Unravelling the bottleneck of phosphonic acid anchoring groups aiming toward enhancing the stability and efficiency of mesoscopic solar cells

Abstract

Novel near-infrared sensitizers with different anchoring groups aiming toward improved stability and efficiency of dye-sensitized solar cells were synthesized. Adsorption of these dyes on the mesoporous TiO₂ surface revealed the dye adsorption rate of –CH=CH–COOH (SQ-139)>–CH=C(CN)COOH (SQ-140)>–PO₃H₂ (SQ-143)>–CH=C(CN)PO₃H₂ (SQ-148)>–CH=C(CN)PO₃H–C₂H₅ (SQ-157)>–PO₃H–C₂H₅ (SQ-151)> –CH=CH–COOH(–PO₃H₂) (SQ-162). The binding strength of these dyes on mesoporous TiO₂ as investigated by dye desorption studies follows SQ-162>SQ-143>SQ-148>SQ-139≫SQ-157~SQ-151≫SQ-140 order. The acrylic acid anchoring group was demonstrated to be an optimum functional group owing to its fast dye adsorption rate and better binding strength on TiO₂ along with good photoconversion efficiency. Results of dye binding on TiO₂ surface demonstrated that SQ-162 bearing double anchoring groups of phosphonic and acrylic acid exhibited>550 times stronger binding as compared to dye SQ-140 having cyanoacrylic acid anchoring group. SQ-140 exhibited the best photovoltaic performance with photon harvesting mainly in the far-red to near-infrared wavelength region having short circuit current density, open-circuit voltage and fill factor of 14.28 mA·cm^–2, 0.64 V and 0.65, respectively, giving the power conversion efficiency of 5.95%. Thus, dye SQ-162 not only solved the problem of very poor efficiency of dye bearing only phosphonic acid while maintaining the extremely high binding strength opening the path for the design and development of novel near-infrared dyes with improved efficiency and stability by further increasing the π-conjugation.

Graphical abstract

Keywords

anchoring groups / adsorption behaviour / dye-binding strength / squaraine dyes / dye-sensitized solar cells

References

[1] Lund H, Mathiesen B V. Energy system analysis of 100% renewable energy systems—the case of Denmark in years 2030 and 2050. Energy, 2009, 34(5): 524–531

[2] Omer A M, Agric J. Environmental and socio-economic aspects of possible development in renewable energy use. Journal of Agricultural Extension and Rural Development, 2010, 2: 1–21

[3] Voudoukis N F. Design, description, implementation, and assessment of a multimedia application with simulations for teaching models of light. European Journal of Electrical and Computer Engineering, 2018, 2(7): 13

[4] Freitag M, Teuscher J, Saygili Y, Zhang X, Giordano F, Liska P, Hua J, Zakeeruddin S M, Moser J E, Grätzel M, . Dye-sensitized solar cells for efficient power generation under ambient lighting. Nature Photonics, 2017, 11(6): 372–378

[5] O’Regan B, Grätzel M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO₂ films. Nature, 1991, 353(6346): 737–740

[6] Ahmad M S, Pandey A K, Rahim N A. Advancements in the development of TiO₂ photoanodes and its fabrication methods for dye-sensitized solar cell (DSSC) applications. A review. Renewable & Sustainable Energy Reviews, 2017, 77: 89–108

[7] Wu J, Lan Z, Lin J, Huang M, Huang Y, Fan L, Luo G. Electrolytes in dye-sensitized solar cells. Chemical Reviews, 2015, 115(5): 2136–2173

[8] Wu J, Lan Z, Lin J, Huang M, Huang Y, Fan L, Luo G, Lin Y, Xie Y, Wei Y. Counter electrodes in dye-sensitized solar cells. Chemical Society Reviews, 2017, 46(19): 5975–6023

[9] Eom K Y, Kang S H, Choi I T, Yoo Y J, Kim J H, Kim H K. Significant light absorption enhancement by a single heterocyclic unit change in the π-bridge moiety from thieno[3,2-b]benzothiophene to thieno[3,2-b]indole for high performance dye sensitized and tandem solar cells. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(5): 2297–2308

[10] Yella A, Lee H W, Tsao H N, Yi C, Chandiran A K, Nazeeruddin M K, Diau E W G, Yeh C Y, Zakeeruddin S M, Grätzel M. Porphyrin-sensitized solar cells with cobalt(II/III)-based redox electrolyte exceed 12 percent efficiency. Science, 2011, 334(6056): 629–633

[11] Kakiage K, Aoyama Y, Yano T, Otsuka T, Kyomen T, Unno M, Hanaya M. An achievement of over 12 percent efficiency in an organic dye-sensitized solar cell. Chemical Communications, 2014, 50(48): 6379–6381

[12] Ji J M, Zhou H, Yu K E, Kim C H, Kim H K. 14.2% efficiency dye-sensitized solar cells by co-sensitizing novel thieno[3,2-b]indole-based organic dyes with a promising porphyrin sensitizer. Advanced Energy Materials, 2020, 15(15): 2000124

[13] Mathew S, Yella A, Gao P, Baker R H, Curchod B F E, Astani N A, Tavernelli I, Rothlisberger U, Nazeeruddin M K, Grätzel M, . Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nature Chemistry, 2014, 6(3): 242–247

[14] Zhang L, Yang X, Wang W, Gurzadyan G G, Li J, Li X, An J, Yu Z, Wang H, Cai B, et al. 13.6% efficient organic dye-sensitized solar cells by minimizing energy losses of the excited state. ACS Energy Letters, 2019, 4(4): 943–951

[15] Kang S H, Jeong M J, Eom Y K, Choi I T, Kwon S M, Yoo Y J, Kim J H, Kwon J, Park J H, Kim H K. Porphyrin sensitizers with donor structural engineering for superior performance dye-sensitized solar cells and tandem solar cells for water splitting applications. Advanced Energy Materials, 2017, 7(7): 1072117

[16] Pradhan A, Kiran M S, Kapil G, Hayase S, Pandey S S. Wide wavelength photon harvesting in dye-sensitized solar cells utilizing cobalt complex redox electrolyte: implication of surface passivation. Solar Energy Materials and Solar Cells, 2019, 195: 122–133

[17] Baranwal A K, Shiki T, Ogomi Y, Pandey S S, Ma T, Hayase S. Tandem dye-sensitized solar cells with a back-contact bottom electrode without a transparent conductive oxide layer. RSC Advances, 2014, 4(88): 47735–47742

[18] Shivashimpi G M, Pandey S S, Watanabe R, Fujikawa N, Ogomi Y, Yamaguchi Y, Hayase S. Efficient far-red sensitization of nanocrystalline TiO₂ films by an unsymmetrical squaraine dye. Journal of Photochemistry and Photobiology A Chemistry, 2014, 273: 1–7

[19] Murakami T N, Yoshida E, Koumura N. Carbazole dye with phosphonic acid anchoring groups for long-term heat stability of dye-sensitized solar cells. Electrochimica Acta, 2014, 131: 174–183

[20] Zhang L, Cole J M. Anchoring groups for dye-sensitized solar cells. ACS Applied Materials & Interfaces, 2015, 7(6): 3427–3455

[21] Brennan B J, Portole’s M J L, Liddell P A, Moore T A, Moore A L, Gust D. Comparison of silatrane, phosphonic acid, and carboxylic acid functional groups for attachment of porphyrin sensitizers to TiO₂ in photoelectrochemical cells. Physical Chemistry Chemical Physics, 2013, 15(39): 16605–16614

[22] Hanson K, Brennaman M K, Luo H, Glasson C R K, Concepcion J J, Song W, Meyer T J. Photostability of phosphonate-derivatized, Ru(II) polypyridyl complexes on metal oxide surfaces. ACS Applied Materials & Interfaces, 2012, 4(3): 1462–1469

[23] Kakiage K, Yamamura M, Fujimura E, Kyomen T, Unno M, Hanaya M. High performance of Si–O–Ti bonds for anchoring sensitizing dyes on TiO₂ electrodes in dye-sensitized solar cells evidenced by using alkoxysilylazobenzenes. Chemistry Letters, 2010, 39(3): 260–262

[24] Higashino T, Nimura S, Sugiura K, Kurumisawa Y, Tsuji Y, Imahori H. Photovoltaic properties and long-term durability of porphyrin-sensitized solar cells with silicon-based anchoring groups. ACS Omega, 2017, 2(10): 6958–6967

[25] Vats A K, Pradhan A, Hayase S, Pandey S S. Synthesis, photophysical characterization and dye adsorption behaviour in unsymmetrical squaraine dyes with varying anchoring groups. Journal of Photochemistry and Photobiology A Chemistry, 2020, 394: 112467

[26] Baktash A, Khoshnevisan B, Sasani A, Mirabbaszadeh K. Effects of carboxylic acid and phosphonic acid anchoring groups on the efficiency of dye sensitized solar cells: a computational study. Organic Electronics, 2016, 33: 207–212

[27] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Mennucci B, Petersson G A D J, . Gaussian 09. Revision A.02, Gaussian, Inc., Wallingford CT, 2009

[28] Shivashimpi G M, Pandey S S, Watanabe R, Fujikawa N, Ogomi Y, Yamaguchi Y, Hayase S. Novel unsymmetrical squaraine dye bearing cyanoacrylic acid anchoring group and its photosensitization behavior. Tetrahedron Letters, 2012, 53(40): 5437–5440

[29] Li J, Chen C Y, Ho W C, Chen S H, Wu C G. Unsymmetrical squaraines incorporating quinoline for near-infrared responsive dye-sensitized solar cells. Organic Letters, 2012, 14(21): 5420–5423

[30] Chen Y H, Qi L W, Fang F, Tan B. Organocatalytic atroposelective arylation of 2-naphthylamines as a practical approach to axially chiral biaryl amino alcohols. Angewandte Chemie, 2017, 56(51): 16308–16312

[31] Brown D G, Schauer P A, Garcia J B, Fancy B R, Berlinguette C P. Stabilization of ruthenium sensitizers to TiO₂ surfaces through cooperative anchoring groups. Journal of the American Chemical Society, 2013, 135(5): 1692–1695

[32] Yum J H, Moon S J, Baker R H, Walter P, Geiger T, Nüesch F, Grätzel M, Nazeeruddin M K. Effect of coadsorbent on the photovoltaic performance of squaraine sensitized nanocrystalline solar cells. Nanotechnology, 2008, 19(42): 424005

[33] Shivashimpi G M, Pandey S S, Hayat A, Fujikawa N, Ogomi Y, Yamaguchi Y, Hayase S. Far-red sensitizing octatrifluorobutoxy phosphorous triazatetrabenzocorrole: synthesis, spectral characterization, and aggregation studies. Journal of Photochemistry and Photobiology A Chemistry, 2014, 289: 53–59

[34] Ren T B, Xu W, Zhang W, Zhang X X, Wang Z Y, Xiang Z, Yuan L, Zhang X B. A general method to increase stokes shift by introducing alternating vibronic structures. Journal of the American Chemical Society, 2018, 140(24): 7716–7722

[35] Inoue T, Pandey S S, Fujikawa N, Yamaguchi Y, Hayase S. Synthesis and characterization of squaric acid-based NIR dyes for their application towards dye-sensitized solar cells. Journal of Photochemistry and Photobiology A Chemistry, 2010, 213(1): 23–29

[36] Li L, Xie Z X, Wang Y L. Wang, Xu H, Xu T M, Zhang Z G, Zhang H L. Expanding the photoresponse range of TiO₂ nanotube arrays by CdS/CdSe/ZnS quantum dots co-modification. Journal of Photochemistry and Photobiology A Chemistry, 2011, 224(1): 25–30

[37] Ogomi Y, Kato T, Hayase S. Dye-sensitized solar cells consisting of ionic liquid and solidification. Journal of Photopolymer Science and Technology, 2006, 19(3): 403–408

[38] Pastore M, Fantacci S, Angelis F D. Modeling excited states and alignment of energy levels in dye-sensitized solar cells: successes, failures, and challenges. Journal of Physical Chemistry C, 2013, 117(8): 3685–3700

[39] Nazeeruddin M K, Angelis F D, Fantacci S, Selloni A, Viscardi G, Liska P, Ito S, Takeru B, Grätzel M. Combined experimental and DFT-TDDFT computational study of photoelectrochemical cell ruthenium sensitizers. Journal of the American Chemical Society, 2005, 127(48): 16835–16847

[40] Improta R, Barone V, Scalmani G, Frisch M J. A state-specific polarizable continuum model time-dependent density functional theory method for excited-state calculations in solution. Journal of Chemical Physics, 2006, 125(5): 054103

[41] Pandey S S, Morimoto T, Fujikawa N, Hayase S. Combined theoretical and experimental approaches for the development of squaraine dyes with small energy barrier for electron injection. Solar Energy Materials and Solar Cells, 2017, 159: 625–632

[42] Pradhan A, Morimoto T, Saikiran M, Kapil G, Hayase S, Pandey S S. Investigation of the minimum driving force for dye regeneration utilizing model squaraine dyes for dye-sensitized solar cells. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(43): 22672–22682

[43] Park H, Bae E, Lee J J, Park J, Choi W. Effect of the anchoring group in Ru-bipyridyl sensitizers on the photoelectrochemical behavior of dye-sensitized TiO₂ electrodes: carboxylate versus phosphonate linkages. Journal of Physical Chemistry B, 2006, 110(17): 8740–8749

[44] Johansson V, Gibbings L E, Clarke T, Gorlov M, Andersson G G, Kloo L. On the correlation between dye coverage and photoelectrochemical performance in dye-sensitized solar cells. Journal of the Chemical Society, Faraday Transactions, 2014, 16: 711–718

[45] Khazraji A C, Hotchandani S, Das S, Kamat P V. Controlling dye (merocyanine-540) aggregation on nanostructured TiO₂ films. An organized assembly approach for enhancing the efficiency of photosensitization. Journal of Physical Chemistry B, 1999, 103(22): 4693–4700

[46] Nazeeruddin M K, Baker R H, Liska P, Grätzel M. Investigation of sensitizer adsorption and the influence of protons on current and voltage of a dye-sensitized nanocrystalline TiO₂ solar cell. Journal of Physical Chemistry B, 2003, 107(34): 8981–8987

[47] Kawano M, Nishiyama T, Ogomi Y, Pandey S S, Ma T, Hayase S. Relationship between diffusion of Co³⁺/Co²⁺ redox species in nanopores of porous titania stained with dye molecules, dye molecular structures, and photovoltaic performances. RSC Advances, 2015, 5(102): 83725–83731

[48] Franz R G. Comparisons of pKa and log P values of some carboxylic and phosphonic acids: synthesis and measurement. AAPS PharmSci, 2001, 3(2): 1–13

[49] Guerrero G, Alauzun J G, Granier M, Laurencin D, Mutin P H. Phosphonate coupling molecules for the control of surface/interface properties and the synthesis of nanomaterials. Dalton Transactions (Cambridge, England), 2013, 42(35): 12569–12585

Acknowledgments

One of the authors, SSP is thankful to the Japanese society for the promotion of science (JSPS) for the financial support by a grant-in-aid for scientific research C (Grant No. 18K05300) to carry out this research.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-021-2117-z and is accessible for authorized users.

RIGHTS & PERMISSIONS

2021 Higher Education Press