AU2009200356B2

AU2009200356B2 - Photosensitizer Dye

Info

Publication number: AU2009200356B2
Application number: AU2009200356A
Authority: AU
Inventors: Chia-Yuan Chen; Jheng-Ying Li; Chun-Guey Wu; Shi-Jhang Wu
Original assignee: National Central University
Current assignee: National Central University
Priority date: 2008-02-19
Filing date: 2009-01-29
Publication date: 2011-03-10
Anticipated expiration: 2029-01-29
Also published as: AU2009200356A1; JP2009215539A; JP5241546B2

Description

59706 JOM:AS P/00/011 Regulation 3.2 AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT ORIGINAL Name of Applicant: NATIONAL CENTRAL UNIVERSITY Actual Inventors: CHUN-GUEY WU, CHIA-YUAN CHEN, SHI-JHANG WU, JHENG-YING LI Address for Service: COLLISON & CO.,1 17 King William Street, Adelaide, S.A. 5000 Invention Title: PHOTOSENSITIZER DYE Details of Associated Applications: Taiwanese Patent No: 97105782 dated 19 February 2008 Taiwanese Patent No: 97148638 dated 12 December 2008 The following statement Is a full description of this invention, including the best method of performing it known to us: 2 PHOTOSENSITIZER DYE BACKGROUND OF THE INVENTION 5 1. Field of the Invention [0001] The present invention relates to a solar cell material. More particularly, the present invention relates to a photosensitizer dye applicable in dye-sensitized solar cells (DSCs). 10 2. Description of Related Art [00021 Not only the supply of fossil fuels is expected to run out in an imminent future, the high consumption of fossil fuels also poses an alarming threat to the environment and public health due to their poisonous emissions. Accordingly, scientists are constantly in searching and developing the renewable and sustainable 15 energy sources. The renewable energy sources include: solar energy, wind energy, hydraulic energy, tidal energy, geothermal energy, biomass energy, and etc. Amongst the various types of energy sources, solar energy has been one of the most pursued due to its abundant supply. Furthermore, the application of solar energy is not limited by the physical environment or geomorphology, and solar energy can be directly converted 20 to electricity with the appropriate devices which are known as solar cells (or photovoltaic cells). 100031 Recently, Gratzel and O'Regan have proposed a new type of solar cell known as dye-sensitized solar cells (DSCs). DSCs offer many advantageous prospects, such as, high photoelectric conversion efficiency, high transparency, colorfulness, and 3 flexibility in which the cell is capable of folding or bending. Hence, the dye-sensitized solar cells are well received in the industry. A dye-sensitized solar cell is typically constituted with four parts including an anode/cathode for current flow, a semiconductor material (such as, titanium dioxide (TiO2) or zinc oxide (ZnO)) for 5 accepting and transporting electrons, a monolayer of photosensitizer (dye) attached onto the surface of the semiconductor material in a self-assembly manner, and an electrolyte for transporting holes. The materials used at each part and the interface between each part in the dye-sensitized solar cell play important roles on the photoelectrical conversion efficiency of the cell. Most particularly, the dye used in the photosensitizer 10 layer is the most critical in determining the efficiency of a dye-sensitized solar cell. 100041 Accordingly, to identify a dye that has a high absorption coefficient for enhancing the photoelectrical conversion efficiency of a dye-sensitized solar cell has been enthusiastically pursued in the dye-sensitized solar cell community. 15 SUMMARY OF THE INVENTION [00051 In view of the foregoing, the present invention is directed to a photosensitizer dye applied to the dye-sensitized solar cell, wherein the photoelectric conversion efficiency of the dye-sensitized solar cell using this dye is enhanced. [0006] The present invention provides a photosensitizer dye, wherein the 20 photosensitizer dye is a ruthenium (Ru) complex represented by the following general formula (1).

4 Fonnula (1) N N Z2 \ N Ru--N\ N N S S 10 Xi represents one of formula (2) to (19) and X2 represents hydrogen, or X, and X 2 both represent one of formula (2) to (19).

5 (2) (3) (4) () Y Y Y 2 Y 2 Y2 2 2Y2R k%( i542 4 (

R

1 2 R 1 R R R 8 R10 1 () (7) () ( ) Y2 r&Y2 2 Y Y 2 Y Y2 0 00 10'' j R25-t)fR1 5

R

2 ioR1 R13 RioRi

R

30

R

3 , (14) (1) (19) SO' '4 ' n n R RMR2 2Y (17) (8)(12) 15 R 1 to 10o in formula (3) to (19) represent independently one of HI, CtHe~- (t=1 to 15),

OC.H

2 yi (vr to 15), SCwHzrj (w=1 to 15) or formula (36) to (37). More specifically, n=0 to 2 and m=1l to 4 in formula (2) to (19). Yi in formula (2) to (19) represents one of sulfur (S), methylene group (CH 2 ), amino group (N-R; R represents one of H or CxH 2 xe (x=1 to 15)), or selenium (Se). It is noted that Y 2 in formula (2) to 20 (19) represents independently one of formula (20) to (37).

6 -H - CiH2+1 --- CH2+ ~ -S-CkH2k+1 (20) (21) (22) (23) -N/ -- 4N -N/IZ--F -N CH---4 \.-C-qH2 \---CqH2q 5 (24) (25) (26) (27) R45R45R R -N-N -N -N |-K NN CqF12q CqH2q -4 -a 10 Q Q 100 NN N -N R Rs, Rss R55 RNg (32) (33) (34) (35) r r (36) (37) 15 (e [0007] Additionally, in formula (1), Z, represents one of formula (38) to (44), and

Z

2 represents hydrogen or one of formula (38) to (44). In other words, Zi and Z 2 can be the identical or different groups. 20 7

COOA

1

-COOA

1

-PO

3 HA1 COQA 1 COOA1 (38) (39) (40) (41) R8 O O s COOA COOCOOA1 (42) (43) (44) [00o8] In formula (38) to (44), At represents hydrogen (H), lithium (Li), sodium (Na), potassium (K) or tetra-alkyl ammonium groups as represented by general formula 10 (45), or any species or groups with positive charge. Moreover, in formula (45), R 63 , 14, le and R 6 independently represent H or CyH2zi (y=l to 15). P-83 R65 (45) 15 10009] it should be noted that, in formula (1), when X 2 represents hydrogen, Z and

Z

2 both represent formula (38) and X, represents one of formula (2) ~ (5) in which n0 and Y, represents sulfur (S), Y2 in formula (2) - (5) does not represent one of formula (20)-(22). 20 [0010) Besides, in formula (1), when Z, and Z 2 both represent formula (38) and X, and X2 both represent one of formula (2) ~ (5) in which n=0 and Y 1 represents sulfur (S), Y 2 in formula (2) - (5) does not represent one of formula (20) ~ (22).

8 [00111 In addition, in formula (1), when Zi and Z2 both represent formula (38) in which Ai represents hydrogen (H) and X 1 and X 2 both represent formula (10) or formula (12) in which n=0 and Yi represents sulfur (S), Y2 in formula (10) or formula (12) does not represent one of formula (20) - (23). 5 [0012] According to an embodiment of the present invention, a structure of the photosensitizer dye is represented by the following formula (61) to (67). R72 R73 R68 RyoR1 7 N A10 N- -N AN RN NRR SS 10 S $/ /\/\ /\ /\S -N N AjOO-' -RuN----SA100C41 N- R-N=C=S N

A

1 00C / \N Ru-NZC=S A 1 00C / N Ru N=C= N N N

A

1 00C (61) Aooc (62) 2\ N0NC-S AOC N N 1 N \(63) A 1 00C (64) 20

A

1

OOC

9 R7 9 Roo Ra/ 0 0 R2 $ S N N AOOC blu 4 N A000 Nc=-RU"N=C=S 5 N N N

A

1 000 (65)

A

1 00C (66) RR81 R02

H

0 0 10R -0 S N

A

1 00C1/0NcNRRu'"N=C=S NN N \ / c N1N 15 S 15 AOOC (67) [00131 In formula (61), R.6, Rca, R and R7o independently represent one of H, CEH2E+1 (E-1 to 6), OCpH2Fi (F=1 to 6), SCoH 2 o+1(G-l to 15) or formula (36) to (37). 20 In formula (62), R71, R72, R73 and R 7 4 independently represent one of H, CAH2A4 (A=l to 15), OCaH 2

+

1 (B=1 - 15), SCDIH2D+l (D=1 to 15) or formula (36) to (37). In formula (63), R7 and R76 independently represent one of H, C 1 H2t+1 (1=1 to 15),

OC,H

2 v+ 1 (v=1 to 15), SCH2w+ (w=1 to 15) or formula (36) to (37). In formula (64) to (66), R-7, R&. R 7 9 , R 50 , Rg, and Rgz independently represent one of SCGH 23 +I (G-1 to 25 15) or formula (36) to (37). In formula (67), Rua, RPs, Rss and R 6 independently 10 represent one of H, CAH2A-I (A-1 to 15), OCBHmBn (B=1 to 15), SCDH2DIJ (D1> to 15) or formula (36) to (37). In formula (61) to (67), A independently represents hydrogen (H), lithium (Li), sodium (Na), potassium (K) or tetra-alkyl ammonium groups as represented by general formula (45). Moreover, in formula (45), R 63 , R 6 4 , R 65 and R66 5 independently represent H or CyH2y* (y=i to 15). R6 Re6---N--R,4 Rs (45) 10 [0014] According to an embodiment of the present invention, a structure of the photosensitizer dye is represented by the following formula (68) to (74). 15 I NN N sN S / S N N 20 / k\ N N N / I A(00C A1OOC-(-N) A0C (8 A 1 OC0 (9) 11 s \s\ s s A000 \ AN RU N C=S A 1 00C / N-Rii 5 N INI $ S \ (70) A,00 (71)

A

1 00C C e C H e C e H k A t S p e H 2 \ NN 0 0 S, 10-N N N 15 \/ oN=R."r~ 20

A

1 00C / R N N

A

1 000 (74) 12 [00151 In formula (68) to (74), A, independently represents hydrogen (H), lithium (Li), sodium (Na), potassium (K) or tetra-alkyl ammonium groups as represented by general formula (45). As for formula (45), R6, R6 4 , R6s and R6, independently represent H or CyH2yI- (y=1 to 15).

R

6 3 5 Rrer-N-RG4 (45) 100161 According to an embodiment of the present invention, a structure of the 10 photosensitizer dye is represented by the following formula (75) to (76). COOA,

A

1 0C I .

SIR8 N OCN S NN S N Ru" N z N 15 CS N SS (75) COOA A1OOCS 20 N S N N RU N N / s (76) 13 [0017] In formula (75) to (76). R 8 7, Rls, Rs and Rgo independently represent H or CJHJ,,, (J-1 to 15). In formula (75) to (76), A 1 independently represents hydrogen (H), lithium (Li), sodium (Na), potassium (K) or tetra-alkyl ammonium groups as represented by general formula (45). R, R>4, R4s and R66 of formula (45) 5 independently represent H or CyHazy (y=1 to 15). Rs (45) 10 [0018] As mentioned above, the photosensitizer dye in the present invention contains the foregoing special groups (XI, X 2 , Zi and Z 2 ). The photosensitizer dye of the present invention has a desirable light absorption capability. In other words, the absorption spectrum of the photosensitizer dye of the present invention is close to the 15 solar light spectrum. Moreover, the absorption coefficient of the photoseisitizer dye of the present invention is very high, which suggests that dye-sensitized solar cell using the photosensitizer dye of the present invention can effectively absorb solar light and convert it into an output current. [00191' In order to make the aforementioned items, other features, and advantages of 20 the present invention more comprehensible, preferred embodiments accompanied with figures are described in detail below. BRIEF DESCRIPTION OF THE DRAWINGS [0020] The accompanying drawings are included to provide a further understanding 14 of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. [0021] Figure 1 depicts, in an absorption spectrum, the comparisons between the 5 photosensitizer dyes according to embodiments of the present invention and a conventional photosensitizer dye. DESCRIPTION OF THE EMBODIMENTS [0022] Reference will now be made in detail to the present preferred embodiments 10 of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts. [0023] The present invention provides a photosensitizer dye, wherein the photosensitizer dyes is a ruthenium (Ru) complex represented by the following general 15 formula (1). Formula (1) Z, X1 NN X2 20Z2 N- Ru-N 202 N N h/foC S S 25 [0024] In formula (1), X, represents one of formula (2) to (19) and X 2 represents 15 hydrogen or, in the alternative, X 1 and X 2 both represent one of formula (2) to (19). t< Y2 Y2 (2 Y2R, R 2 3R~ R7 (2) (3) (4) R,(5) Y5I -~ 3 tjY 2 {tS Y2 Yijly2m 2 4t% 1m 2 5 2nQ1n 0 0 O)+0 R9)KRI

R

12

R

13 R15 RiPRI 1 5 (6) (7) (6) Y 2 S~~~ )<n S.r R20 R2 2 2 Y2 410) (11) (12) (13)

Y

2

V

2 10 y 1 Y2 \ R~ 2aRz 9

>KZR

32 (14)

(

5 )t 5 10 Y2

Y

2 Y2 Y2 Y2 2 nY.2 0 0 3 0 R4 R R a R 3 1 40 1519 [0025] In formula (3) to (19), R 1 to R 4 0 represent independently one of H, CQH 2 &i (t=1 to 15), OCH2r1 (v-I to 15), SCwHzri (w=1 to 15) or fonnula (36) to (37). Moreover, n=0 to 2 and rn=1 to 4. In formula (2) to (19), Yi represents one of sulfur (5), miethylene group (CH12), amino group (N-R; R represents one of H or CjHtu (X=1 20 to 15)), or selenium (Se). Y2 in formula (2) to (19) represents independently one of 16 formula (20) to (37). -H -CiH 2

-

1 -O-CjH 2 j+1 -S-CkH2k+1 (20) (21) (22) (23) Rd42 8 S --- N--N R 41 -N -N 5 CqH2q \.C>H2q \qCqH2 (24) (25) (26) (27)

R

45 -N -N -N -NK4 (28) (29) (30) (31) 10 10R5 R2 R54Re -N -N S -N 0 N R51 R53 R55 eaRr~ (32) (33) (34) (35) 15 Q R0O RGO (36) (37) 17 (0026] Additionally, in formula (1), Z, represents one of formula (38) to (44), and Z2 represents hydrogen or one of formula (38) to (44). In other words, Z, and Z2 can be the identical or different groups.

-COOA

1

-PO

3 HA1 COOA1

COOA

1 (38) (39) (40) (41) oR O 0 0 I-O~ 00U s 000 COOA1 s 0

COOA

1 (42) (43) {44 10 [0027] In formula (38) to (44), A, represents hydrogen (H), lithium (Li), sodium (Na), potassium. (K) or tetra-alkyl ammonium groups as represented by general formula (45), or any species or groups with positive charge. Moreover, in formula (45), R 63 , R,4, &5 and l6 independently represent H or CyH2yt 1 (y=i to 15). 15 R63

R

66

~N-R

4 (45) 20 [0028] It is worthy to note that, in formula (1), when X 2 represents hydrogen, Zi and Z2 both represent formula (38) and X, represents one of formula (2) - (5) in which n=0 and Y 1 represents sulfur (S), Y2 in formula (2) - (5) does not represent one of formula 18 (20) - (22). Furthermore, in fbnnula (1), when Z, and Z2 both represent formula (38) and X 1 and X2 both represent one of formula (2) - (5) in which n=0 and Yi represents sulfur (S), Y 2 in formula (2) - (5) does not represent one of formula (20) - (22). In addition, in formula (1), when Z 1 and Z 2 both represent formula (38) in which A, 5 represents hydrogen (H) and X, and X 2 both represent formula (10) or formula (12) in which n=0 and Yi represents sulfur (S), Y 2 in formula (10) or formula (12) does not represent one of formula (20) - (23). [0029] More particularly, in formula (1), when Z, and Z 2 both represent formula (38), Xi represents formula (2) in which n=P0 and Yi represents sulfur (S) and X 2 10 represents hydrogen or a group the same as Xi (formula (2)), the photosensitizer dye of the present invention is represented as formula (46) and (47), which means Y2 does not represent one of formula (20) - (22) or formula (31). That is to say, Y2 in formula (2) merely represents one of formula (23) (30) or one of formula (32) -(37).

Y

2

Y

2 15 r" \ ' A,OOC S ' \/ \/ Y2 -- Y2Y2 Y2 N N N N H

A

1 OOC ,N Ru-N

A

1 00C \ N -- N N N N C C C G I's " ' S 20 (46) [00301 In formula (1), when Z, and Z2 both represent formula (38), X represents formula (3) in which n-O and Yi represents sulfur (S) and X 2 represents hydrogen or a group the same as X, (formula (3)), the photosensitizer dye of the present invention is 25 represented as formula (48) and (49), Y 2 in formula (48) to (49) does not represent 19 one of formula (20) - (22) or formula (31). That is to say, Y 2 in formula (48) to (49) merely represents one of formula (23) - (30) or one of formula (32) - (37).

Y

2

Y

2 S M AOOC m AOOC 5 \

R

1 R1 \ _ N HRR 5~~R /2 / ~ N N N N

A

1 00C \ N- RU?? 4 k AOOC \/ , H- RR N / A4 (48) (49) 10 [0031] In formula (1), when Zi and Z2 both represent formula (38). X, represents formula (4) in which n=O, Yi represents sulfur (S) and R 3 represents hydrogen (H) and

X

2 represents hydrogen or a group the same as X (formula (4)), the photosensitizer dye of the present invention is represented as formula (50) and (51). Y 2 in formula (50) to (51) does not represent one of formula (20) ~ (22). That is to say, Y 2 in fonnula (50) 15 to (51) merely represents one of formula (23) - (37). Y2 \)NN N N 2 oOc 0 N--R 20 N N N N 20C C d' c (50) (51) [0032] In formula (1), when Z, and Z 2 both represent formula (38), X, represents formula (5) in which n=0, Y 1 represents sulfur (S) and RrR7 represent hydrogen (H) 25 and X 2 represents hydrogen or a group the same as X, (formula (5)), the photosensitizer 20 dye of the present invention is represented as formula (52) and (53). Y 2 in formula (52) and (53) does not represent one of formula (20) - (22). That is to say, Y2 in formula (52) and (53) merely represents one of formula (23)~ (37). y 2

Y

2

A

1 00 s\

A

1 00 N N - / /S \m

A

1 00C \ N 7 7 UNV2A 1 OC0 -- - J Y2. N N N N rn \j % Ij 01 (52) (53) 10 (0033J According to the present invention, the photosensitizer dye contains the above functional groups, that is, X 1 , X 2 , Z, and Z 2 - Hence, the photosensitizer dye is provided with a desirable light absorption capability- hn other words, the absorption 15 spectrum of the photosensitizer dye of the present invention is close to the solar light spectrum, and the absorption coefficient of the photosensitizer dye of the present invention is pretty high. [0034] In general, the potential energy level of the excited state, Le. lowest unoccupied molecular orbital (LUMO), of the photosensitizer dye has to match the 20 potential energy level of the conduction band of the metal oxide (for example, titanium dioxide or zinc oxide, etc.) used in the dye-sensitized solar cells. Accordingly, electrons can be effectively transported from the photosensitizer dye to the metal oxide, and energy loss during the transfer process is minimized. 10035] Additionally, the oxidation potential, i.e. energy level of the highest 25 occupied molecular orbital (HOMO), of the photosensitizer dye has to be slightly lower 21 than the redox potential of the electrolytes (such as, iodine ions) or other materials having hole-transporting property. Accordingly, the photosensitizer dye, after losing an electron, can effectively retrieve an electron from the electrolytes or other hole-transporting materials. 5 100361 Since the photosensitizer dye of the present invention contains the above special groups (XI, X2, Z, and Z 2 ), the energy level of the HOMO and LUMO of the photosensitizer dye is compatible well with the oxidation potential of the electrolyte and the conduction band of the anode in a dye-sensitized solar cell (DSC). As a result, the dye-sensitized solar cells (DSCs) using the above-mentioned photosensitizer dye has 10 higher photoelectric conversion efficiency. [00371 In the following embodiments, some of the chemical structures in the foregoing ruthenium (Ru) complexes having a desirable light absorption capability will be introduced. [00381 In an embodiment of the present invention, a structure of the photosensitizer 15 dye is represented by the following formula (61) to (67).

R

68 RRR RZ6 R70 R1o7 N-N N SS / S / \ / \ 20 N N

A

1 00C / N- Ru-N=C=S -N W / S S \ 1N

N

N A,OOC N-Ru-NC=S N %N

A

1 00C ( -- S

A

1 00C (2 22 R75 R76 R77 RyS / \! NN N N/ N A10C / r"=C SA100CC Nr_ Ru- ,N=C=S 5 N N N N S

A

1 OOC (64) (63) AIOOC Aoooc 0RS R 7 9 AN 10

A

1 OOC / RU-"N=C S A 1 00C = -Ru-,N=C=S N N N N C C S S

A

1 00C (65) A 1 00C (66) R8 RaS 15

A

1 OOC / RN - N=CS N N 2000C "

A

1 CCC (67) 23 [0039] In formula (61), R47, Ra, R6) and R7o independently represent one of I, CEHE+1 (E=1 to 6), OCpH2rt (F=1 to 6), SCaH2c+i(G-1 to 15) or formula (36) to (37). In formula (62), R71, R72, R73 and R14 independently represent one of H, CAH2A+1 (A=1 to 15), OCH2-t- (B-1 to 15), SCjHji (D-1 to 15) or formula (36) to (37). In 5 formula (63), R75 and R, 6 independently represent one of H, CtH2t+ (trl to 15), OCyH2v+i (v-# to 15), SC.H2w+i (vl to 15) or formula (36) to (37). In formula (64) to (66), R77, R79, R79, RSO, RBI and Rs2 independently represent one of SCH 2 G (G=1 to 15) or formula (36) to (37). In formula (67), P, R&, Rg 5 and RE independently represent one of H, CAH2As] (A=1 to 15), OCH2+i (B=1 to 15), SCnHn.i (D=1 to 15) 10 or formula (36) to (37). In formula (61) to (67), A, independently represents hydrogen (H), lithium (Li), sodium (Na), potassium (K) or tetra-alkyl ammonium groups as represented by general formula (45). Moreover, in formula (45), Ra3, R6, REs and R66 independently represent H or CyHmy1 (y=1 to 15). R63 15 R -- N- R4 Ros (45) [0040] In an embodiment of the present invention, a structure of the photosensitizer 20 dye is represented by the following formula (68) to (74).

24 5 NN N A100C N --- N=C=S ASOOC 6 N--N=C=S N. N N / c % "I- S AOOC (88) A 1 00C (69) COH17COH17 AN00 N /joc , \N u- - N=N=C= 15 N N (70)c A1OC A 1 0 0 N / AoOC 72 A 1 00C (71) CoGkis C 5 E1 1 g-Th 200 -N N N N-K

A

1 000 ,NC-

A

1 000I Nc-RuN~ N N 1 N N /\ V

A

1 00C (72) AOOC (73) 25 / \o 0 -- N O 0 N S 5 N N Aooc (74) 10 (0041] In formula (68) to (74), Al independently represents hydrogen (H), lithium (Li), sodium (Na), potassium (K) or tetra-alkyl anmonium groups as represented by general formula (45). As for formula (45), R 63 , 144, R6s and 146 independently represent H or CyH2y+1 (Y=I to 15). R63 15 R 66 -N--R6 4 Res (45) [00421 In an embodiment of the present invention, a structure of the photosensitizer 20 dye is represented by the following formula (75) to (76)- 26 COOAj

A

1 00C N A R87 NN N Ru N Nl: S / 5 *C O(75)

COOA

1 10

N

-u C N N S S 0 15 (76) [00431 In formula (75) to (76). R 87 , R 88 , R8, and Ro independently represent H or C;H2i (J=1 to 15). In formula (75) to (76), A, independently represents hydrogen (H), lithium (Li), sodium (Na), potassium (K) or tetra-alkyl arnmonium groups as 20 represented by general formula (45). Rr, R64, R 65 and l 6 of formula (45) independently represent H or Cyl2yel (y=1 to 15). (0044] The following disclosure describes the synthesis of three ruthenium (Ru) complex dyes of the present invention, and also an analysis of the experimental data regarding to the light absorption capability of these ruthenium (Ru) complexes. It 25 should be appreciated that the following description is provided for illustration purposes, 27 and is not construed to limit the scope of the present invention. [0045] The First Synthesis Example [0046] The chemical compound (represented as CYC-B5 hereinafter) is used as an 5 example to illustrate the synthesis of a ruthenium (Ru) photosensitizer dye according to the first synthesis example of the present invention. [0047] cuHIT CjH 17 10 HOOC =s / * C HOOC CYC-05 10048] CYC-B5 is a compound with a structure of formula (1) when Xi and X2 in formula (1) are the same group and Xi represents the above formula (3), Y 1 in formula (3) represents sulfur (S), n=0, m=2, R, and R2 both represent hydrogen (H), Y 2 represents formula (21), and C;H2i- in formula (21) is C&Hi. Wherein Zi and Z2 are 20 the same group and Z, represents the group of formula (40), and A represents hydrogen (HI). [0049] The processes in synthesizing an ancillary ligand (represented as Ligand-1), which is 4,4'--bis(5-octyl-2,2'-bithophen-5-y)-2,2'-bipyridine), of CYC-B5 is presented as the following: 28 (1)0.0 ag Biuu. THF,-7r8 (54) (54) (2) 1.3 pq, MtSrCi. other. J (t (54) (55) nl. eq. dibromo t pYPd(PPhA n (55) D rx2 iand-1 10 wherein THF represents tetrahydrofuran

(C

4 HO), DMF represents dimethylformamide

(C

3

H

7 NO), and ether is ethyl ether (C 4

H

10 0). 100501 The process is commenced by placing about 4 g of bithiophene in a round-bottom flask with a side arm, followed by adding an anhydrous THF solvent to dissolve the bithiophene. The temperature of the resulting solution is then lowered to 15 -78*C (for example, using liquid nitrogen plus ethanol as a cryogen). Thereafter, about 7.6 ml of n-buty) lithium (n-BuLi) (2.5 M, dissolved in hexane) is gradually drop-added into the bithiophene solution. After the temperature of the resulting solution has returned to the room temperature, the solution is continuously stirred for about 15 minutes. 20 [0051] The process is then continued by adding 4.6 ml of 1 -bromooctane (Br-CBH 7 ) to the solution, and the solution is continuously stirred for about 10 hours. After a predetermined period of reaction time, demonized water is added to terminate the reaction, and then the product is extracted with ether. An organic layer is collected, and the impurty in the organic layer is extracted by using respectively a saturated 29 sodium hydrogen carbonate aqueous solution, deionized water and a saturated sodium chloride aqueous solution. The resulting crude product is purified using column chromatography (using hexane as an eluent) to obtain 5.4 g of an intermediate product. The intermediate product is 5-oatyl-2,2'-bithiophene (CoH2S2), which is represented 5 by formula (54). The yield is about 80.5%. 100521 Thereafter, about 4.2 g of 5-octyl-2,2'-bithiophene is dissolved in anhydrous THF. The temperature of the solution is lowered to -78*C using a cryogen, followed by gradually drop-adding 6.0 ml of n-BuLi (2.5M, dissolved in hexane) to the solution. After this, the temperature of the solution is returned to room temperature, and the 10 solution is stirred for about two hours. Then, the temperature of the solution is again lowered to -78 0 C, and about 3-16 g of chlorotrimethyl stannane (C3HgCISn) (dissolved in an appropriate amount of THF) is added to the solution. [0053] After the temperature of the solution is returned to room temperature, the solution is continuously stirred for about 12 hours. Thereafter, demonized water is 15 added to terminate the reaction, and an extraction is perfonned using respectively a saturated sodium hydrogen carbonate aqueous solution, deionized water and a saturated sodium chloride solution. An organic layer is then collected, and the solvent is removed to obtain about 6.0 g of the crude product, which is trimethyl (5-octyl-2, 2 '-bithiophene) stannane (C 19

H

3 oS 2 Sn) and represented by formula (55). 20 [0054] Thereafter, about 6.0 g of 8-(trimethyltin)-2-octylbithiophene and about 2.0 g of 4-4'-dibromO-2,2'-bipyridine (the method for synthesizing this compound can be referred to 1. Murase, Nippon Kagaku Zasshi, 1956, 77, 682; G. Mnerker and F. H. Case, J. Am. Chem. Soc, 1958, 80, 2745; and D. Wenkert and R. B. Woodward, J. Org. Chem., 1983, 48, 283) are dissolved in 60 ml of anhydrous dimethylformanide

(DMF),

30 About 0.44 g of tetrakis(triphenylphosphine) palladium [Pd(PPha)4] is added as a catalyst, After this, the solution is heated and refluxed for about 22 hours- When the temperature of the solution returns to room temperature, about 5 wt/o of ammonium chloride aqueous solution is added to terminate the reaction. 5 [00551 After this, an extraction is performed using dichlorornethane, and an organic layer is collected. Extraction of the organic layer is conducted using respectively a sodium hydrogen carbonate aqueous solution, deionized water and a saturated sodium chloride aqueous solution. After removing the solvent of the organic layer, a crude product is obtained. The crude product is purified by column chromatography (using 10 hexane as an eluent), and the remaining solid substance is further extracted with ethyl acetate using a Soxhlet extractor to obtain 5,0 of the first ligand (represented as Ligand-1). The yield is about 47.0% [0056] The process in synthesizing a ruthenium (Ru)-containing photosensitizer dye (CYC-B5) is as follows. 15 [00571 S (1)2eq. Ligand-1. DMF ,0 %. 4h (2)2eq.dovbpyDMF.100.4h HODC (,) Exess NH4NCS, DMF,130t ,5hr 20 S HUOC CYC-05 31 [0058] After Ligand-l was prepared, 0.4323 g of {RuC2(p-cymene)]2 and 1.0 g of Ligand-! are dissolved in 30 ml of the anhydrous DMF. The solution is then heated to about 80*C for about 4 hours. After this, about 0.4183 g of 4,4'-bis(E-carboxyvinyl) 2,2'-bi-pyridine (dcvbpy; the synthesis method can be referred to Klein et al., Inorg. 5 Chem., 2005, 44, 178) is added to the solution, followed by heating the solution to about 160 0 C for 4 hours. It is worthy to note that the above reaction must be conducted in the dark to prevent the generation of isomers. [00591 Then, an excessive amount of N1I4NCS is added to the solution, and the reaction is allowed to continue for about 5 hours at a temperature about 130*C. After 10 the reaction completed, the temperature of the solution is returned to room temperature. The solution is concentrated by removing the solvent DMF using a vacuum system, followed by a washing process using respectively deionized water, sodium hydroxide solution at pH 12 and ethyl ether to obtain a solid substance. A crude product is ultimately obtained after vacuum filtration. 15 [0060] After dissolving the crude product in methanol and passing the solution through a column (using methanol as an eluent), a dark color portion is collected and methanol is removed by rotary evaporation. The resulting black solid substance is purified using ethyl acetate to remove the soluble impurities. Then, acetone is used as a solvent to remove the impurities that are dissolvable in acetone. The black solid 20 substance, after being sequentially washed with ethyl acetate and acetone, is dissolved in a mixture solution of methanol and tetra-butyl ammonium hydroxide aqueous solution. The resulting solution then passes through a column (using Sephadex LH-20 as a packing material), and a darker color portion of the solution is collected. Few drops of a 0.01M nitric acid aqueous solution are added to the solution for adjusting the 32 pH to 3, and a precipitation of about 0.69 g is obtained. The precipitation is the product (CYC-B5), and the yield of CYC-B5 is about 40.0%. (0061] Structural analysis and evaluation of the product (CYC-BS) are discussed as follows. 5 [0062] Mass spectrometry (LRMS (FAB)) analysis: theoretical value: m/z -1222.2 ([Mf); experimental value: m/z -1222.2 (m) ([M]*). HRMS (FAB): experimental value: m/z -1222.2004. Elemental analysis of CYC-B5 (CeooHoN 6

O

4

S

6 Ru): theoretical value: C, 58,94; H, 4.95; N, 6.87 %; experimental values: C, 58.82; H4, 5.79. N, 6.43 %. 'H-NMR spectrum signal (500 MHz, Sj/ppm in d 6 -DMSO, J Hz): 9.26 (H); 9.15 (2 10 protons); 9.05 (H); 8.99 (1); 8.91 (H); 8.22 (2 protons); 8.15 (H); 8.02 (H); 7.80 (H); 7.73 (H); 7,55 (H); 7.51 (H); 7.48 (2 protons); 7.39 (2 protons); 7.34 (H); 7.25 (H); 7.21 (H); 6.98 (H); 6.90 (H); 6.84 (H); 2.81 (2H); 2.78 (2H); 1.65 (2H); 1.62 (2H); 1.26 (20H); 0.85 (6H) 15 [0063] The Second Synthesis Example [0064] The second synthesis example is used to illustrate the synthesis of a chemical compound according to another embodiment of invention. This compound is represented as CYC-B6S.

~33 [0065] COOH NN NHN 5 -N! 'N NN CYC-B6S 10 [0066] CYC-B6S is a compound with a structure of formula (1) when X, and X2 in formula (1) are the same group, and Xi represents the group of formula (3), and Yi of formula (3) represents sulfur (S), n=0, m-l, R, and F 0 both represent hydrogen (H), and

Y

2 represents formula (30). R 46 and R 4 7 in formula (30) both represent C 4

H

9 . Wherein Z and Z2 are the same group and Z, represents the group of formula (38), and 15 A 1 represents hydrogen (H). [0067] The process flow in synthesizing the ancillary ligand (represented as Ligand-6S) of CYC-B6S is presented as follows: 34 H MN t-BuCl, ZanC 2 nitramethane (6 Cu-bronze, K 2 C0 3 (56) + nitrobenzene, reflux (57) (1) 1.2 eq. ri-BuLi, ehter, -78' Sn N (2) 1.3 eq. Me 3 SnCI, ether. -78' (58) 10 Br Br 0.4 eq, dibromo-bpy, Pd(PPha) 4 / N N (58)+ ~N N DMF, reflux 22h N N Ligand-6S 15 wherein nitromethane represents CH 3 N0 2 , nitrobenzene represents C 6

H

5

NO

2 , THF represents tetrahydrofuran, DMF represents dimethylforiamide, ether represents ethyl ether. 20 [00681 The process is commenced by placing about 10 g of carbazole (C] 2 H9N) in a round-bottom flask with a side anm, followed by adding 300 ml of nitromethane and 25 g of ZnC . Then, 20 ml of tert-butyl chloride (t-BuCI) is gradually drop-added to the solution and the solution is continuously stirred at room temperature for about 20 hours. The resulting solution is transferred to a beaker, and 350 ml of water is added to the 35 beaker for performing a hydrolysis reaction. [0069] After a predetermined period of reaction time, dichloromethane

(C

2

C

2 ) is added to perform an extraction, and an organic layer is collected. Extraction of the impurity in the organic layer is carried out using respectively demonized water and a 5 saturated sodium chloride aqueous solution. The resulting crude product is purified using a recrystallization method (the solvent being hexane) to obtain a first intermediate product, 3,6-di-tert-butylcarbazole (represented by formula (56)), in which the yield is about 60.6%. [0070] About 10.13 g of the first intermediate product (represented by formula (56)), 10 6.6 g of potassium carbonate (K 2 C0 3 ), 6.7 g of Cu-bronze and 7.1 g of 2-bromo-thiopene (C4H3B4S) axe placed in a round-bottom flask with a side arm. -Nitrobenzene

(C

6

H

5 N0 2 ) is further added to the flask and a reflux reaction is conducted under nitrogen gas for 80 hours. Thereafter, the solvent is removed, and ammonia aqueous solution is added. The resulting solution is continuously stirred for about 2 15 hours. A large amount of water and CHC13 are added to perform an extraction, and an organic layer is collected. Then, the water in the organic layer is removed using magnesium sulfate (MgSO4), and a majority of the solvent is removed after filtering and rotary evaporation. After this, further purification is performed using column chromatography to obtain a second intermediate product (represented by formula (57)). 20 Wherein the yield of the second intermediate product is about 57.2%. 100711 Then, 1.48 g of the second intermediate product is placed in a round-bottom flask with a side arm. Approximately 60 ml of anhydrous tetrahydrofuran is added to the flask. The temperature of the round-bottom flask is controlled at about -78CC (use ethanol and liquid nitrogen to control the temperature). After this, 2.0 ml of n-butyl 36 lithium (n-BuLi) solution (2.5 M, dissolved in hexane) is slowly injected into the flask After the temperature of the solution has returned to room temperature, the solution is stirred for 2 hours. Afterwards, 1.1 g of Me 3 SnCl is slowly injected into the solution, and then the solution is stirred for another 10 hours. A large amount of water and 5 dichloromethane (CH7Cl 2 ) are added (to dissolve the organic layer) to perform an extraction. After an organic layer (lower layer) is collected, the organic layer is readily washed with saturated NaCl (aq). The solvent in the collected product is removed using a rotary evaporator to obtain 2.1 g of the third intermediate product, as represented by formula (58). 10 [00721 About 2.1 g of the third intermediate product and 2.0 g of 4,4'-dibromo 2,2'-biphyridine (the method of synthesis of this compound can be referred to . Murase, Nippon Kagaku Z.asshi, 1956, 77, 682; G. Mnerker and F. 1. Case, J. Am- Chem. Soc., 1958, 80, 2745; and D. Wenkert and R- B. Woodward, J. Org. Chem., 1983, 48, 283) are dissolved in 60nl of anhydrous dimethylformamide (DMF), and about 0.25 g of 15 tetrakis(triphenylphosphine) palladium is added as a catalyst. The mixture is heated and refluxed for about 22 hours. When the temperature of the mixture returns to room temperature, about 5 wt% of ammonium chloride aqueous solution is added to terminate the reaction. An extraction is performed using dichloromethane, and an organic layer is collected. 20 [0073] Thereafter, another extraction of the organic layer is conducted using respectively a sodium hydrogen carbonate aqueous solution, deionized water and a saturated sodium chloride aqueous solution. When the solvent of the organic layer is removed, a crude product is obtained. The crude product is purified by column chromatography (using hexane as an eluent), and the remaining solid substance is 37 further extracted with a Soxhlet extractor (using ethyl acetate as a solvent) to obtain 1.1 g of product, Ligand-6S. The yield of Ligand-65 is about 71.1%. [0074J The process flow in synthesizing a ruthenium (Ru)-containing photosensitizer dye (CYC-B6S) is described as follows: 5 COON N (1) 2eq. Ligand4S, DMF, B0 t, 4h HOOC N \ (2) 2eq. dcbpy. DMF, 100 't. 4h NRu% N C V - (3) Excess NH 4 NCS, DMF. 130 , 5hN N .0N C S N 10 CYC-BOS wherein DMF represents dimethylformamide. [0075] After Ligand-6S was prepared, 0.3848 g of [RuCl 2 (p-cymnne)]2 and 1.1 g of Ligand-6S are dissolved in 80 ml of anhydrous dinethylformamide, and the resulting 15 solution is heated to 80*C. After allowing the reaction to continue for 4 hours, 0.31 g of dcbpy (4,4'-dicarboxylic acid-2,2'-bipyridine) is added. The solution is heated to 160 0 C and the reaction is continued for another 4 hours. The subsequent purification procedure of the resulting product is the same as the purification process of CYC-B5, as mentioned above. Thereafter, the product (CYC-B6S) of about 0.68 g in weight is 20 obtained, and the yield of CYC-B6S is about 40.3%. f0076] Structural analysis and evaluation of the product (CYC-B6S) are discussed as follows. [0077] Mass spectrometry analysis (LRMS (FAB)): theoretical value: n/z -1336.3 ([M)); experimental value: m/z -1336.0 (m) ((M]). (HRMS (FAB)): experimental 38 value: m/z -1336.3160. Elemental analysis of CYC-B6S (CnHGNSO4S4RU): theoretical value: C, 64.70; H, 4.98; N, 8.38 %; experimental value: C, 64.15; H, 6.10; N, 7.83 %. 'H-IvNMR spectrum signal (500 MHz,bx/ppm in d6-DMSO, JHz): 9.45 (H); 9.25 (H); 9.17 (H); 9.13 (H); 9.01 (H); 8.97 (H); 8.34- 8-29 (6 protons); 8.19 (H); 7.95 5 (H); 7.67 (21); 7.62-7-57 (4 protons); 7.55 (H); 7.50 (6 protons); 1.43 (18H); 1.39 (18H) 10078] The Third Synthesis Example [00791 The third synthesis example is used to illustrate the synthesis of a chemical 10 compound according to another embodiment of this invention. This chemical compound is represented as pre-CYC-B12. [0080] N 15 s S N HOOC NC=-Ru"' INCS -IN C H 0C 20 pre-CYC-BIZ 39 [0081] Pre-CYC-B12 is a compound with a structure of formula (1) when X 1 and X 2 in formula (1) are the same group, and X represents the group of formula (10), n=0, R in formula (10) represents hydrogen (H), Yi represents sulfur (S), and Y 2 represents formula (30). R46 and R 1 4 7 in formula (30) both represent C 4

H

9 . Wherein ZI and Z 2 5 are the same group and Z] represents the group of formula (38), and Ai represents hydrogen (H). [0082] The process flow in synthesizing an ancillary ligand (represented as Ligand-12), which is 4,4'-bis(3,6-di-tert-butyl-carbazol-9-y-thieno[3,2-b]thiophen-5 yl)-2,2'-bipyridine, is presented in the following. 10 (1)' .2 eq. n-uLi, sh', -70' (2)1.3 eq. Me 3 SnCI, ether, -7M (59) (60) 15 N S S 0.4 eq. dbrom o-bpy, Pd(PP h,), DMF, relux 22h N Ligand-12 20 [00831 The process is commenced by placing 5.11 g of a reactant (represented by formula (59)) in a round-bottom flask with a side arm, followed by adding approximately 65 ml of anhydrous tetrahydrofuran. The temperature of the 25 round-bottom flask is controlled at about -78"C (may use ethanol and liquid nitrogen to 40 control the temperature). After this, 5.9 ml of n-butyl lithium (n-BuLi) solution (2.5 M, dissolved in hexane) is slowly injected into the flask. After the temperature of the solution has returned to room temperature, the solution is stirred for 2 hours. Subsequently, 3.3 g of Me 3 SnCl is slowly injected into the solution, and then the 5 solution is stirred for another 10 hours. A large amount of water and chloroform (CHC1 3 ) are added (to dissolve the organic layer) to perform an extraction. After an organic layer (lower layer) is collected, the organic layer is readily washed with saturated NaCl (aq). The solvent in the collected product is removed using a rotary evaporator to obtain 7.0 g of the intermediate product, as represented by formula (60). 10 10084) About 7.0 g of the intermediate product (formula (60)) and 1.7 g of 4,4'-dibromo-2,2'-biphyridine (the method for synthesizing this compound can be referred to 1 Murase, Nippon Kagaku Zasshi, 1956, 77, 682; G. Mnerker and F. H. Case, J Am. Chem. Soc., 1958, 80, 2745; and D. Wenkert and R. B. Woodward, J Org. Chem., 1983, 48, 283) are dissolved in 150 nl of anhydrous dimethylformamide (DMF), 15 and about 0.76 g of tetrakis(triphenylphosphinle) palladium is added as a catalyst. The mixture is heated and refluxed for about 22 hours. When the temperature of the mixture returns to room temperature, about 5 wt% of ammonium chloride aqueous solution is added to terminate the reaction. An extraction is performed using chloroform, and an organic layer is collected. Thereafter, another extraction of the 20 organic layer is conducted using respectively a sodium hydrogen carbonate aqueous solution, deionized water and a saturated sodium chloride aqueous solution. When the solvent of the organic layer is removed, a crude product is obtained. The crude product is purified by a Soxhlet extractor (solvent being hexane), and the remaining solid substance is'further extracted with a Soxhlet extractor (using chloroform as a 41 solvent) to obtain 4.54 g of product, which is Ligand-12, and the yield of Ligand-12 is about 82.7%. 100851 Structural analysis and evaluation of the product (Ligand-12) are discussed as follows. 5 [0086] Mass spectrometry analysis (WRMS (FAB)): theoretical value: m/z -986.35 ([Mf); experimental value: m/z -986.2540 ([Mfl). 'H-NMR spectrum signal (300 MHz, SH/PPm in d-choloform): 8.77 (4H); 8.12 (4H); 7,93 (2H); 7.60 (2H); 7.51 (8H); 7.43 (2H); 1.47 (36H). 100871 The process flow in synthesizing a ruthenium (Ru)-containing 10 photosensitizer dye (CYC-B6S) is described as follows: N S s "Vs N I(1) 2utq. Ugarul.I2, DMF. BO t, 4hI 15 r1 'C 3) ea 811NJC %DM F.130' h / \. Hooc N rZ'N=C MS -- s HoOC pre-CYC-B12 20 wherein DMF represents dimethylformanide. [00881 After the Ligand-12 was prepared, 0.456 g of (RuCl2 (p-cymene)]2 and 1.5 g of Ligand-12 are dissolved in 125 nil of anhydrous dimethylfornamide, and the resulting solution is heated to 80*C, After allowing the reaction to continue for 4 hours, 0.375 g of dcbpy (4,4'-dicarboxylic acid-2,2'-bipyridine) is added. The 42 solution is heated to 160"C and the reaction is continued for another 4 hours. The subsequent purification procedure of the resulting product is the same as the purification process of CYC--B5, as mentioned above. Thereafter, the product (pre-CYC-B12) of about 2.30 g in weight is obtained, and the yield of pre-CYC-B12 is about 53.2%. 5 [0089) Structural analysis and evaluation of product (pre-CYC-B12) are discussed as follows. [0090] Mass spectrometry analysis (LRMS (FAB)): theoretical value: m/z -1448.26 ([M]*); experimental value: m/z -1449.6 (m) ([M-H]*). (HRMS (FAB)): experimental value: m/z -1448.2581. Elemental analysis ofpre-CYC-B12

(C

7 6H 6 6NSO 4 S6Ru -H20) 10 theoretical value: C, 62.23; H, 4.67; N, 7.64 %; experimental value: C, 62.00; 1, 4.88; N, 7.45 % 'H-NMR spectrum signal (500 MHz, Sn/ppm in d 6 -DMSO): 9.49 (H); 9.28 (H); 9.23 (H); 9.17 (H); 9.08 (14); 9.01 (H); 8.72 (H); 8.53 (1); 8.36 (H); 8.33 (2 protons); 8.29 (3 protons); 8.06 (H); 8.00 (H); 7.90 (H); 7.69 (H); 7.56 (4 protons); 7.51 (6 protons); 1.43(18 protons); 1.40 (18 protons). 15 [0091] The method in measuring the absorption coefficient of the photosensitizer dye of the present invention and the comparisons between the absorption position and coefficients of CYC-B5, CYC-B6S, pre-CYC-B12, and various conventional photosensitizer dyes are presented in the following. The method in measuring the 20 absorption coefficient of a photosensitizer dye of the present invention includes providing a photosensitizer dye solution of a known concentration and then placing an appropriate amount of the solution in a quartz sample cell. The sample cell is further placed in a UV[Vis Spectrophotometer for analysis. The absorption coefficient can be calculated by using the Beer's law (A = ebc, A: absorbance; s: absorption coefficient; b: 43 beam path; c: concentration of the sample). The absorption coefficients of the photosensitizer dyes of the present invention (CYC-B5, CYC-B6S and pre-CYC-B12) are compared with the absorption coefficients of various conventional photosensitizer dyes, and the results are summarized in Table 1. 5 [0092] It is worthy to note that the conventional photosensitizer dye, 'N3", listed in Table 1, is disclosed by M. Gratzel (J Photochem. A, 2004, 164, 3) and M. K. Nazeeruddin er al. (.T Am. Chem. Soc. 1993, 115, 6382); the conventional photosensitizer dye, "Black dye", listed in Table 1, is disclosed by M. K. Nazeeruddin et aL (J. Am. Chem. Soc., 2001, 123, 1613); the conventional photosensitizer dye, 10 "Z-910", listed in Table 1, is disclosed by P. Wang, et aL (Adv. Mater. 2004,16, 1806).

44 [00931 Table 1 Absorption coefficient of the Position of the longest wavelength Photosensitizert longest wavelength absorption peak Dye absorption peak (urm) CYC-BS 562 25100 CYC-B6S 548 16100 pre-CYC-B12 555 21000 N3 530 14500 Black dye 600 7640 Z910 543 16850 [00941 Based on the results reviewed in Table 1, the absorption coefficient of the photosensitizer dyes CYC-BS, CYC-B6S and pre-CYC-B1 2 are higher and the 5 absorption wavelength of the photosensitizer dyes CYC-B5, CYC-B6S and pre-CYC-Bl2 in the present invention are longer than those of the conventional photosensitizer dyes, respectively. Since the photosensitizer dye of the present invention contains the above-mentioned special groups (X 1 , X 2 , Zi and Z 2 ), the photosensitizer dye has a better light absorption capability as compared with the 10 conventional photosensitizer dyes, In other words, a dye-sensitized solar cell using the photosensitizer dye of the present invention can effectively absorb solar light and convert the solar light into an output current.

45 [0095] Additionally, the above detection method is used to obtain an absorption spectra for CYC-B5, CYC-B6S, pre-CYC-B12 and N3, as shown in Figure 1. Referring to Figure 1, the curve 110 represents the absorption spectrum of CYC-B5, the curve 120 represents the absorption spectrum of CYC-B65, and the curve 130 5 represents the absorption spectrum of pre-CYC-B12, the curve 140 represents the absorption spectrum of N3, and the curve 150 represents the solar spectrum disclosed in Axnual Book of ASTM Standard, G159-98 Standard tables for references solar spectral irradiance at air mass 1.5: direct normal and hemispherical for a 37* tilted surface, Vol. 14.04 (2003). As compared with the solar spectrum (curve 150), curves 110, 120 and 10 130 are closer to the solar spectrum curve 150 than curve 130. In other words, the absorption spectra of CYC-B5, CYC-B6S and pre-CYC-B12 are much closer to the solar spectrum than the absorption spectrum of N3. Accordingly, a dye-sensitized solar cell using the photosensitizer dye of the present invention can effectively absorb solar light and convert the solar light into an output current. 15 100961 Thereafter, the photosensitizer dyes CYC-B5, CYC-B6S and pre-CYC-B12 of the present invention are respectively used as a material for a dye layer in a dye-sensitized solar cell and the efficiency of the cell is then measured. [0097] The method of forming a dye-sensitized solar cell using respectively CYC-B5, CYC-B6S and pre-CYC-B12 as a material of the dye layer is described as 20 follows. A titanium dioxide (TiO2) electrode submerged in a CYC-B5- or CYC-B6S or pre-CYC-B12-containing solution for a period of time, such that CYC-B5 or CYC-B6S or pre-CYC-B12 attaches to the surface of the TiO 2 electrode in a self-assembly manner. [0098] The TiO2 electrode is removed from the dye-containing solution, and is 46 further rinsed using a solvent and dried. The TiO 2 electrode is assembled with a counter electrode, and then the electrodes are sealed with epoxy- After filling with an electrolyte solution and sealing the injection opening, the fabrication of a dye-sensitized solar cell is completed. A dye-sensitized solar cell is fabricated using CYC-B5 or 5 CYC-B6S or pre-CYC-B12 as a material of the dye layer, and thereupon, the voltage, the current and the photoelectric conversion efficiency of the respective cells are measured under irradiation of a virtual sun light with a light source AM1.5G (light intensity of 100 mW/ci 2 ). The results of the measurements are summarized in Table 2. 10 [00991 Table 2 Short circuit Open circuit Fill factor, Photoelectric Photosensitizer current density, voltage, F conversion efficiency, Dye Jsc (mA/cm 2 ) VOC (mV) FF () CYC-B5 20.1 680 0.638 8.71 CYC-B6S 19.8 777 0.633 9.72 Prc-CYC-B12 144 731 0.636 6.72 0100]- Based on the results presented in Table 2, using CYC-B5 or CYC-B6S or pre-CYC-B12 as a dye to fabricate a dye-sensitized solar cell, the photoelectric conversion efficiency is about 8.71% or 9.72% or 6.72%. The photoelectric 15 conversion efficiency of a dye-sensitized solar cell, in general, ranges between 6% and 10%. That is to say, due to the presence of the special groups (XI, X 2 , Z, and Z2) in the photosensitizer dye of the present invention, the solar cell containing the photosensitizer dye of the present invention is provided with excellent photoelectric 47 conversion efficiency. [0101) In view of the above, due to the presence of the special groups (XI, X 2 , Z 1 and Z 2 ) in the photosensitizer dye of the present invention, the absorption spectrum of the photosensitizer dye of the present invention is closer to the solar spectrum and the 5 absorption coefficient of the photosensitizer of the present invention is higher. Moreover, the HOMO and LUMO energy level of the photosensitizer dye in the present invention is compatible well with the oxidation potential of the electrolyte and the conduction band of the anode of a typical dye-sensitized solar cell (DSC). Accordingly, the resulting dye-sensitized solar cell (DSC) of the present invention has 10 higher photoelectric conversion efficiency than the conventional dye-sensitized solar cell (DSC). [0102] It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the 15 present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents.

Claims

1. A photosensitizer dye applicable to a dye-sensitized solar cell, wherein the photosensitizer dye is a ruthenium (Ru) complex represented by the following general formula (1), 5 Formula(1): Z1 N N 10 Z2\N Ru-N N N C C 15 S S wherein X, represents one of formula (2) to (19) and X 2 represents hydrogen, or X, and X 2 both represent one of formula (2) to (19); 48

2 Y2 '\Y22 Y2 Y2R 1 R 2 R R4 0 R (2) R

3 R 5 R6 (2) (3) (4) 3(5) Y 2 y2 Y 2 Y 2 Y2 Y 2 2 R2 0 0 0 0 S S S R5 - j Ri

4 -H R17R 1 R 9 RIO R 12 R 13 R 15 R 16 RI R1 (6) (7) (8) (9) S 2 S2y Y13!R Y, n S 10 R R 2

5 R 2 8 R 29 0 R 0 R 3 2 24 R26 R27 R32 R31 (14) (15) (16) Y2Y2 Y2 y Y2 2 YY 10 R R5 4 - 'R2 8 RX R R4 R 3

6 R 3

7 R 3 R 4 (17) (18) (19) 15 wherein Ri to R 4 0 represent independently one of H, C 1 H 2 + 1 (t=1 to 15), OCl 2 H~v+ 1 (v=l to 15), SCJ-H 2 w+ 1 (w=1 to 15) or formula(36) to (37), and n=0 to 2, m=1 to 4, and wherein Yi represents one of sulfur (S), methylene group (CH] 2 ), amino group (N-R;'R represents one of H or CxH 2 x+ 1 (x=1 to 15)) or selenium (Se), and Y 2 in formula (2)~ (1 9) represents independently one of formula (20) to (37); 20 49 -H -CiH2+OC H2j+1 -S-CkH2k+1 (20) (21) (22) (23) __ R 43 -N -N -R4 -NR -N CqH2q --- CqH2q \-CqH2q (24) (25) (26) (27) 5 R4 R46 R48 R44 -N -N -N -N/Z CqH 2 q CqH2q R 47 47 4 (28) (29) (30) (31) R49 R 50 R2 R54 10 __7 R 5 N -N S -N 0 -N R 57 S R 51 R 53 R 55 R 5 8 (32) (33) (34) (35) 0 R 5 9 o " 6 15 (36) (37) wherein i=I to 15 in formula (21), j= I to 15 in formula (22), and K= I to 15 in formula (23), wherein R41, R 42 , R 43 , R 44 , R 45 , R48, R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 independently represent one of H, CAH2AI (A=l to 15), OC 1 3 H 2 1 + 1 (B=1 to 20 15), SCDIH2D+I (D=l to 15) or formula (36) to (37), wherein R 46 and R 47 independently 50 represent one of H or CEH2E+l (E=l to 6) or OCFH 2 F+ 1 (F=1 to 6) or SCGH2G+I (G=1 to 15), and wherein R 59 and R 60 in formula (36) and formula (37) represent independently H or CjH 2 3+ 1 (J=1 to 15) and r=O to 6, wherein q=1 to 3 of CqH2q in formula (24), formula (26), formula (27), formula (28) and formula (29); 5 wherein Z, represents one of formula (38) to (44), and Z 2 represents hydrogen or one of formula (38) to (44) or a group the same as Zi; R 61 -- COOA -PO 3 HA1 /COOA 1 COOA1 (38) (39) (40) (41) R62 10 0 0 0 0 SCOOA1 S COOA 1 K g COOA 1 (42) (43) (44) 15 wherein R,6 and R 6 2 independently represent one of H, C 1 H 2 1 + 1 (1=1 to 15), OCjH2+II (J=1 to 15) or SCKH2K+I (K=1 to 15); wherein A, represents hydrogen (H), lithium (Li), sodium (Na), potassium (K), tetra-alkyl ammonium groups as represented by general formula (45), or any species or groups with positive charge; 20 R63 R 65 (45) 51 wherein R 63 , R4, R 65 and R 66 independently represent H or CyH2y+I (y=l to 15); when Z, and Z 2 both represent formula (38) and X, represents formula (2) and n in formula (2) represents 0 to 2 and Yi in formula (2) represents sulfur (S) and X 2 represents hydrogen or a group the same as X, (formula (2)), Y 2 does not represent one 5 of formula (20) ~ (22) or formula (31) wherein one of Y 2 in formula (2) merely represents one of formula (23) (30) or one of formula (32) (37); when Z, and Z 2 both represent formula (38) and X, represents formula (3) and n in formula (3) represents 0 to 2 and Y, in formula (3) represents sulfur (S) and X 2 represents hydrogen or a group the same as X, (formula (3)), Y 2 does not represent one 10 of formula (20) ~ (22) or formula (31) wherein Y 2 merely represents one of formula (23) (30) or one of formula (32) - (37); when Zi and Z 2 both represent formula (38) and X, represents formula (4) and n in formula (4) represents 0 and Y, in formula (4) represents sulfur (S) and R 3 in formula (4) represents hydrogen (H) and X 2 represents hydrogen or a group the same as Xi 15 (formula (4)), Y 2 does not represent one of formula (20) ~ (22) wherein Y 2 merely represents one of formula (23) - (37); when Z, and Z 2 both represent formula (38) and X, represents formula (5) and n in formula (5) represents 0 to 2 and Y, in formula (5) represents sulfur (S) and R 4 - R7 in formula (5) represent hydrogen (H) and X 2 represents hydrogen or a group the same 20 as X, (formula (5)), Y 2 does not represent one of formula (20) - (22) wherein Y 2 merely represents one of formula (23) ~ (37). when Z, and Z 2 both represent formula (38) in which A, represents hydrogen (I) and X, and X 2 both represent formula (10) or formula (12) in which n=0 and Y, represents sulfur (S), Y 2 in formula (10) or formula (12) does not represent one of 52 formula (20) (23) wherein Y 2 merely represents one of formula (24) (37). 53 Editorial note: Application Number: 2009200356 The Claims pages end on Page 53 and the Abstract pages begin on Page 59.