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Supplementary Information Structurally simple D-A type organic sensitizers for dye-sensitized solar cells: Effect of anchoring moieties on the cell performance Praveen Naik a , Rui Su b , Dickson D Babu a , Ahmed El-Shafei b,* , Airody Vasudeva Adhikari a,* a Organic Materials Laboratory, Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Mangalore-575 025, India (Corresponding Author: Vasudeva Adhikari, [email protected] , Tel.: +91-824-2474000, Ext n : 3203; Fax: +91-824-2474033.) b Polymer and Color Chemistry Program, North Carolina State University, Raleigh, NC, 27695, USA (Corresponding Author: Ahmed El-Shafei, [email protected] ) Contents 1. DFT Calculations…………………………………………………….. 02- 07 2. Spectroscopic data…………………………………………………… 07 - 15 2.1 FTIR…………………………………………………………….....07 - 09 2.2 1 H NMR………………………………………………………….. 09 - 11 2.3 13 C NMR......................................................... .................................11 - 13 2.4 TOF ESI HRMS……………………………..…………………… 13 - 15 3. Device fabrication and photovoltaics studies………………………… 15 - 16 1
Transcript of static-content.springer.com10.1007... · Web viewFluorine‐doped tin oxide (FTO) coated glasses...
Supplementary Information
Structurally simple D-A type organic sensitizers for dye-sensitized solar cells:
Effect of anchoring moieties on the cell performance
Praveen Naika, Rui Sub, Dickson D Babua, Ahmed El-Shafeib,*, Airody Vasudeva Adhikaria,*
aOrganic Materials Laboratory, Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Mangalore-575 025, India (Corresponding Author: Vasudeva Adhikari, [email protected], Tel.: +91-824-2474000, Extn: 3203; Fax: +91-824-2474033.)
bPolymer and Color Chemistry Program, North Carolina State University, Raleigh, NC, 27695, USA (Corresponding Author: Ahmed El-Shafei, [email protected])
Contents
1. DFT Calculations…………………………………………………….. 02- 07
2. Spectroscopic data…………………………………………………… 07 - 15
2.1 FTIR…………………………………………………………….....07 - 09
2.2 1H NMR………………………………………………………….. 09 - 11
2.3 13C NMR..........................................................................................11 - 13
2.4 TOF ESI HRMS……………………………..…………………… 13 - 15
3. Device fabrication and photovoltaics studies………………………… 15 - 16
1. DFT Calculations
1
1.1 Cartesian coordinates of the A1 dye
ATOM CARTESIAN COORDINATES
1 c 0.03078208923355 0.38938639306404 0.40949370052398
2 c 2.62549671644532 0.15945605218183 0.53492055301853
3 c 4.21102863955170 2.17642299121908 -0.26422130746013
4 c 3.00993664144506 4.40033112448395 -1.17981180438934
5 c 0.41025771601269 4.60510323086583 -1.29729395800558
6 c -1.19382918310079 2.60290620784618 -0.50622983288924
7 n 6.79029498533344 1.98399000713331 -0.15709829679802
8 c 8.37839610902354 4.08147470221661 -0.96539699496961
9 c 7.97682191317967 -0.31553477649864 0.77918374011489
10 c -3.90272515826409 2.52697496187229 -0.51204580674312
11 c -5.91019600820534 4.06795366383015 -1.17642915924599
12 c -5.77593831057829 6.62555435274965 -2.23135284964280
13 n -8.09045742930027 7.81746166971839 -2.76410770511167
14 c -10.48554265419572 6.77270844884240 -2.37210070473129
15 n -10.55151998447468 4.33781811365599 -1.36763438274947
16 c -8.42299932152498 2.88544020201559 -0.72625234945346
17 o -8.70454470054467 0.75247733561388 0.15728891868457
18 o -3.81885625126989 7.80971746751130 -2.68730090043544
19 o -12.43904622597815 7.91220915351935 -2.87490324025935
20 c -13.07630021183784 3.26466393662734 -0.96718811842940
21 c -7.95542809502539 10.37625645846185 -3.81951021219542
22 h 10.03077714412065 -0.10207437485522 0.68515133200618
23 h 7.44675681399786 -1.97195706998880 -0.36509878469046
24 h 7.45586873967876 -0.70094428676194 2.75813126789239
25 h 10.36302649883881 3.55916065497796 -0.71663401776202
26 h 8.01487197319808 5.79619794309447 0.15717084134212
27 h 8.07720606145025 4.54450199800709 -2.97261998052082
28 h -9.88840281740110 11.02216998648631 -4.13954321895602
29 h -6.88757974749204 10.34898844328182 -5.59415248981948
2
30 h -6.97411521314680 11.63334967920153 -2.49716577799736
31 h -12.81475387636188 1.36563382412850 -0.20289203379001
32 h -14.10896029902015 3.19791775122692 -2.76090588934538
33 h -14.14721737007553 4.44332354751811 0.35731763401505
34 h 3.43997017956326 -1.58483719787494 1.25475507405057
35 h 4.14526398490974 5.99379185697658 -1.81162101910653
36 h -4.62740943006785 0.72965341942891 0.21742853430291
37 h -0.46044997296603 6.32482139694249 -2.00712966543387
38 h -1.13592755191770 -1.19119605007538 1.03786037867910
1.2 Cartesian coordinates of A2 dye
ATOM CARTESIAN COORDINATES
1 c 0.03078208923355 0.38938639306404 0.40949370052398
2 c 2.62549671644532 0.15945605218183 0.53492055301853
3 c 4.21102863955170 2.17642299121908 -0.26422130746013
4 c 3.00993664144506 4.40033112448395 -1.17981180438934
5 c 0.41025771601269 4.60510323086583 -1.29729395800558
6 c -1.19382918310079 2.60290620784618 -0.50622983288924
7 n 6.79029498533344 1.98399000713331 -0.15709829679802
8 c 8.37839610902354 4.08147470221661 -0.96539699496961
9 c 7.97682191317967 -0.31553477649864 0.77918374011489
10 c -3.90272515826409 2.52697496187229 -0.51204580674312
11 c -5.91019600820534 4.06795366383015 -1.17642915924599
12 c -5.77593831057829 6.62555435274965 -2.23135284964280
13 n -8.09045742930027 7.81746166971839 -2.76410770511167
14 c -10.48554265419572 6.77270844884240 -2.37210070473129
15 n -10.55151998447468 4.33781811365599 -1.36763438274947
16 c -8.42299932152498 2.88544020201559 -0.72625234945346
17 o -8.70454470054467 0.75247733561388 0.15728891868457
18 o -3.81885625126989 7.80971746751130 -2.68730090043544
19 o -12.43904622597815 7.91220915351935 -2.87490324025935
20 c -13.07630021183784 3.26466393662734 -0.96718811842940
3
21 c -7.95542809502539 10.37625645846185 -3.81951021219542
22 h 10.03077714412065 -0.10207437485522 0.68515133200618
23 h 7.44675681399786 -1.97195706998880 -0.36509878469046
24 h 7.45586873967876 -0.70094428676194 2.75813126789239
25 h 10.36302649883881 3.55916065497796 -0.71663401776202
26 h 8.01487197319808 5.79619794309447 0.15717084134212
27 h 8.07720606145025 4.54450199800709 -2.97261998052082
28 h -9.88840281740110 11.02216998648631 -4.13954321895602
29 h -6.88757974749204 10.34898844328182 -5.59415248981948
30 h -6.97411521314680 11.63334967920153 -2.49716577799736
31 h -12.81475387636188 1.36563382412850 -0.20289203379001
32 h -14.10896029902015 3.19791775122692 -2.76090588934538
33 h -14.14721737007553 4.44332354751811 0.35731763401505
34 h 3.43997017956326 -1.58483719787494 1.25475507405057
35 h 4.14526398490974 5.99379185697658 -1.81162101910653
36 h -4.62740943006785 0.72965341942891 0.21742853430291
37 h -0.46044997296603 6.32482139694249 -2.00712966543387
38 h -1.13592755191770 -1.19119605007538 1.03786037867910
1.3 Cartesian coordinates of the A3 dye
ATOM CARTESIAN COORDINATES
1 c 0.03078208923355 0.38938639306404 0.40949370052398
2 c 2.62549671644532 0.15945605218183 0.53492055301853
3 c 4.21102863955170 2.17642299121908 -0.26422130746013
4 c 3.00993664144506 4.40033112448395 -1.17981180438934
5 c 0.41025771601269 4.60510323086583 -1.29729395800558
6 c -1.19382918310079 2.60290620784618 -0.50622983288924
7 n 6.79029498533344 1.98399000713331 -0.15709829679802
8 c 8.37839610902354 4.08147470221661 -0.96539699496961
9 c 7.97682191317967 -0.31553477649864 0.77918374011489
10 c -3.90272515826409 2.52697496187229 -0.51204580674312
11 c -5.91019600820534 4.06795366383015 -1.17642915924599
4
12 c -5.77593831057829 6.62555435274965 -2.23135284964280
13 n -8.09045742930027 7.81746166971839 -2.76410770511167
14 c -10.48554265419572 6.77270844884240 -2.37210070473129
15 n -10.55151998447468 4.33781811365599 -1.36763438274947
16 c -8.42299932152498 2.88544020201559 -0.72625234945346
17 o -8.70454470054467 0.75247733561388 0.15728891868457
18 o -3.81885625126989 7.80971746751130 -2.68730090043544
19 o -12.43904622597815 7.91220915351935 -2.87490324025935
20 c -13.07630021183784 3.26466393662734 -0.96718811842940
21 c -7.95542809502539 10.37625645846185 -3.81951021219542
22 h 10.03077714412065 -0.10207437485522 0.68515133200618
23 h 7.44675681399786 -1.97195706998880 -0.36509878469046
24 h 7.45586873967876 -0.70094428676194 2.75813126789239
25 h 10.36302649883881 3.55916065497796 -0.71663401776202
26 h 8.01487197319808 5.79619794309447 0.15717084134212
27 h 8.07720606145025 4.54450199800709 -2.97261998052082
28 h -9.88840281740110 11.02216998648631 -4.13954321895602
29 h -6.88757974749204 10.34898844328182 -5.59415248981948
30 h -6.97411521314680 11.63334967920153 -2.49716577799736
31 h -12.81475387636188 1.36563382412850 -0.20289203379001
32 h -14.10896029902015 3.19791775122692 -2.76090588934538
33 h -14.14721737007553 4.44332354751811 0.35731763401505
34 h 3.43997017956326 -1.58483719787494 1.25475507405057
35 h 4.14526398490974 5.99379185697658 -1.81162101910653
36 h -4.62740943006785 0.72965341942891 0.21742853430291
37 h -0.46044997296603 6.32482139694249 -2.00712966543387
38 h -1.13592755191770 -1.19119605007538 1.03786037867910
1.4 Cartesian coordinates of the A4 dye
ATOM CARTESIAN COORDINATES
1 c -0.01707427795282 0.47023199422459 0.63014646600930
2 c 2.57276808103676 0.18369455978355 0.70691765486704
5
3 c 4.18549792509655 2.12539532438859 -0.21664380968404
4 c 3.01444109866939 4.33494939139918 -1.20476545533928
5 c 0.41888614472564 4.59732768801748 -1.27189312179315
6 c -1.21340010694116 2.67098384634270 -0.35569761799229
7 n 6.76011200533136 1.87635326024381 -0.15723173637696
8 c 7.91521996174296 -0.41323783371966 0.84274519948889
9 c 8.37812740049865 3.88932232484356 -1.11057541672351
10 c -3.91990801630857 2.65487255330152 -0.29629206741414
11 c -5.91606716288725 4.21204915828981 -0.97450045016890
12 c -5.76534107209601 6.70532528835325 -2.13945810345024
13 n -8.09009173826620 7.94350151532062 -2.64643312396289
14 c -10.47330246464849 6.94545514189828 -2.19416966562023
15 n -10.56466644296048 4.59383139186609 -1.04157088854830
16 c -8.43026438580756 3.12006770483089 -0.41662918364243
17 o -8.74302158841194 1.02351427932682 0.54267818294572
18 o -3.78797533771981 7.79729199878559 -2.71584159080484
19 s -13.11637033404548 8.50105941413848 -3.00724493747247
20 c -7.86069181929750 10.47764880523843 -3.81375246166170
21 c -7.73554819879706 10.36631587073604 -6.69292272797397
22 c -13.04220962453755 3.43483652008217 -0.44344887535053
23 c -14.04574144897172 1.79633770194519 -2.59309365360502
24 h -15.87229588321444 0.97658553377470 -2.04319520220113
25 h -12.74104115821916 0.23993385945415 -3.00837658526423
26 h -14.33858417732073 2.92530560211563 -4.30759868403017
27 h -7.54743269753566 12.28913433999227 -7.45358273871641
28 h -9.46609680871575 9.53313974853942 -7.47429743077701
29 h -6.09703675662268 9.26254431322804 -7.32252442696299
30 h 10.35504258242113 3.33741369914021 -0.86594783250610
31 h 8.07190493913412 5.67053099994556 -0.07871265346106
32 h 8.04973803416111 4.24644488725691 -3.13512122501578
33 h 9.97110444283872 -0.24568350475105 0.70912338816006
6
34 h 7.33227820215897 -2.09884410465616 -0.23118375576014
35 h 7.41886336992135 -0.71392987012076 2.84204493066381
36 h -14.34133253940071 4.98946169011234 -0.03273726550548
37 h -12.73643320932024 2.29334169279180 1.25399998494414
38 h -6.12840048946750 11.30510700926141 -3.04501345765638
39 h -9.50421944802898 11.56671996512125 -3.19098445099800
40 h 3.36362282398587 -1.54673247905195 1.48416585269330
41 h 4.17126124833906 5.86973268613924 -1.93495123923504
42 h -4.66395383429449 0.90717668688713 0.52732099924559
43 h -0.42650476151183 6.30383643246155 -2.03977929425159
44 h -1.20484184202544 -1.05269743066997 1.35391307038480
2. Spectroscopic data
2.1 FTIR spectra
Fig S1: FTIR spectrum of A1
7
Fig S2: FTIR spectrum of A2
Fig S3: FTIR spectrum of A3
8
Fig S4: FTIR spectrum of A4
2.2 1H NMR Spectra
Fig S5: 1H NMR spectrum of A1 dye
9
Fig S6: 1H NMR spectrum of A2 dye
Fig S7: 1H NMR spectrum of A3 dye
10
Fig S8: 1H NMR spectrum of A4 dye
Fig S9: 13C NMR spectrum of A1 dye
11
Fig S8: 13C NMR spectrum of A2 dye
Fig S10: 13C NMR spectrum of A3 dye
12
Fig S12: 13C NMR spectrum of A4 dye
2.3 TOF HRMS ESI Spectra
13
Fig S13: TOF HRMS of A1
Fig S14: TOF HRMS of A2
Fig S15: TOF HRMS of A3
14
Fig S16: TOF-HRMS of A4
3. TiO2 Electrode Preparation and Device Fabrication
Fluorine‐doped tin oxide (FTO) coated glasses (2.2 mm thickness, sheet resistance of 8 Ω/cm2,
TEC, Pilkington) were washed with detergent, water, acetone and ethanol, sequentially. After
this FTO glass plates were immersed into a 40 mM aqueous TiCl4 solution at 70 C for 30 min
and washed with water and ethanol. Thin layer (8-12 μm thick) of TiO2 (Solaronix, Ti-Nanoxide
D/SP) was deposited (active area, 0.18 cm2) on transparent conducting glass by squeegee
printing followed by drying at 350 C for 10 min and curing at 500 C for 30 min. Next, after
drying the electrodes, scattering layer (5 μm thick) TiO2 particles (Solaronix, Ti-Nanoxide R/SP)
were printed onto the already deposited TiO2 layer. The TiO2 electrodes were heated under an air
flow at 350 C for 10 min, followed by heating at 500 C for 30 min. After cooling to room
temperature, the TiO2 electrodes were treated with 40 mM aqueous solution of TiCl4 at 70 C for
15
30 min and then washed with water and ethanol. The electrodes were heated again at 500 C for
30 min and left to cool to 80 C before dipping them into the dye solution. The dye solutions
(0.3 mM) were prepared in 10 mL 1:1:1 acetonitrile, tert-butanol and dimethyl sulfoxide.
Chenodeoxycholic acid (CDCA) was added at a concentration of 10 mM. The electrodes were
immersed in the dye solutions and then kept at 25 °C for 20 hours to adsorb the dye onto the
TiO2 surface.
For preparing the counter electrode, pre-cut TCO glasses were washed with water followed by
0.1M HCl in EtOH, and sonication in acetone bath for 10 min. These washed TCO were then
dried at 400 C for 15 min. Thin layer of Pt-paste (Solaronix, Platisol T/SP) on TCO was printed
and the printed electrodes were then cured at 450 C for 10 min. The dye sensitized TiO2
electrodes were sandwiched with Pt counter electrodes and the electrolyte (Solaronix, Iodolyte
HI-30) was then injected into the cell, while the two electrodes were held together with the clips.
Photoelectrochemical Measurements
Photocurrent-voltage characteristics of DSCs were measured using a Keithley 2400 source meter
under illumination of AM 1.5 G solar light from solar simulator (SOL3A, Oriel) equipped with a
450 W xenon lamp (91160, Oriel). The incident light intensity was calibrated using a reference
Si solar cell (Newport Oriel, 91150V) to set 1 Sun (100 mW/cm2). The measurement was fully
controlled under Oriel IV Test Station software.
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