Tiiu ban Khoa hoc vdt lieu ISBN 978 604 913 '''' THIET KE CHE TAO PIN MAT TROfI DIEN ClTC ZnO StT DUNG CHAT MAU NHAY SANG HMP CO HE SO DAP TAT CAO Nguvin H6ng Minh Nguyen Thi Thu Trang, Van Trong Hieu, N[.]
Tiiu ban Khoa hoc vdt lieu ISBN: 978-604-913-' THIET KE CHE TAO PIN MAT TROfI DIEN ClTC ZnO StT DUNG CHAT MAU NHAY SANG HMP CO HE SO DAP TAT CAO Nguvin H6ng Minh Nguyen Thi Thu Trang, Van Trong Hieu, Nguyen Due Tuyin, Tran Phuong Hoa, Nguyen Due Nghla Vien Hda Hpc, 18 Hoang Qudc Viet, Ciu Giiy, Ha Ndi Email: ducnghia264@fpt.vn Tom t^t Hai phuc ruthenium mdi dgng cis-[Ru(H2dcbpy)(L)(NCS)2], dd H2dcbpy la 4,4'-dicarboxy-2,2'-bipyridine vd L la 4,4'-bis-(4-di-p4,4'-bis-(4-(Nhexyloxyphenylamino)-styryl-2,2'-bipyridine (HMP-9) vd carbazolyl)-phenyl-2-vinyl)-2,2'-bipyridine (HMP-II) dd dugc tdng hgp vd nghiin ciiu tinh chdt Anh hudng cua nhung ligand khdc cd cdu triic liin hgp lin tinh chdt cita phuc chdt dd dugc thuc Men bdi phd hdp thu UV-Vis vd diin lugng tudn hodn Nhirng phuc chdt ndy thi Men rd nhung viing hdp thu rdng vd cd hi sd (Tap tdt cao vd dd dugc itng dung ldm chdt nhay sdng pin mdt trdi ZnO Kit qua cho thdy sit khdc biit vi hiiu sudt giua HMP-9 vd HMP-I cd lien quan chii yiu tdi tinh chdt hdp thu ciia chdt mdu vd muc ndng lugng HOMOLUMO Hiiu sudt chuyin hda ndng lugng ciig pin mat trdi ZnO su dung HMP-I I la 7.09% trang HMP-9 cho hiiu sudt thdp han (5.34%,) ciing diiu kiin chi tgo vd dgc Abstract Two novel ruthenium complexes cis-[Ru(H2dcbpy)(L)(NCS)2], where H2dcbpy is 4,4'-dicarboxy-2,2 '-bipyridine and L is 4,4'-bis-(4-di-p-hexyloxyphenylamino)styryl-2,2'-bipyridine (HMP-9) and 4,4'-bis-(4-(N-carbazolyl)-phenyl-2-vinyl)2,2'-bipyridine (HMP-I I) have been synthesized and characterized The influence of differently conjugated bipyridine ligands on these complexes was studied using UV-Vis spectroscopy and cyclic voltammetry These heteroleptic complexes show appreciably broad absorption ranges and quite high extinction coefficients These new dyes M'ere used as photosensitizers in nanocrystalline ZnO dye-sensitized solar cells It was found that the difference in light-harvesting property between HMP-9 and HMP-I I is associated mainly with dye absorptivity and the alignment of the HOMO-LUMO energy levels The power conversion efficiencies of solar cells based on HMP-I I is 7.09% while the HMP-9 delivered a lower efficiency of 5.34% under the same device fabrication and measuring conditions L GIOI THIEU Nhijng quan tam ve pin mat trdi chk mau nhay sang (DSSCs) tir hai thap ky trudc Cling vdi su phat trien nhijng chit nhay sang mdi dua tren phuc ruthenium polypyridyl cd he sd dap tat cao, dai hap thu dich ve phia budc sdng hdng ngoai gin dd md triln vpng mdi vi kha nang thay the pin mat trdi dua tren silic [1,2] Nhiing chit mau nhay sang mdi tdng hgp gin day nhu Z907, ClOl va C106 cho hieu suit 9-11 % [3] Trong so nhimg ban dan loai p cd viing cam rpng, ZnO dugc tap trung nghien cuu cd dp linh dpng dien tir cao, qui trinh cbl tao don gian, \'a su da dang ve hinh thai hpc bao gdm: hat nano, tim nano, dng nano day nano, tetrapod cau tnic hierarchical, nanoflower, nanotip, va nhijng ciu triic nano phan nhanh Tuy nliien nhirng cau tnic cd nhugc diem la cd dien tich be mat thip ban sc m 232 Hoi nghi Khoa hoc ky- niim 35 ndm Vien KH&CNVN- Hd Not -10/2010 ciu tnic mang xdp nano (dien tich bl mat Idn la cin thilt dl mang lugng chat mau tdi da), lam giam hieu qua chuyin hda nang lugng ddi vdi mpt don ldp chat mau hap phu len be mat oxit kem Nhiing cdng bd gin day cho thiy tam quan trpng ciia hinh thai hpc ZnO, dac biet la nhimg ciu tnic nano dan hudng cho phep van chuyen dien tich true tiep hudng -ye dien cue, tranh su nhay ngau nhien ciia dien tich va bay d bien hat nano [4] Cho den nay, cisdithiocyanatobis(4,4'-dicarboxylic acid-2,2'-bipyridine)-ruthenium(n) (N3) van thudng dugc su dung cho DSSCs dua tren ZnO Nhimg giai phap nhu thay ddi hinh thai hpc, dp day, da khdng cai thien dang kl hieu suat cua pin mat trdi ZnO [5,6] Trong mdt sd it thdng bao, bien ddi cau tnic ZnO nhu tao ciu tnic ldp pha tap Ga cd the cho hieu suat 5-6 % [7-9] Xii ly be mat hoac thiet ke nhiing chat mau mdi cd he sd dap tat cao, la mdt each tiep can cd hieu qua de tang hieu suat ciia pin mat trdi ZnO [6,10] Trong pin mat trdi ZnO, giam thieu su tao phiic Zn^"^/dye, la ldp each dien ngan can qua trinh van chuyen dien tich pin gay nen sir giam hi.eu suat, la mdt thach thiic can giai quyet [6] Cau tnic chat mau, gan them nhiing cau tnic cho dien tir, su tao nhiing lien ket lien hgp, va su tuong thich giira obital phan tir thap nhat chua bi chiem (LUMO) ciia chat mau va dai dan eiia oxit kim loai gdp phan cai thien hieu suat cua pin mat trdi Trong bai bao nay, chimg tdi thiet ke, tdng hop cau tnic mdi ciia chat nhay sang cd cdng thiic chung c/5-[Ru(H2dcbpy)(L)(NCS)2], dd Hidcbpy = 4,4'-dicarboxylic acid2,2'-bipyridine va L = 4,4'-bis-(4-di-p-hexyloxyphenylamino)-styryl-2,2'-bipyridine (HMP-9) va 4,4'-bis-(4-(N-carbazolyl)-phenyl-2-vinyl)-2,2'-bipyridine (HMP-11) nham cai thien hieu suat pin mat trdi dua tren dien cue ZnO cau tnic nano Han niia, ket qua nhan dupe cho thay hieu suat cao hon so vdi sir dung chat mau HMP-2 (Ru(H2dcbpy) (4-(4-(N,N-di-(phexyloxyphenyl)-amino)styryl)-4'-methyl-2,2'-bipyridine) (NCS)2) da cdng bd trudc day [10] II KET QUA VA THAO LUAN Cau tnic phan tir ciia chat mau dupe chi tren Hinh Chat mau HMP-9 chiia nhdm triphenyl amin va cd nhdm the hexyloxy, chat mau HMP-11 chira nhdm 9-phenyl-9Hcacbazol dugc gan lien hgp len ligan the nham muc dich thay ddi tinh chat ciia chat mau va nghien ciiu anh hudng cua nhirng thay ddi dd den hieu suat cua pin mat trdi HMPJ! K.MJ-ll Hinh I: Cdu trite phdn tu ciia chat mdu HMP-9, HMP-11 Hinh cho thiy phd hip thu ciia HMP-9, HMP-11 (10"^M) DMF Cue dai dac tnmg cho chuyen dien tich kim loai-ligan (MLCT) tai 526 nm ddi vdi HMP-9 va 539 nm ddi vdi HMP-11 Su cd mat ciia cacbazol HMP-11 dan din sir dich chuyin cue dai dai MLCT vl phia sdng dai nm so vdi chit mau N3 Khao sat ciia Chen va cdng sir cung cho 233 ISBN: 978-604-913-0! • Tiiu ban Khoa hgc vdt lieu kit qua tuong tu [10,24] Sir tang dp dai lien hgp JI HMP-9, HMP-11 din din su iimg 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' 'cm"' va21.4x 10^M"'cm"', cao ban nhieu so vdi N3 (14.5 x 10^M"'cm"') 70O Birac song (nm) Hinh 2: Phd hdp thu ciia HMP-9 (k), HMP-I I (f), vd N3 (m) DMF Tinh chat quang va dien hda cua chat mau dugc the hien tren Bang Chat mau HMP11 vdi cacbazol phan tir da dich chuyen quy dao phan tir dien day cao nhat (HOMO) len duang ban so vdi N3 la 0.14 eV so vdi miic chan khdng dd HMP-9 vdi nhdm triphenyl amin cd chuoi hexyloxy lam miic HOMO dich len 0.11 eV so vdi HOMO ciia N3 Bdng I; Tinh chdt quang vd diin hda cua chdt mdu HMP-9, HMP-I I, vd N3 Dyes N3"^J HMP HMP 11 HOMO (eV)[^' -5.52 -5.41 -5.38 Band gap (eV)'^! 1.68 2.06 2.05 LUMO (eV) -3.84 -3.35 -3.33 UV-Vis 8(M"'cm'') (Amax, nm ) 530 14,500 526 23,576 539 21,435 100 , 80- 60 ' A • V X iL • •' 20 • AJ y •' D 4C)0 500 800 700 81)0 Bifo^c song (nm) Hinh 3; Hiiu sudt chuyin ddi tit photon sang ddng diin ciia DSSCs dua trin HMP-9 (k.) HMP-I (y),vdN3 (u) 234 -10 2010 Hgi nghi Khoa hoc ky- niem 35 ndm Viin KH&CNVN - HdoiN> Hieu suit chuyin ddi photon sang ddng dien (IPCE) ciia linh kien pin mat trdi sir dung chit mau HMP-9, HMP-11 dugc chi tren Hinh Cue dai IPCE ciia HMP-11 dat 84 % t^i 525 nm HMP-9 cd gia tri IPCE thip hon tai 70 % mac dii HMP-9 cd he sd dap tat ciia dai MLCT cao ban Dieu cho thiy can cd nhimg hieu biet sau han ve sir phat sinh dien tieh, ca ehl tap hgp dien tich, tai hgp dien tich qua lien be mat ZnO/chat mau/chat dien li vaZnO/FTO Phd tdng trd dien hda (EIS) thudng dugc sir dung de phan tich ban chat cua qua trinh van chuyen dien tich, dien trd chuyen dien tich (Ret), tdc dp van chuyen dien tir va sir tai hgp dien tich pin mat trdi sir dung chat dien li Idng ciing nhu chat dien li ran [16,17] He va cpng sir ciing da sir dung ky thuat de he sd khuech tan va thdi gian sdng ciia dien tir [16,17] Dien trd FTO/chat dien li (Rh) va viing ban nguyet dac trung cho dien trd lien be mat Pt/chat dien li (Ri) va ZnO/chat mau/chat dien li (R2) -vimg tan sd cao va trung binh, viing tan sd thap dac trung cho dien trd khuech tan chat dien li (R3) Hinh cho thay dac tnmg phd EIS ciia linh kien sir dung chat mau nhay sang HMP-9, HMP-11 \'ung tan sd trung binh, chat mau N3 cd R2 Idn nhat cho thay dien tich tai hgp nhanh ban ca HMP-9 va HMP-11, thdi gian sdng ciia dien tir ngan hon ban chat khdi ciia cac nhdm hiru ca nhu triphenyl amin va cacbazol, dan den gia tri Foe ciia N3 la Idn nhat (0.61 V) Nhiing thay ddi ve hinh thai hpc ciia mang xdp ZnO, thdi gian nhupm mau, dung mdi cd the giiip nang cao gia tri Voc cua HMP/DSSCs igg iig igg Dien thi (V) Hinh 4; Phd EIS dgng Nyquist cua DSSCs diiu kiin chiiu sdng (100 mW/cm^), HMP-9 HMP-9 (k), HMP-11 (Wf vdN3 (m) Hinh 5; Ddc trung J-V ciia DSSC diiu kiin AM 1.5 G (100 mW/cm^), HMP-9 (k), HMP-I I (Wf vd N3 (m) Dac trung J - F cua pin mat trdi sir dung HMP-9, HMP-11 dugc the hien tren Hinh Trong dilu kien AM 1.5G (100 mW/cm^) chit mau HMP-11 dat hieu suit 7.09 %, phin Idn dugc ddng gdp bdi mat dp ddng ngan mach Jsc cao 23.5 mA/cm^ Ket qua cho thay anh hudng ciia he so dap tat va dac tnmg hap thu len hieu suat ciia pin mat trdi Chat mau HMP-9 cd he sd dap tat eao, nhien gia tri Jsc chi dat 16.5 mA/cm^, khdng cao hon nhieu so vdi N3 (14 mA/cm ) nen cho hieu suat 5.34 % Su cd mat ciia cacbazol phan tir phiic ruthenium nhu la tac nhan cho dien tir cd hieu qua ban so vdi dan xuit triphenyl amin Linh kien HMP11/DSSC cd he sd lap day (ff) kha thip (0.49), nhung cai thien xir ly bl mat nhu dua them 4tert-butylpiridin, Li(CF3S02)2N, [23] hoac tao nhiing ciu tnic Idi-vd [24] 235 Tiiu ban Khoa hgc vdt lieu ISBN: 978-604-913-' III KET LUAN Nhimg chat mau nhay sang ruthenium cd gan nhirng nhdm giau dien tir nhu triphenyl amin cd nhdm the, cacbazol da dugc tdng hgp Nhiing chat mau cd he sd dap tat cao, co dai hap thu dich chuyen vl phia budc sdng dai Pin mat trdi sir dung chit nhay sang HMP-11 cho hieu suit cao nhit (7.09 %) chit mau HMP-9 (5.34 %>) khdng cho cai thien dang ke so vdi N3 (4.94 %) Hieu suit cao hon dugc ddng gdp chii yeu bdi cd mat dp ddng ngan mach (Jsc) cao.Nhirng thay ddi nhim tdi uu hda ciu true ciia HMP-11 cd the dan den nhiing cai thien hieu suat ban niia ciia pin mat trdi va md trien vpng mdi cho nhirng img dung ciia pin mat trdi dua tren dien cue ZnO Loi cam on Cac tac gia xin chan cam on quy NAFOSTED da tai trg de thuc hien de tai nghien ciiu vdi ma sd 104.04.28.09 TAI LIEU THAM KHAO F Gao, Y Wang, D Shi, J Zhang, M Wang, X Jing, R Humphry Baker, P Wang, S M Zakeeriddin, M Grptzel, J Am Chem Soc, 130, 10720 (2008) J J Cid, J H Yum, S R Jang, M K Nazeeriddin, E Martinez-ferroro, E Palomares, J Ko, M Gratzel, T Ton-es, Angew Chem Int Ed., 46, 8358 (2007) Y Cao, Y Bai, Q Yu, Y Cheng, S Liu, D Shi, F Gao, P Wang, J Phys Chem C, 113,6290(2009) Gonzalez-valls, M Lira-Cantu, Energy Environ Sci., 2, 19 (2009) Q Zhang, T.P Chou, B Russo, S.A Jenekhe, G Cao, Adv Funct Mater., 18, 1654 (2008) T Ganesh, R S Mane, G Cai, J H Chang, S H Han, J Phys Chem C, 113, 7666 (2009) Q Zhang, T.P Chou, B Russo, S.A Jenekhe, G Cao, Ange'w Chem Int Ed., 47, 2402 (2008) K Keis, E Magnusson, H Lindstrom, S E Lindquist, A Hagfeldt, Solar Energy Mater Solar Cells, 73, 51 (2002) 10 A de souza goncalves, M R Dvolos, N Masaki, S Yanagida, A Morandeira, J R Durrant, J N Freitas A F Nogueira, Dalton Trans., 11, 1487 (2008) 11 H M Nguyen, R.S Mane, T Ganesh, S H Han, N Kim, J Phys Chem C, 113, 9206-9209 (2009) 12 J V Grazulevicius, P Shohriegl, J Pielichowski, K Pielichowski, Prog Polym Sci., 28, 1297-1353 (2003) 13 Z S Wang, N Koumura, Y Cui, M Takahashi, H Sekiguchi, A Mori, T Kubo, A Furube, K Hara, Chem Mater, 20, 3993 (2008) 14 Z Ning, Q Zhang, W Wu, H Pei, B Liu, H Tian, J Org Chem 73, 3791 (2008) 15 N Koumura, Z S Wang, S Mori, M Miyashha, E Suzuki, K Hara, J Am Chem Soc, 128, 14256(2006) 16 C Y Chen, H C Lu, C G Wu, J G Chen, K C Ho, Adv Funct Mater., 17, 29 (2007) 17 F Fabregant-Santiago, J Bisquert, L Cevery, P Chen., M Wang, S M Zakeeruddin M Gratz'el, J Am Chem Soc, 131, 558 (2009) 236 Hoi nghi Khoa hoc ky- niim 35 ndm Viin KH&CNVN - Hd Noi -10 2010 18 M Wang, P Chen R Humphr-'-Baker, M S Zakeeruddin M Gratzel Chem Phys Chem., 10 290(2009) 19 C He, L Zhao, Z Zheng, F Lu, J Phys Chem C, 112, 18730 (2008) 20 L Han, N Koide, Y Chiba, T Mitate, Appl Phys Lett, 84, 2433 (2004) 21 J Rochford, D Chu, A Hagfeldt E Galoppini, J Am Chem Soc, 129 4655 (2007) 22 S K Hau, H L Yip, O Acton, N S Back, H Ma, A K.-Y Jen J Mater Chem 18 5113(2008) 23 R Zhu, C Y Jiang, B Liu S Ramkrishna, Adv Mater., 21, 994 (2009) 24 N O V, Plank, S J Snaith, C Ducati, J S Bendall, L Schmidt-Mende M E Welland, Nanotechnology, 19, 465603 (2008) 25 CY Chen, J.G Chen, S.J Wu, J.Y Li, C.G Wu, K.C Ho Angew Chem 120, 7452 (2008) 237 ... nhirng thay ddi dd den hieu suat cua pin mat trdi HMPJ! K.MJ-ll Hinh I: Cdu trite phdn tu ciia chat mdu HMP- 9, HMP- 11 Hinh cho thiy phd hip thu ciia HMP- 9, HMP- 11 (10"^M) DMF Cue dai dac tnmg... dung chit mau HMP- 9, HMP- 11 dugc chi tren Hinh Cue dai IPCE ciia HMP- 11 dat 84 % t^i 525 nm HMP- 9 cd gia tri IPCE thip hon tai 70 % mac dii HMP- 9 cd he sd dap tat ciia dai MLCT cao ban Dieu cho... HMP- 9 HMP- 9 (k), HMP- 11 (Wf vdN3 (m) Hinh 5; Ddc trung J-V ciia DSSC diiu kiin AM 1.5 G (100 mW/cm^), HMP- 9 (k), HMP- I I (Wf vd N3 (m) Dac trung J - F cua pin mat trdi sir dung HMP- 9, HMP- 11 dugc