Tiiu ban Khoa hoc vdt lieu ISBN: 978-604-913-'<br />
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<br />
THIET KE CHE TAO PIN MAT TROfI DIEN ClTC ZnO StT DUNG<br />
CHAT MAU NHAY SANG HMP CO HE SO DAP TAT CAO<br />
Nguvin H6ng Minh. Nguyen Thi Thu Trang, Van Trong Hieu,<br />
Nguyen Due Tuyin, Tran Phuong Hoa, Nguyen Due Nghla<br />
Vien Hda Hpc, 18 Hoang Qudc Viet, Ciu Giiy, Ha Ndi.<br />
Email: ducnghia264@fpt.vn<br />
Tom t^t<br />
Hai phuc ruthenium mdi dgng cis-[Ru(H2dcbpy)(L)(NCS)2], trong dd<br />
H2dcbpy la 4,4'-dicarboxy-2,2'-bipyridine vd L la 4,4'-bis-(4-di-p-<br />
hexyloxyphenylamino)-styryl-2,2'-bipyridine (HMP-9) vd 4,4'-bis-(4-(N-<br />
carbazolyl)-phenyl-2-vinyl)-2,2'-bipyridine (HMP-II) dd dugc tdng hgp vd<br />
nghiin ciiu tinh chdt. Anh hudng cua nhung ligand khdc nhau cd cdu triic liin<br />
hgp lin tinh chdt cita phuc chdt dd dugc thuc Men bdi phd hdp thu UV-Vis vd do<br />
diin lugng tudn hodn. Nhirng phuc chdt ndy thi Men rd nhung viing hdp thu rdng<br />
vd cd hi sd (Tap tdt cao vd dd dugc itng dung ldm chdt nhay sdng trong pin mdt<br />
trdi ZnO. Kit qua cho thdy sit khdc biit vi hiiu sudt giua HMP-9 vd HMP-I 1 cd<br />
lien quan chii yiu tdi tinh chdt hdp thu ciia chdt mdu vd muc ndng lugng HOMO-<br />
LUMO. Hiiu sudt chuyin hda ndng lugng ciig pin mat trdi ZnO su dung HMP-I I<br />
la 7.09% trang khi HMP-9 cho hiiu sudt thdp han (5.34%,) trong ciing diiu kiin<br />
chi tgo vd do dgc.<br />
Abstract<br />
Two novel ruthenium complexes cis-[Ru(H2dcbpy)(L)(NCS)2], where H2dcbpy<br />
is 4,4'-dicarboxy-2,2 '-bipyridine and L is 4,4'-bis-(4-di-p-hexyloxyphenylamino)-<br />
styryl-2,2'-bipyridine (HMP-9) and 4,4'-bis-(4-(N-carbazolyl)-phenyl-2-vinyl)-<br />
2,2'-bipyridine (HMP-I I) have been synthesized and characterized. The influence<br />
of differently conjugated bipyridine ligands on these complexes was studied using<br />
UV-Vis spectroscopy and cyclic voltammetry. These heteroleptic complexes show<br />
appreciably broad absorption ranges and quite high extinction coefficients. These<br />
new dyes M'ere used as photosensitizers in nanocrystalline ZnO dye-sensitized<br />
solar cells. It was found that the difference in light-harvesting property between<br />
HMP-9 and HMP-I I is associated mainly with dye absorptivity and the alignment<br />
of the HOMO-LUMO energy levels. The power conversion efficiencies of solar<br />
cells based on HMP-I I is 7.09% while the HMP-9 delivered a lower efficiency of<br />
5.34% under the same device fabrication and measuring conditions.<br />
<br />
<br />
L GIOI THIEU<br />
Nhijng quan tam ve pin mat trdi chk mau nhay sang (DSSCs) tir hai thap ky trudc<br />
Cling vdi su phat trien nhijng chit nhay sang mdi dua tren phuc ruthenium polypyridyl cd he<br />
sd dap tat cao, dai hap thu dich ve phia budc sdng hdng ngoai gin dd md ra triln vpng mdi vi<br />
kha nang thay the pin mat trdi dua tren silic. [1,2] Nhiing chit mau nhay sang mdi tdng hgp<br />
gin day nhu Z907, ClOl va C106 cho hieu suit 9-11 %. [3] Trong so nhimg ban dan loai p cd<br />
viing cam rpng, ZnO dugc tap trung nghien cuu do cd dp linh dpng dien tir cao, qui trinh cbl<br />
tao don gian, \'a su da dang ve hinh thai hpc bao gdm: hat nano, tim nano, dng nano day<br />
nano, tetrapod. cau tnic hierarchical, nanoflower, nanotip, va nhijng ciu triic nano phan<br />
nhanh. Tuy nliien nhirng cau tnic nay cd nhugc diem la cd dien tich be mat thip ban sc m<br />
232<br />
Hoi nghi Khoa hoc ky- niim 35 ndm Vien KH&CNVN- Hd Not -10/2010<br />
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ciu tnic mang xdp nano (dien tich bl mat Idn la cin thilt dl mang lugng chat mau tdi da), lam<br />
giam hieu qua chuyin hda nang lugng ddi vdi mpt don ldp chat mau hap phu len be mat oxit<br />
kem. Nhiing cdng bd gin day cho thiy tam quan trpng ciia hinh thai hpc ZnO, dac biet la<br />
nhimg ciu tnic nano dan hudng cho phep van chuyen dien tich true tiep hudng -ye dien cue,<br />
tranh su nhay ngau nhien ciia dien tich va bay d bien hat nano. [4] Cho den nay, cis-<br />
dithiocyanatobis(4,4'-dicarboxylic acid-2,2'-bipyridine)-ruthenium(n) (N3) van thudng dugc<br />
su dung cho DSSCs dua tren ZnO. Nhimg giai phap nhu thay ddi hinh thai hpc, dp day, da<br />
khdng cai thien dang kl hieu suat cua pin mat trdi ZnO. [5,6] Trong mdt sd it thdng bao, bien<br />
ddi cau tnic ZnO nhu tao ciu tnic ldp. pha tap Ga cd the cho hieu suat 5-6 %. [7-9] Xii ly be<br />
mat hoac thiet ke nhiing chat mau mdi cd he sd dap tat cao, la mdt each tiep can cd hieu qua<br />
de tang hieu suat ciia pin mat trdi ZnO. [6,10]<br />
Trong pin mat trdi ZnO, giam thieu su tao thanh phiic Zn^"^/dye, la ldp each dien ngan<br />
can qua trinh van chuyen dien tich trong pin gay nen sir giam hi.eu suat, la mdt thach thiic can<br />
giai quyet. [6] Cau tnic chat mau, gan them nhiing cau tnic cho dien tir, su tao nhiing lien ket<br />
lien hgp, va su tuong thich giira obital phan tir thap nhat chua bi chiem (LUMO) ciia chat mau<br />
va dai dan eiia oxit kim loai gdp phan cai thien hieu suat cua pin mat trdi.<br />
Trong bai bao nay, chimg tdi thiet ke, tdng hop cau tnic mdi ciia chat nhay sang cd<br />
cdng thiic chung c/5-[Ru(H2dcbpy)(L)(NCS)2], trong dd Hidcbpy = 4,4'-dicarboxylic acid-<br />
2,2'-bipyridine va L = 4,4'-bis-(4-di-p-hexyloxyphenylamino)-styryl-2,2'-bipyridine (HMP-9)<br />
va 4,4'-bis-(4-(N-carbazolyl)-phenyl-2-vinyl)-2,2'-bipyridine (HMP-11) nham cai thien hieu<br />
suat pin mat trdi dua tren dien cue ZnO cau tnic nano. Han niia, ket qua nhan dupe cho thay<br />
hieu suat cao hon so vdi khi sir dung chat mau HMP-2 (Ru(H2dcbpy) (4-(4-(N,N-di-(p-<br />
hexyloxyphenyl)-amino)styryl)-4'-methyl-2,2'-bipyridine) (NCS)2) da cdng bd trudc day.<br />
[10]<br />
<br />
<br />
II. KET QUA VA THAO LUAN<br />
Cau tnic phan tir ciia chat mau dupe chi ra tren Hinh 1. Chat mau HMP-9 chiia nhdm<br />
triphenyl amin va cd nhdm the hexyloxy, chat mau HMP-11 chira nhdm 9-phenyl-9H-<br />
cacbazol dugc gan lien hgp len ligan the nham muc dich thay ddi tinh chat ciia chat mau va<br />
nghien ciiu anh hudng cua nhirng thay ddi dd den hieu suat cua pin mat trdi.<br />
<br />
<br />
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3<br />
<br />
HMPJ! K.MJ-ll<br />
<br />
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Hinh I: Cdu trite phdn tu ciia chat mdu HMP-9, HMP-11<br />
Hinh 2 cho thiy phd hip thu ciia HMP-9, HMP-11 (10"^M) trong DMF. Cue dai dac<br />
tnmg cho chuyen dien tich kim loai-ligan (MLCT) tai 526 nm ddi vdi HMP-9 va 539 nm ddi<br />
vdi HMP-11. Su cd mat ciia cacbazol trong HMP-11 dan din sir dich chuyin cue dai dai<br />
MLCT vl phia sdng dai 9 nm so vdi chit mau N3. Khao sat ciia Chen va cdng sir cung cho<br />
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Tiiu ban Khoa hgc vdt lieu ISBN: 978-604-913-0! •<br />
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kit qua tuong tu. [10,24] Sir tang dp dai lien hgp JI trong HMP-9, HMP-11 din din su iimg<br />
he sd dap tit so vdi N3. He sd dap tit ciia dai MLCT ciia HMP-9 va HMP-11 la 23.5 x 10' M'<br />
'cm"' va21.4x 10^M"'cm"', cao ban nhieu so vdi N3 (14.5 x 10^M"'cm"').<br />
<br />
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<br />
<br />
70O<br />
<br />
Birac song (nm)<br />
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Hinh 2: Phd hdp thu ciia HMP-9 (k), HMP-I I (f), vd N3 (m) trong DMF<br />
Tinh chat quang va dien hda cua chat mau dugc the hien tren Bang 1. Chat mau HMP-<br />
11 vdi cacbazol trong phan tir da dich chuyen quy dao phan tir dien day cao nhat (HOMO) len<br />
duang ban so vdi N3 la 0.14 eV so vdi miic chan khdng trong khi dd HMP-9 vdi nhdm<br />
triphenyl amin cd chuoi hexyloxy lam miic HOMO dich len 0.11 eV so vdi HOMO ciia N3.<br />
Bdng I; Tinh chdt quang vd diin hda cua chdt mdu HMP-9, HMP-I I, vd N3<br />
<br />
Dyes HOMO Band gap LUMO UV-Vis 8(M"'cm'')<br />
(eV)[^' (eV)'^! (eV) (Amax, nm )<br />
N3"^J -5.52 1.68 -3.84 530 14,500<br />
HMP 9 -5.41 2.06 -3.35 526 23,576<br />
HMP 11 -5.38 2.05 -3.33 539 21,435<br />
<br />
100 .,<br />
<br />
<br />
80-<br />
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60.<br />
' A 1<br />
•<br />
<br />
V. X<br />
iL •<br />
20. •'<br />
•' AJ y<br />
•<br />
D.<br />
<br />
4C)0 500 800 700 81)0<br />
<br />
Bifo^c song (nm)<br />
<br />
Hinh 3; Hiiu sudt chuyin ddi tit photon sang ddng diin ciia DSSCs dua trin HMP-9 (k.)<br />
HMP-I 1 (y),vdN3 (u)<br />
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234<br />
Hgi nghi Khoa hoc ky- niem 35 ndm Viin KH&CNVN - HdoiN><br />
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Hieu suit chuyin ddi photon sang ddng dien (IPCE) ciia linh kien pin mat trdi sir dung<br />
chit mau HMP-9, HMP-11 dugc chi ra tren Hinh 3. Cue dai IPCE ciia HMP-11 dat 84 % t^i<br />
525 nm trong khi HMP-9 cd gia tri IPCE thip hon tai 70 % mac dii HMP-9 cd he sd dap tat<br />
ciia dai MLCT cao ban. Dieu nay cho thiy can cd nhimg hieu biet sau han ve sir phat sinh<br />
dien tieh, ca ehl tap hgp dien tich, tai hgp dien tich qua lien be mat ZnO/chat mau/chat dien li<br />
vaZnO/FTO.<br />
Phd tdng trd dien hda (EIS) thudng dugc sir dung de phan tich ban chat cua qua trinh<br />
van chuyen dien tich, dien trd chuyen dien tich (Ret), tdc dp van chuyen dien tir va sir tai hgp<br />
dien tich trong pin mat trdi sir dung chat dien li Idng ciing nhu chat dien li ran. [16,17] He va<br />
cpng sir ciing da sir dung ky thuat nay de do he sd khuech tan va thdi gian sdng ciia dien tir<br />
[16,17] Dien trd FTO/chat dien li (Rh) va 3 viing ban nguyet dac trung cho dien trd lien be<br />
mat Pt/chat dien li (Ri) va ZnO/chat mau/chat dien li (R2) trong -vimg tan sd cao va trung binh,<br />
viing tan sd thap dac trung cho dien trd khuech tan trong chat dien li (R3). Hinh 4 cho thay<br />
dac tnmg phd EIS ciia linh kien sir dung chat mau nhay sang HMP-9, HMP-11. 6 \'ung tan sd<br />
trung binh, chat mau N3 cd R2 Idn nhat cho thay dien tich tai hgp nhanh ban trong ca HMP-9<br />
va HMP-11, thdi gian sdng ciia dien tir ngan hon do ban chat khdi ciia cac nhdm hiru ca nhu<br />
triphenyl amin va cacbazol, dan den gia tri Foe ciia N3 la Idn nhat (0.61 V). Nhiing thay ddi<br />
ve hinh thai hpc ciia mang xdp ZnO, thdi gian nhupm mau, dung mdi cd the giiip nang cao gia<br />
tri Voc cua HMP/DSSCs.<br />
<br />
<br />
<br />
<br />
igg iig igg<br />
<br />
Dien thi (V)<br />
<br />
Hinh 4; Phd EIS dgng Nyquist cua DSSCs trong Hinh 5; Ddc trung J-V ciia DSSC trong<br />
diiu kiin chiiu sdng (100 mW/cm^), HMP-9 diiu kiin AM 1.5 G (100 mW/cm^),<br />
HMP-9 (k), HMP-11 (Wf vdN3 (m) HMP-9 (k), HMP-I I (Wf vd N3 (m)<br />
Dac trung J - F cua pin mat trdi sir dung HMP-9, HMP-11 dugc the hien tren Hinh 5.<br />
Trong dilu kien AM 1.5G (100 mW/cm^) chit mau HMP-11 dat hieu suit 7.09 %, phin Idn<br />
dugc ddng gdp bdi mat dp ddng ngan mach Jsc cao 23.5 mA/cm^. Ket qua nay cho thay anh<br />
hudng ciia he so dap tat va dac tnmg hap thu len hieu suat ciia pin mat trdi. Chat mau HMP-9<br />
cd he sd dap tat eao, tuy nhien gia tri Jsc chi dat 16.5 mA/cm^, khdng cao hon nhieu so vdi N3<br />
(14 mA/cm ) nen cho hieu suat 5.34 %. Su cd mat ciia cacbazol trong phan tir phiic ruthenium<br />
nhu la tac nhan cho dien tir cd hieu qua ban so vdi dan xuit triphenyl amin. Linh kien HMP-<br />
11/DSSC cd he sd lap day (ff) kha thip (0.49), nhung cai thien xir ly bl mat nhu dua them 4-<br />
tert-butylpiridin, Li(CF3S02)2N, [23] hoac tao ra nhiing ciu tnic Idi-vd. [24]<br />
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235<br />
Tiiu ban Khoa hgc vdt lieu ISBN: 978-604-913-'<br />
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<br />
III. KET LUAN<br />
Nhimg chat mau nhay sang ruthenium cd gan nhirng nhdm giau dien tir nhu triphenyl<br />
amin cd nhdm the, cacbazol da dugc tdng hgp. Nhiing chat mau nay cd he sd dap tat cao, co<br />
dai hap thu dich chuyen vl phia budc sdng dai. Pin mat trdi sir dung chit nhay sang HMP-11<br />
cho hieu suit cao nhit (7.09 %) trong khi chit mau HMP-9 (5.34 %>) khdng cho cai thien dang<br />
ke so vdi N3 (4.94 %). Hieu suit cao hon dugc ddng gdp chii yeu bdi cd mat dp ddng ngan<br />
mach (Jsc) cao.Nhirng thay ddi nhim tdi uu hda ciu true ciia HMP-11 cd the dan den nhiing<br />
cai thien hieu suat ban niia ciia pin mat trdi va md ra trien vpng mdi cho nhirng img dung ciia<br />
pin mat trdi dua tren dien cue ZnO.<br />
<br />
Loi cam on<br />
Cac tac gia xin chan thanh cam on quy NAFOSTED da tai trg de thuc hien de tai<br />
nghien ciiu nay vdi ma sd 104.04.28.09.<br />
<br />
<br />
TAI LIEU THAM KHAO<br />
1. F. Gao, Y. Wang, D. Shi, J. Zhang, M. Wang, X. Jing, R. Humphry<br />
2. Baker, P. Wang, S. M. Zakeeriddin, M. Grptzel, J. Am. Chem. Soc, 130, 10720<br />
(2008).<br />
3. J. J. Cid, J. H. Yum, S. R. Jang, M. K. Nazeeriddin, E. Martinez-ferroro, E. Palomares,<br />
J. Ko, M. Gratzel, T. Ton-es, Angew. Chem. Int. Ed., 46, 8358 (2007).<br />
4. Y. Cao, Y. Bai, Q. Yu, Y. Cheng, S. Liu, D. Shi, F. Gao, P. Wang, J. Phys. Chem. C,<br />
113,6290(2009).<br />
5. 1. Gonzalez-valls, M. Lira-Cantu, Energy Environ. Sci., 2, 19 (2009).<br />
6. Q. Zhang, T.P. Chou, B. Russo, S.A. Jenekhe, G. Cao, Adv. Funct. Mater., 18, 1654<br />
(2008)<br />
7. T. Ganesh, R. S. Mane, G. Cai, J. H. Chang, S. H. Han, J. Phys. Chem. C, 113, 7666<br />
(2009).<br />
5. Q. Zhang, T.P. Chou, B. Russo, S.A. Jenekhe, G. Cao, Ange'w. Chem. Int. Ed., 47,<br />
2402 (2008).<br />
9. K. Keis, E. Magnusson, H. Lindstrom, S. E. Lindquist, A. Hagfeldt, Solar Energy<br />
Mater. Solar Cells, 73, 51 (2002).<br />
10. A. de souza goncalves, M. R. Dvolos, N. Masaki, S. Yanagida, A. Morandeira, J. R.<br />
Durrant, J. N. Freitas A. F. Nogueira, Dalton Trans., 11, 1487 (2008).<br />
11. H. M. Nguyen, R.S. Mane, T. Ganesh, S. H. Han, N. Kim, J. Phys. Chem. C, 113,<br />
9206-9209 (2009).<br />
12. J. V. Grazulevicius, P. Shohriegl, J. Pielichowski, K. Pielichowski, Prog. Polym. Sci.,<br />
28, 1297-1353 (2003).<br />
13. Z. S. Wang, N. Koumura, Y. Cui, M. Takahashi, H. Sekiguchi, A. Mori, T. Kubo, A.<br />
Furube, K. Hara, Chem. Mater, 20, 3993 (2008).<br />
14. Z. Ning, Q. Zhang, W. Wu, H. Pei, B. Liu, H. Tian, J. Org. Chem. 73, 3791 (2008).<br />
15. N. Koumura, Z. S. Wang, S. Mori, M. Miyashha, E. Suzuki, K. Hara, J. Am. Chem.<br />
Soc, 128, 14256(2006).<br />
16. C. Y. Chen, H. C. Lu, C. G. Wu, J. G. Chen, K. C. Ho, Adv. Funct. Mater., 17, 29<br />
(2007).<br />
17. F. Fabregant-Santiago, J. Bisquert, L. Cevery, P. Chen., M. Wang, S. M. Zakeeruddin<br />
M. Gratz'el, J. Am. Chem. Soc, 131, 558 (2009).<br />
<br />
<br />
236<br />
Hoi nghi Khoa hoc ky- niim 35 ndm Viin KH&CNVN - Hd Noi -10 2010<br />
<br />
<br />
18. M. Wang, P. Chen. R. Humphr-'-Baker, M. S. Zakeeruddin. M. Gratzel. Chem. Phys.<br />
Chem., 10. 290(2009).<br />
19. C. He, L. Zhao, Z. Zheng, F. Lu, J. Phys. Chem. C, 112, 18730 (2008).<br />
20. L. Han, N. Koide, Y. Chiba, T. Mitate, Appl. Phys. Lett, 84, 2433 (2004).<br />
21. J. Rochford, D. Chu, A. Hagfeldt. E. Galoppini, J. Am. Chem. Soc, 129. 4655 (2007).<br />
22. S. K. Hau, H. L. Yip, O. Acton, N. S. Back, H. Ma, A. K.-Y. Jen. J. Mater. Chem.. 18.<br />
5113(2008).<br />
23. R. Zhu, C. Y. Jiang, B. Liu. S. Ramkrishna, Adv. Mater., 21, 994 (2009).<br />
24. N. O. V, Plank, S. J. Snaith, C. Ducati, J. S. Bendall, L. Schmidt-Mende. M. E.<br />
Welland, Nanotechnology, 19, 465603 (2008).<br />
25. CY. Chen, J.G. Chen, S.J. Wu, J.Y. Li, C.G. Wu, K.C. Ho. Angew. Chem.. 120, 7452<br />
(2008).<br />
<br />
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237<br />
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