolt Operation of Printed Organi c Ferroel ectricCapacit o r", Adv. Mater., 27 , 6475F6481 (2015). 4. S. Inoue, H. Minemawari, J. Tsutsumi, M. Chikamatsu, T. Yamada, S. Horiuchi , M. Tanaka, R. Kumai, M. Yoneya, and T. Hasegawa, “Effectsof Substituted Alkyl ChainLengthon SolutionFProcessabl e L a ye re d Org a n i c Se mi c o n d u cto r Cry s ta l s”, Ch e m. Ma te r., 27, 3809–3812 (2015). 4u 1. » ø þĂ ï îñæ Ā èðā ó èì Ñ'ÄÊ ±8~BTBTWa: Ò«u¼ ¹TYjo42015??b0 2. » ø ā ðĂ °1wWa:κ FX3(CatFEDTFTTF)2 (X = H, D)ÑÀÄß*]¼ r¹TYjo42015??b0 3. » RCatFTTFWa:β‘F[H3(CatFEDOFTTF)2]BF4ÑÀÄß _¡ wć d $ ¤Ò;Vâ ¿ 1¥ă jH /¼ %r¹TYjo42016??b0 4. » °}@Wa:θmF(BEDTFTTF)2TlZn(SCN)4ÑÀÄß° sBÒ f ºX¹TYjo42016??b0 5. » äÿçÿMBTBTWa:ÒU_¡\ć 1õî çĂ éÀÜ Ô1 ¬ă π° 1¢¬ Ò v ¼ =C¹TYjo42016??b0 ÐuOă4u K. Kobayashi et al. , 水素結合を有する有機導体の構造と物性 BL# 8A 0.18 mm 0.1 mm ªÚÒ[lUâ üìÍQ 8ÒÊÚ¹ NéþìÍêĄïåĂé (K#9Ò°-!ÑÜ ß / 40 kV/cm 0 kV/cm -5 5 2 ~40 kV/cm 720 V/0.18 mm 0 kV/cm Monoclinic (P21/ n) → Orthorhombic (Aea2) TFMNI (antiferroelectric, P21/ n) °-U_¡ Space gr oup: A ea2(#41) Or t hor hombic, a=14.0466, b=14.6089, c=10.0264, V= 2057.4712, Z=8, Rint=0.0262 R1(I>2σ)=0.0347, wR2=0.1094, GOF=1.027 N H N CF3 HN N CF3 HN N CF3 HN N CF3 NH N CF3 NH N CF3 NH N CF3 P P P P HN N CF3 HN N CF3 HN N CF3 HN N CF3 HN N CF3 HN N CF3 °-ÑÜß^N #D°v D°v 有機半導体材料の高機能化のための構造的知見からの分子設計指針の構築 P h'BTBT'10 ´bfUw¹àÊiH¹μ ĉ10 cm2/ (V*s ) ³¦Ý¹2013?{3Gj19a0C507 H. Iino et al., Nat. Commun. 6. 6828 (2015). ! i 56HÒ' ëäÿçÿBTBTfUwċ1 00ºC ZPÁeÉÖ² øþĂïîñæĀèðāóèìZPÎÇÌ ! àÊhB ! <lUH ă´¾BÒunÑF ă!ÑÜßÒÇÛÉÆ <l_¡ <l_¡âEJÇоZP l ¸ ¯ă ¨lUJ ª µ ! ´¾ kH M,]Òv M,ÁhB¹ijH¹U_¡Ñ"ØÉ]âvÑ S S Cn Ph#BTBT#Cn S. Inoue et al., Chem. Mater. 2015 S S Cn monoCn#BTBT U_¡\ "1õîçĂéÒäÿçÿ©ª2H "hBăijHÕÒM,] "1¬ÎÒwą|4Ć äÿçÿ©ªÎ1õîçĂé¶ #C3 #C4 #C5 #C6 #C8 #C10 &EÒ 1<_¡¹ ùþĂúĄĂ+Ò¥ 1ªS'Ñ ¾£¾Ñ¥' Ph#BTBT#CnÒ-$ äÿçÿ©ªÎ1õîçĂé· monoCn#BTBTÒ-$ o a c c o a b o b a o b c o a c o a b o b c o a b &EÒ 1<_¡¹ ùþĂúĄĂ+Ò¥ <l_¡Ó EJÆàо monoC2 monoC3 monoC4 monoC9 hBăijHÒ©ª2H hB@25ºC wgB Cr→ SmE SmE→SmA Melting point S S Cn S S Cn Ph#BTBT#Cn monoCn# ùþĂúĄĂ¥ÑÀÄß©Ò] ®L1ÒHOMO¢¬Ò *A DFø ā éýû(P W9 1 /TZP ) monoCn# BTBT Ph#BTBT#Cn diCn#BTBT "1¬wqÒ0ÂÆÎÓ tÐßtSHâzÉ "©ªÑÜËÌÒÓ0ÂÃ/Éß "©Áª¾×ÏùþĂúĄĂ<ÍSvÐÁ7n x¾äÿçÿ©ÍÓ`ºÐõîçĂéÁpÈßÒÑ8Ç̹ª©äÿçÿâ:ÇÊ-$Ó<l_¡âEJǹ÷ãìòĄ]ÑÜËÌ©¬Ò¯ÁDÃÐß äÿçÿ,ÒªÆÑGÈÌhBÒ¹®L1¬ÒwqÒ.0Ápȹ<ÒÓÜÞSvÑÐß κFH3(CatFE DTFTTF)2, H'TTFQSL Crystal Polymorphism in κ0H3(Cat0EDT0TTF)2 50 mKÙÍ yc}@¹wÐÇ ,AlIĈ »§1ìöĂf¼ T. Iso n o , et al ., PRL(2014) U_¡ÓĊ ÎÅáÁ¹½ßôîíÒP ( H'TTF50K) ÍÓ¹T ~ 50KÑ À¾Ì°mÑbvt> or #D° co lla b o ra tio n w ith Dr. Ha shimoto ( Sa sa ki Gr., IMR, To h oku Univ.) [O···H···O]–1 HFb o n d πFelectron conducting layer a c T. Iso n o , et al . , Natu re C o mmu n . (2 0 1 4 ) Crystal Structure Determination of H-TTF 50K +0.094(4) 1.399(3) Å 1.344(3) Å 1.366(2) Å O···O: 2.501(2) Å O···D: 1.265(7) Å O···O: 2.501(3) Å O···D: 1.02(5), 1.51(5) Å 1.366(2) Å +0.5 +0.5 +0.906(4) D'TTF Tc ~ 185 K C2/c @270 K PF1 @50 K H'TTF50K KEK PF, BLF8A C2/c @270 K →isostructural with H'TTFQSL and HTP of D'TTF 1.365(3) Å O···O: 2.478(3) Å O···H: 1.243(5) Å 1.365(3) Å +0.5 +0.5 PF1 @4 K Tc ~ 50 K +0.129(4) 1.381(5) Å 1.349(4) Å O···O: 2.491(5) Å O···H: 1.22(6), 1.33(6) Å +0.871(5) →isostructural with LTP of D'TTF Not ferroelectric but antiFferroelectric transition A. Ueda et al . JACS 136,12184(2014) H- TTFQS L (Ref. 1) H-TTF50K (this work) D -TTF (Ref. 2) D -ST (Ref. 2) 293 K 270 K 4 K 270 K 50 K 270 K 50 K b1 213 220 334 218 338 365 425 b2 78 79.4 80.8 79.0 78.9 163 139 p1 41 42.6 –46.4 42.7 28.9 78.8 70.3 q1 –16 –14.7 18.8 –15.5 2.4 –29.6 –49.3 b3 180 52.0 260 b4 90.1 2.9 141 p2 –56.3 21.7 74.2 q2 5.4 –7.1 5.4 Comparison of Electronic Structures c b a +0.91 (D-TTF) +0.80 (D-S T) +0.87 (H'TTF50K) +0.09 (D-TTF) +0.20 (D-S T) +0.13 (H'TTF50K) p1 b3 b4 q1 q2 p2 D-TTF, 50 K energy / eV EF 2.4 –0.4 Γ Γ C Y X V Γ C Y X V ka kb D-S T, 50 K Γ Γ C Y X V EF 1.0 –0.6 Γ C Y X V ka kb H-TTF50K, 4 K (this work) EF 0.8 –0.6 Γ Γ C Y X V Γ C Y X V ka kb b2 b1 Transfer integrals (in meV) Band insul a tor [1] Uedaet a l .JACS1 36, 12184(2014), [2]Uedaetal. Chem. Eur . J.2 1, 150 20 (20 15 ) charge ordered state (LTP)

Upload: others

Post on 06-Jul-2020

1 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: 2014S2&001 ECK …pf › outline › PF-S › PFSympo33 › 14S2-001web.pdf · 2016-05-27 · ³¦Ý¹2013cm?{3Gj2/(V*s)# 19a 0C5 7 H.#Iino#et#al.,#Nat.#Commun.#6.#6828#(2015).! i56HÒ

E CKStructural(sciences(for(the(understanding(of(the(origin(of(physical(properties(and(optimization(of(

functions(in(the(organic(molecular(assemblies.

1   25 5 5 5 5 2 5 5 5 5 5 2033 5 5 5 5 5

5 5 5 5 5 5 5 5~ 4 )~&

7 5 M M O M EO E M M 5 55 F M F 5 7 5 5 5 M L O L MR PS BL#8A,','BL#8B,'BL#3A,'BL#4C,'BL#7C

(~

水素結合系有機反強誘電体の電場誘起構造相転移 BL#8A,'8B

2014S2&001

BL# 8A,'8B, 7C

�O

1. S.(Horiuc h i ,(K.(Kobay as hi ,(R.(Kumai ,(N.(Minami ,(F.(Kagawa(and(Y.(Tok ura,("Quantum(ferroe lec tric i ty in (chargeFtransfer(c omplex(c ry sta ls", Nature'Commun.,(6 ,(7469:1F7((2015).2 . Ak i ra (Ueda,(Ak ari Hatak ey ama,(Mas ay a(Enomoto,(Rei j i (Kumai ,(Youic hi Murak ami ,(and Hats umi Mori ,("Modulation(of(Molec ular(πFElec tron(Sy stem(in (a (Pure ly(Organic (Conduc tor(that(Shows (Hy drogenFBondFDy namic s FBas ed(Swi tc h ing(of(Conductivi ty (and(Magnetism", Chem.'Eur.'J .,(21 ,(15020–15028((2015).3 . Yuk i (Noda,(Tos hik az u(Yamada,(Kens uke(Kobayas hi,(Rei j i (Kumai ,(Sachio(Horiuch i ,(Fumi taka(Kagawa,(and(Tatsuo(Has egawa,("FewFVol t(Operation(of(Prin ted(Organic (Ferroe lec tric(Capac i tor",(Adv .'Mater.,(27,(6475F6481((2015).4 . S.(Inoue,(H.(Minemawari ,(J .(Ts uts umi ,(M.(Chik amats u,(T.(Yamada,(S.(Horiuc h i,(M.(Tanak a,(R.(Kumai ,(M.(Yoney a,(and(T.(Hasegawa,(“Effec ts(o f(Substi tu ted(Alk yl (Chain(Length(on(Solution FProc ess able Layered(Organic(Semic onductor(Cry s ta ls”,(Chem.'Mater.,(27 ,(3809–3812((2015).

4u�

1. »øþĂïîñæĀèðāóèìÑ'Äʱ8~BTBT�Wa�: Ò«u¼ ���¹TYjo42015??b02. »øāðĂ °1w­��Wa: κ FX3(CatFEDTFTTF)2( (X(=(H,(D)ÑÀÄß*��]¼ �r�¹TYjo42015??b03. »R�CatFTTF�Wa: β‘ F[H3(CatFEDOFTTF)2]BF4ÑÀÄß_¡ w��ćd ��$ ¤Ò;Vâ ¿� 1¥�ăjH /�¼ %r�¹TYjo42016??b04. »°�}@�Wa: θmF(BEDTFTTF)2TlZn(SCN)4ÑÀÄß°�� sBÒ f ) ��¼ �ºX�¹TYjo42016??b05. »äÿçÿ�MBTBTWa�: Ò �U_¡�\ć� 1õîçĂéÀÜÔ�1 ¬�ăπ° 1�¢¬ ��� �Ò� �v� �¼ =C�¹TYjo42016??b0

�Ðu��Oă4u�

K.(Kobayashi(et'al.,(

水素結合を有する有機導体の構造と物性 BL# 8A

0.18(mm

0.1(mmªÚÒ[l�Uâ

üìÍ�Q

��8�ÒÊÚ¹

NéþìÍêĄïåĂé

(K#9Ò°-!�ÑÜß/�

40(kV/cm

0 k V/cm

-5 5 2

~40 kV/c m720 V/0 .18 mm

0 k V/cm

Monoclinic((P21/n)(→ Orthorhombic((Aea2)

TFMNI(antiferroelectric,(P21/n)

°-��U_¡

Space group: Aea2(#41)Orthorhombic,a=14.0466, b=14.6089, c=10.0264, V= 2057.4712, Z=8, Rint=0.0262R1(I>2σ)=0.0347, wR2=0.1094, GOF=1.027

NH

NCF3

HN N

CF3

HN N

CF3

HN N

CF3

NHN

CF3

NHN

CF3

NHN

CF3

P

P

P

P

HN N

CF3

HN N

CF3

HN N

CF3

HN N

CF3

HN N

CF3

HN N

CF3

°-ÑÜß�^N�

#D�°v D�°v

有機半導体材料の高機能化のための構造的知見からの分子設計指針の構築Ph'BTBT'10

´bfUw¹�àÊ�iH¹µ ĉ10#cm2/ (V*s )#³¦Ý¹2013?{3Gj 19a0C507

H.#Iino#et#al.,#Nat.#Commun.#6.#6828#(2015).

! i56HÒ'�ëäÿçÿBTBTfUw��ċ100#ºC

ZPÁ�eÉÖÂ�²

øþĂïîñæĀèðāóèìZPÎÇÌ

! �àÊh�B

! <l�UH

ă´¾��BÒunÑF�ă!�ÑÜß��ÒÇÛÉÆ

<l_¡<l_¡âEJÇоZP

��l¸

�¯ă¨l�UJªµ

! ´¾� kH

�M,�]��v��

�M,Áh�B¹ijH¹�U_¡Ñ"ØÉ�]â��vÑ��

S

SCn

Ph#BTBT#CnS.#Inoue#et#al.,#Chem.#Mater.#2015

S

SCn

monoCn#BTBT

�U_¡�\"�1õîçĂéÒäÿçÿ©ª�2H"h�BăijHÕÒ�M,�]"�1¬�Î����Òw­��ą��|4Ć

äÿçÿ©ªÎ�1õîçĂé¶

#C3 #C4 #C5 #C6 #C8 #C10&EÒ��1<_¡¹ùþĂúĄĂ+Ò¥�

�1ª�S'Ñ�¾£¾Ñ¥'

Ph#BTBT#CnÒ-$äÿçÿ©ªÎ�1õîçĂé·

monoCn#BTBTÒ-$

o

ac

co a

b

o b

a

o b

c

o a

c

o a

b

ob

c

o

a

b

&EÒ��1<_¡¹ùþĂúĄĂ+Ò¥�

<l_¡ÓEJÆàо

monoC2 monoC3 monoC4 monoC9

h�BăijHÒ©ª�2Hh�B@25ºC w��gB

Cr→SmESmE→SmA

Melting# point

S

S

Cn

S

S

Cn

Ph#BTBT#Cn

monoCn#

ùþĂúĄĂ¥�ÑÀÄß©Ò�]

®L�1ÒHOMO�¢¬Ò����*ADFøāéýû(PW91 /TZP )

monoCn#BTBTPh#BTBT#Cn diCn#BTBT

"�1¬w��qÒ0ÂÆÎÓtÐßtSHâzÉ"©ªÑÜËÌ����Ò�Ó0ÂÃ/�Éß"©Áª¾×ÏùþĂúĄĂ<�Í�SvÐ�Á7n

x¾äÿçÿ©ÍÓ`ºÐõîçĂéÁpÈßÒÑ8Ç̹ª©äÿçÿâ:�ÇÊ-$Ó<l_¡âEJǹ÷ãìòĄ�]ÑÜËÌ©¬Ò�¯�ÁDÃÐßäÿçÿ,ÒªÆÑGÈÌh�BÒ��¹®L�1¬Òw��qÒ.0Ápȹ<�Ò����ÓÜÞ�SvÑÐß

κFH3(CatFEDTFTTF)2,( H'TTFQSL

Crystal#Polymorphism#in#κ0H3(Cat0EDT0TTF)2

50(mKÙÍyc}@¹w��ÐÇ,AlIĈ»§1ìöĂf ¼T.# Isono ,#et#a l . , #P RL# (2 0 1 4)

�U_¡ÓĊ

ÎÅáÁ¹½ßôîíÒ�P(H'TTF50K)ÍÓ¹T ~(50(KÑÀ¾Ì�°mÑ�b��vt>→D�°or#D�°��collaboration#with#Dr.#Hashimoto#(Sasaki#Gr.,#IMR,#Tohoku#Univ.)

[O···H···O]–1HFbond

π Fe lec tronc onduc ting(lay er

a

c

T.# Isono ,#et#a l . , #Natu re#Commun .# (2 0 1 4 )

Crystal#Structure#Determination#of#H-TTF50K

+0.094(4)

1.399(3)9 Å

1.344(3)9 Å

1.366(2)(Å

O···O:( 2.501(2)( ÅO···D:( 1.265(7)( Å

O···O:( 2.501(3)( ÅO···D:( 1.02(5),(

1.51(5)( Å1.366(2)(Å

+0.5+0.5 +0.906(4)

D'TTF Tc ~(185(K

C2/c @270( K PF1( @50( K

H'TTF50KKEK(PF,(BLF8A

C2/c @270( K

→isostructural(with(H'TTFQSLand( HTP( of(D'TTF 1.365(3)(Å

O···O:( 2.478(3)( ÅO···H:( 1.243(5)( Å1.365(3)(Å

+0.5+0.5

PF1 @4(KTc ~(50(K

+0.129(4)

1.381(5)9 Å

1.349(4)9 Å O···O:( 2.491(5)( ÅO···H:( 1.22(6),(

1.33(6)( Å

+0.871(5)

→isostructural( withLTP(of( D'TTF

Not( ferroelectric( but( antiFferroelectric( transition

A.(Ueda(et(a l.(JACS(136,12184((2014)(

H-TTFQS L

(Ref. 1)

H-TTF50K

(this work)D-TTF(Ref. 2)

D-ST(Ref. 2)

293 K 270 K 4 K 270 K 50 K 270 K 50 K

b1 213 220 334 218 338 365 425

b2 78 79.4 80.8 79.0 78.9 163 139

p1 41 42.6 –46.4 42.7 28.9 78.8 70.3

q1 –16 –14.7 18.8 –15.5 2.4 –29.6 –49.3

b3 – – 180 – 52.0 – 260

b4 – – 90.1 – 2.9 – 141

p2 – – –56.3 – 21.7 – 74.2

q2 – – 5.4 – –7.1 – 5.4

Comparison#of#Electronic#Structures

c

b

a

+0.91 (D-TTF)+0.80 (D-S T)+0.879(H'TTF50K)

+0.09 (D-TTF)+0.20 (D-S T)+0.139(H'TTF50K)

p1b3

b4

q1

q2

p2

D-TTF, 50 K

energy(/(eV

EF

2.4

–0.4Γ ΓC Y X V

Γ

CY

X Vk a

k b

D-S T, 50 KΓ ΓC Y X V

EF

1.0

–0.6

Γ

CY

XV

k a

k b

H-TTF50K, 4 K(this9work )

EF

0.8

–0.6Γ ΓC Y X V

Γ

CY

X Vk a

k b

b2

b1

Transfer(integrals((in(meV)

Band(ins u lator

[1 ](Ueda(et(al .(JACS(136, 12184((2014)(,([2 ]Ueda(et(a l.(Chem.(Eur.(J.(21, 15020((2015)(

charge(ordered(state((LTP)