1. Kakiage K, Aoyama Y, Yano T, Oya K, Fujisawa J -i., Hanaya M.

Highly-efficient dye-sensitized solar

cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes. Chem Commun.
2015;51:15894.

2. Xie Y, Zhou X, Mi H, Ma J, Yang J, Cheng J. High efficiency ZnO-based dye-sensitized solar cells with a
1H,1H,2H,2H-perfluorodecyltriethoxysilane chain barrier for cutting on interfacial recombination.
Appl Surf Sci. 2018;434:1144-1152.

3. Canto-Aguilar, E.J. Rodriguez-Perez M, Garcia-Rodriguez R, Lizama-Tzec FI, De Denko AT, Osterloh FE,
Oskam G. ZnO-based dye-sensitized solar cells: Effects of redox couple and dye aggregation.
Eelectrochimica Acta. 2017;258:396-404.

4. Guillen E, Peter LM, Anta JA. Electron Transport and Recombination in ZnO-Based Dye-Sensitized
Solar Cells. Phys Chem C. 2011;115(45):22622-22632.

5. Memarian N, Concina I, Braga A, Rozati SM, Vomiero A, Sberveglieri G. Hierarchically assembled ZnO
nanocrystallites for high-efficiency dye-sensitized solar cells. Angrew Chem, Int Ed. 2011;50:12321-
12325.

6. Guillen E, Casanueva F, Anta JA, et al. Photovoltaic performance of nanostructured zinc oxide
sensitized with xanthene dyes. J Photochem Photobiol , A. 2008;200:364-370.

7. Keis K, Lindgren J, Lindquist SE, Hagfeldt A. Studies of the adsorption process of Ru complexes in
nanoporous ZnO electrodes. Langmuir. 2000;16:4688-4694.

8. Lee CP, Li CT, Fan MS, et al. Microemulsion-assisted zinc oxide synthesis: morphology control and its
applications in photoanodes of dye-sensitized solar cells. Electrochim Acta. 2016;210:483-491.

9. Falgenhauer J, Fiehler F, Richter C, Rudolph M, Schlettwein D. Consequences of changes in the ZnO

trap distribution on the performance of dye-sensitized solar cells. Phys Chem Chem Phys.
2017;19(24):16159-16168.

10. Joly D, Palleja L, Narbey S, et al. Metal-free organic sensitizers with narrow absorption in the visible
for solar cells exceeding 10% efficiency. Energy Environ Sci. 2015;8:2010-2018.

11. Idígoras J, Godfroy M, Joly D, et al. Organic dyes for the sensitization of nanostructured ZnO
photoanodes: effect of the anchoring functions. RSC Adv. 2015;5:68929-68938.

12. Al-Alwani MAM, Mohamad AB, Ludin NA, Kadhum AAH, Sopian K. Dye-sensitised solar cells:
development, structure, operation principles, electron kinetics, characterisation, synthesis materials
and natural photosensitisers. Renew Sustain Energy Rev. 2016;65:183-213.

13. Bella F, Galliano S, Gerbaldi C, Viscardi G. Cobalt-based electrolytes for dye-sensitized solar cells:
recent advances toward stable devices. Energies. 2016;9(5):384.

14. Boschloo G, Hagfeldt A. Characteristics of the iodide/triiodide redox mediator in dye-sensitized solar
cells. Acc Chem Res. 2009;42(11):1819-1826.

15. Yella A, Lee HW, Tsao HN, Yi CY, Chandiran AK. Porphyrin-sensitized solar cells with Cobalt (II/III) -
based redox electrolyte exceed 12 percent efficiency. Science (80- ). 2011;334(6060):1203-1203.

16. Habibi MH, Karimi B, Zendehdel M, Habibi M. Preparation of nanostructure mixed copper-zinc oxide
via co-precipitation rout for dye-sensitized solar cells: The influence of blocking layer and
Co(II)/Co(III) complex redox shuttle. J Ind Eng Chem. 2014;20:1462-1467.

17. Heo YW, Norton DP, Tien LC, et al. ZnO nanowire growth and devices. Mater Sci Eng R. 2004;47:1.
18. Saito M, Fujihara S. Large photocurrent generation in dye-sensitized ZnO solar cells. Energy Environ
Sci. 2008;1:280-283.

19. Ambade SB, Mane RS, Han SH, Lee SH, Sung MM, Joo OS. Indoline-dye immobilized ZnO nanoparticle
for whopping 5.44% light conversion efficiency. J Photochem Photobiol A Chem. 2011;222:366-369.

20. Lin CY, Lai YH, Chen HW, et al. Highly efficient dye-sensitized solar cell with a ZnO nanosheet-based
photoanode. Energy Environ, Sci. 2011;4:3448-3455.

21. Qiu J, Guo M, Wang X. Electrodeposition of hierarchical ZnO nanorod-nanosheet structures and their
applications in dye-sensitized solar cells. ACS Appl Mater Interfaces 3. 2011;108:2358-2367.

22. Liu Z, Liu C, Ya J, Lei E. Controlled synthesis of ZnO and TiO2 nanotubes by chemical method and
their application in dye-sensitized solar cells. Renew Energy. 2011;36(4):1177-1181.

23. Zhang YZ, Wu LH, Liu Y., Xie EQ, Yan D, Chen JT. Preparation of ZnO nanospheres and their
applications in dye-sensitized solar cells. Chin Phys Lett. 2009;26(26):038201.

24. Xu C, Wu J, Desai V, Gao D. Multilayer Assembly of Nanowire Arrays for Dye-Sensitized Solar Cells. J
Am Chem Soc. 2011;133(21):8122-8125.

25. Suh DI, Lee SY, Kim TH, et al. The fabrication and characterization of dye-sensitized solar cells with a
branched structure of ZnO nanowires. Chem Phys Lett. 2007;442:348-353.

26. Yao Z, Wu H, Li Y, et al. Dithienopicenocarbazole as the kernel module of low-energy-gap organic

dyes for efficient conversion of sunlight to electricity. Energy Environ Sci. 2015;8(11):3192-3197.

27. Xu L, Aumaitre C, Kervella Y, et al. Increasing the efficiency of organic dye-sensitized solar cells over
10.3% using locally ordered inverse opal nanostructures in the photoelectrode. Adv Funct Mater.
2018;28(15):1706291.

28. Giribabu L, Bolligarla R, M. P. Recent Advances of Cobalt(II/III) Redox Couples for Dye-Sensitized
Solar Cell Applications. Chem Rec. 2015;15:760-788.

29. Klahr BM, Hamann TW. Performance Enhancement and Limitations of Cobalt Bipyridyl Redox
Shuttles in Dye-Sensitized Solar Cells. J Phys Chem C. 2009;113:14040-14045.

30. Tsao HN, Yi C, Moehl T, et al. Cyclopentadithiophene Bridged Donor-Acceptor Dyes Achieve High
Power Conversion Efficiencies in Dye-Sensitized Solar Cells Based on the Tris-Cobalt Bipyridine Redox
Couple. ChemSusChem. 2011;4:591-594.

31. Sapp SA, Elliott CM, Contado C, Caramori S, Bignozzi CA. Substituted Polypyridine Complexes of
Cobalt(II/III) as Efficient Electron-Transfer Mediators in Dye-Sensitized Solar Cells. J Am Chem Soc.
2002;124:11215-11222.

32. Kashif MK, Nippe M, Duffy NW, et al. Stable Dye-Sensitized Solar Cell Electrolytes Based on
Cobalt(II)/(III) Complexes of a Hexadentate Pyridyl Ligand. Angew Chem Int. 2013;52:5527-5531.

33. Nakade S, Makimoto Y, Kubo W, Kitamura T, Wada Y, Yanagida S. Roles of Electrolytes on Charge
Recombination in Dye-Sensitized TiO2 Solar Cells (2): The Case of Solar Cells Using Cobalt Complex
Redox Couples. J Phys Chem B. 2005;109:3488-3493.

34. Koh TM, Nonomura K, Mathews N, et al. Influence of 4-tert-Butylpyridine in DSCs with CoII/III Redox
Mediator. J Phys Chem C. 2013;117:15515-15522.

35. Gao J, Bhagavathi Achari M, Kloo L. Long-Term Stability for Cobalt-Based Dye-Sensitized Solar Cells
 Obtained by Electrolyte Optimization. Chem Commun. 2014;50:6249-6951.

36. Gao J, Yang W, Pazoki M, Boschloo G, Kloo L. Cation-Dependent Photostability of Co(II/III)-Mediated

Dye-Sensitized Solar Cells. J Phys Chem C. 2015;119:24704-24713.

37. Xiang W, Chen D, Caruso RA, Cheng YB, Bach U, Spiccia L. The Effect of the Scattering Layer in Dye-
Sensitized Solar Cells Employing a Cobalt-Based Aqueous Gel Electrolyte. ChemSusChem.
2015;8:3704-3711.

38. Lennert A, Guldi DM. Homoleptic and Heteroleptic Copper Complexes as Redox Couples in Dye-
Sensitized Solar Cells. Chem Photo Chem. 2019;3:636-644.

39. Vlachopoulos N, Freitag M, Hagfeldt A. Cu Complex Redox Couples Open Up New Possibilities for
Dye-Sensitized Solar Cells. Count Electrodes Dye Perovskite Sol Cells. Published online 2018:349-365.

40. Hattori S, Wada Y, Yanagida S, Fukuzumi S. Blue Copper Model Complexes with Distorted Tetragonal
Geometry Acting as Effective Electron-Transfer Mediators in Dye-Sensitized Solar Cells. J Am Chem
Soc. 2005;127:9648-9654.

41. Bai Y, Yu Q, Cai N, Wang Y, Zhang M, Wang P. High-efficiency organic dye-sensitized mesoscopic solar
cells with a copper redox shuttle. Chem Commun (Camb). 2011;47(15):4376-4378.

42. Cao Y, Liu Y, Zakeeruddin SM, Hagfeldt A, Grätzel M. Direct Contact of Selective Charge Extraction
Layers Enables High-Efficiency Molecular Photovoltaics. Joule. 2018;2(6):1108–1117.

43. Freitag M, Giordano F, Yang W, et al. Copper Phenanthroline as a Fast and High-Performance Redox
Mediator for Dye-Sensitized Solar Cells. J Phys Chem C. 2016;120(18):9595-9603.

44. Hamann TW. The end of Iodide? Cobalt complex redox shuttles in DSSCs. Dalt Trans. 2012;41:3111.

45. Feldt SM, Gibson EA, Gabrielsson E, Sun L, Boschloo G, Hagfeldt A. Design of organic dyes and
cobalto polypyridine redox mediators for high-efficiency dye-sensitized solar cells. J Am Chem Soc.
2010;132(46):16714-16724.

46. Freitag M, Teuscher J, Saygili Y, et al. Dye-sensitized solar cells for efficient power generation under
ambient lighting. Nat Photonics. 2017;11:372-378.

47. Ahmad S, Yum JH, Zhang XX, Grätzel M, Butt H., Nazeeruddin MK. Dye-sensitized solar cells based on
poly (3,4-ethylenedioxythiophene) counterelectrode derived from ionic liquids, Journal of Materials
Chemistry. J Mater Chem. 2010;20:1654–1658.

48. Ahmad S, Bessho T, Kessler F, et al. A new generation of platinum and iodine free efficientdye-
sensitized solar cells. Phys Chem Chem Phys. 2012;14:10631–10639.

49. Ellis H, Vlachopoulos N, Haggman L, et al. PEDOT conter electrodes for dye-sensitized solar cells
prepared by aqueous micellar electrodeposition. Eelectrochimica Acta. 2013;107:45-51.

50. Garcia-Rodriguez R, Jiang R, Canto-Aguilar EJ, Oskam G, Boschloo G. Improving the mass transport
of copper-complex redox mediators in dye-sensitized solar cells by reducing the inter-electrode
distance. Phys Chem Chem Phys. 2017;19(47):32132-32142.

51. Fabregat-Santiago, F.; Garcia-Belmonte, G.; Mora-Seró, I.; Bisquert, J. Characterization of

nanostructured hybrid and organic solar cells by impedance spectroscopy. Phys. Chem. Chem. Phys.
2011, 13, 9083−9118.

52. Bisquert, J. Theory of the Impedance of Electron Diffusion and Recombination in a Thin Layer. J.
 Phys. Chem. B 2002, 106, 325−333.

53. Idígoras, J.; Guillén, E.; Ramos, F. J.; Anta, J. A.; Nazeeruddin, M. K.; Ahmad, S. Highly efficient
flexible cathodes for dye sensitized solar cells to complement Pt@TCO coatings. J. Mater. Chem. A
2014, 2, 3175−3181.

54. A. J. Riquelme, V. M. Mwalukuku, P. Sánchez-Fernández, J. Liotier, 5 R. Escalante, G. Oskam, R.

Demadrille, J. A. Anta, ACS Appl. 6 Energy Mater. 2021, 4, 8941.

55. Xie, Y.; Joshi, P.; Darling, S. B.; Chen, Q.; Zhang, T.; Galipeau, D.; Qiao, Q. Electrolyte Effects on
Electron Transport and Recombination at ZnO Nanorods for Dye-Sensitized Solar Cells. J. Phys.
Chem. C 2010, 114, 17880−17888.

56. Hoshikawa, T.; Ikebe, T.; Kikuchi, R.; Eguchi, K. Effects of electrolyte in dye-sensitized solar cells and
evaluation by impedance spectroscopy. Electrochim. Acta 2006, 51, 5286−5294.

57. Anta, J. A.; Idígoras, J.; Guillén, E.; Villanueva-Cab, J.; Mandujano-Ramírez, H. J.; Oskam, G.; Pelleja,
L.; Palomares, E. A ̀ continuity equation for the simulation of the current-voltage curve and the
time-dependent properties of dye-sensitized solar cells. Phys. Chem. Chem. Phys. 2012, 14,
10285−10299

58. Guillén, E.; Peter, L. M.; Anta, J. A. Electron Transport and Recombination in ZnO-Based Dye-
Sensitized Solar Cells. J. Phys. Chem. C 2011, 115, 22622−22632.

59. Raga, S. R.; Barea, E. M.; Fabregat-Santiago, F. Analysis of the Origin of Open Circuit Voltage in Dye
Solar Cells. J. Phys. Chem. Lett. 2012, 3, 1629−1634.

60. Wang, Q.; Moser, J.-E.; Grätzel, M. Electrochemical Impedance Spectroscopic Analysis of Dye-
Sensitized Solar Cells. J. Phys. Chem. B 2005, 109, 14945−14953.

61. Wang, Q.; Ito, S.; Grätzel, M.; Fabregat-Santiago, F.; MoraSeró, I.; Bisquert, J.; Bessho, T.; Imai, H.
Characteristics of High Efficiency Dye-Sensitized Solar Cells†. J. Phys. Chem. B 2006, 110,
25210−25221.

62. Bisquert, J.; Zaban, A.; Salvador, P. Analysis of the mechanisms of electron recombination in
 nanoporous TiO2 dye-sensitized solar cells. Nonequilibrium steady-state statistics and interfacial
electron transfer via surface states. J. Phys. Chem. B 2002, 106, 8774−8782.

63. Bisquert, J.; Mora-Seró, I. Simulation of Steady-State Characteristics of Dye-Sensitized Solar Cells and
the Interpretation of the Diffusion Length. J. Phys. Chem. Lett. 2010, 1, 450−456.

64. Bisquert, J. Chemical capacitance of nanostructured semiconductors: its origin and significance for
nanocomposite solar cells. Phys. Chem. Chem. Phys. 2003, 5, 5360−5364

65. Bisquert, J.; Fabregat-Santiago, F.; Mora-Seró, I.; GarciaBelmonte, G.; Giménez, S. Electron Lifetime
in Dye-Sensitized Solar Cells: Theory and Interpretation of Measurements. J. Phys. Chem. C 2009,
113, 17278−17290.

66. Bisquert, J.; Vikhrenko, V. S. Interpretation of the time constants measured by kinetic techniques in
nanostructured semiconductor electrodes and dye-sensitized solar cells. J. Phys. Chem. B 2004, 108,
2313−2322.

67. Fisher, A. C.; Peter, L. M.; Ponomarev, E. A.; Walker, A. B.; Wijayantha, K. G. U. Intensity Dependence
of the Back Reaction and Transport of Electrons in Dye-Sensitized Nanocrystalline TiO2Solar Cells. J.
Phys. Chem. B 2000, 104, 949−958.

68. Walker, A. B.; Peter, L. M.; Lobato, K.; Cameron, P. J. Analysis of Photovoltage Decay Transients in
Dye-Sensitized Solar Cells†. J. Phys. Chem. B 2006, 110, 25504−25507.

69. Villanueva-Cab, J.; Wang, H.; Oskam, G.; Peter, L. M. Electron Diffusion and Back Reaction in Dye-
Sensitized Solar Cells: The Effect of Nonlinear Recombination Kinetics. J. Phys. Chem. Lett. 2010, 1,
748−751.

70. Jennings, J. R.; Li, F.; Wang, Q. Reliable Determination of Electron Diffusion Length and Charge
Separation Efficiency in DyeSensitized Solar Cells. J. Phys. Chem. C 2010, 114, 14665−14674.

71. Bertoluzzi, L.; Ma, S. On the methods of calculation of the charge collection efficiency of dye
sensitized solar cells. Phys. Chem. Chem. Phys. 2013, 15, 4283−4285.

72. Riquelme, A.; Gálvez, F. E.; Contreras-Bernal, L.; Míguez, H.; Anta, J. A. Internal quantum efficiency
and time signals from intensity-modulated photocurrent spectra of perovskite solar cells. J. Appl.
Phys. 2020, 128, 133103.

73. Bertoluzzi, L.; Bisquert, J. Investigating the Consistency of Models for Water Splitting Systems by
Light and Voltage Modulated Techniques. J. Phys. Chem. Lett. 2017, 8, 172−180.

74. Brivio, F.; Walker, A. B.; Walsh, A. Structural and electronic properties of hybrid perovskites for high-
efficiency thin-film photovoltaics from first-principles. APL Mater. 2013, 1, 042111.

75. Villanueva-Cab, J.; Anta, J. A.; Oskam, G. The effect of recombination under short-circuit conditions
on the determination of charge transport properties in nanostructured photoelectrodes. Phys.
Chem. Chem. Phys. 2016, 18, 2303−2308.
a b c)
) )

c) d e
) )

f) g h
) )

Figure S6. IPCE measurement of different configuration of DSSCs.

 Figure S7. DSSCs
measurements using Platinum and PEDOT on the counter electrode.

Figure S8. Recombination lifetime extracted from IMVS measurements