Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells

Harnessing solar energy is a key issue in solving the global energy challenge. The Sun's radiant energy can be converted into electricity by photovoltaics. One of the most promising, emerging PV technologies is the dye-sensitized solar cell. In order to develop this technology, understanding th...

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Päätekijä: Antila, Liisa
Muut tekijät: Faculty of Mathematics and Science, Matemaattis-luonnontieteellinen tiedekunta, University of Jyväskylä, Jyväskylän yliopisto
Aineistotyyppi: Väitöskirja
Kieli:eng
Julkaistu: 2013
Linkit: https://jyx.jyu.fi/handle/123456789/95477
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author Antila, Liisa
author2 Faculty of Mathematics and Science Matemaattis-luonnontieteellinen tiedekunta University of Jyväskylä Jyväskylän yliopisto
author_facet Antila, Liisa Faculty of Mathematics and Science Matemaattis-luonnontieteellinen tiedekunta University of Jyväskylä Jyväskylän yliopisto Antila, Liisa Faculty of Mathematics and Science Matemaattis-luonnontieteellinen tiedekunta University of Jyväskylä Jyväskylän yliopisto
author_sort Antila, Liisa
datasource_str_mv jyx
description Harnessing solar energy is a key issue in solving the global energy challenge. The Sun's radiant energy can be converted into electricity by photovoltaics. One of the most promising, emerging PV technologies is the dye-sensitized solar cell. In order to develop this technology, understanding the dynamics of charge separation and electron transfer reactions in the cell is of fundamental importance. In this thesis, rates of electron transfer in dye-sensitized titanium dioxide films and complete solar cells were investigated by means of transient absorption and transient emission spectroscopies, as well as with electrochemical impedance spectroscopy. The effect of altering electron transfer rates on the performance of the cells was monitored by recording the current-voltage response of the cells under simulated sunlight. Electron transfer from two ruthenium dyes to titanium dioxide film (electron injection) in neat solvent and in the presence of an iodide/triiodide electrolyte was studied by following the ultrafast temporal evolutions of the absorptions of oxidized dye and of injected electrons. Electron injection was found to be almost two orders of magnitude slower in the presence of the complete electrolyte compared to injection in neat solvent. Comparison of the transient absorption signals of the oxidized dye and injected electrons of the sensitized TiO2 films in contact with the I-/I3- electrolyte revealed the picosecond time scale of dye regeneration for the first time, twenty years after the invention of the cell. This observation also paves the way for understanding the detailed molecular mechanisms of the function of the electrolyte redox couple in the cell. Metal oxide barrier layers deposited on the nanocrystalline TiO2 film were studied as a means to improve cell performance. The desired effect of the barrier layer is to slow down recombination reactions while maintaining good electron injection efficiency. Barrier layers were prepared with atomic layer deposition for better controllability of layer thickness and morphology. Aluminum oxide was found to slow down injection more than recombination, which led to deterioration of cell performance. Hafnium oxide barriers up to four atomic layer cycles retarded injection much less than the corresponding aluminum oxide layers, and in practice, retained cell performance. According to this result, increasing hafnium oxide layer thickness and improving its penetration into TiO2 film would provide a means to improve cell performance. Surprisingly, a relatively thick (about 1nm) tantalum oxide coating resulted in enhancement of the injection efficiency and led to about a 10% increase in the current output of the cell. This finding was significant as no barrier layer on TiO2 so far has been reported to have shown an increase in injection efficiency. More interestingly, improved cell performance was obtained for the TiO2 film with only the top quarter of the film covered with tantalum oxide.
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The Sun's radiant energy can be converted into electricity by photovoltaics. One of the most promising, emerging PV technologies is the dye-sensitized solar cell. In order to develop this technology, understanding the dynamics of charge separation and electron transfer reactions in the cell is of fundamental importance. In this thesis, rates of electron transfer in dye-sensitized titanium dioxide films and complete solar cells were investigated by means of transient absorption and transient emission spectroscopies, as well as with electrochemical impedance spectroscopy. The effect of altering electron transfer rates on the performance of the cells was monitored by recording the current-voltage response of the cells under simulated sunlight. Electron transfer from two ruthenium dyes to titanium dioxide film (electron injection) in neat solvent and in the presence of an iodide/triiodide electrolyte was studied by following the ultrafast temporal evolutions of the absorptions of oxidized dye and of injected electrons. Electron injection was found to be almost two orders of magnitude slower in the presence of the complete electrolyte compared to injection in neat solvent. Comparison of the transient absorption signals of the oxidized dye and injected electrons of the sensitized TiO2 films in contact with the I-/I3- electrolyte revealed the picosecond time scale of dye regeneration for the first time, twenty years after the invention of the cell. This observation also paves the way for understanding the detailed molecular mechanisms of the function of the electrolyte redox couple in the cell. Metal oxide barrier layers deposited on the nanocrystalline TiO2 film were studied as a means to improve cell performance. The desired effect of the barrier layer is to slow down recombination reactions while maintaining good electron injection efficiency. Barrier layers were prepared with atomic layer deposition for better controllability of layer thickness and morphology. Aluminum oxide was found to slow down injection more than recombination, which led to deterioration of cell performance. Hafnium oxide barriers up to four atomic layer cycles retarded injection much less than the corresponding aluminum oxide layers, and in practice, retained cell performance. According to this result, increasing hafnium oxide layer thickness and improving its penetration into TiO2 film would provide a means to improve cell performance. Surprisingly, a relatively thick (about 1nm) tantalum oxide coating resulted in enhancement of the injection efficiency and led to about a 10% increase in the current output of the cell. This finding was significant as no barrier layer on TiO2 so far has been reported to have shown an increase in injection efficiency. More interestingly, improved cell performance was obtained for the TiO2 film with only the top quarter of the film covered with tantalum oxide.", "language": "en", "element": "description", "qualifier": "abstract", "schema": "dc"}, {"key": "dc.description.provenance", "value": "Submitted by Harri Hirvi (hirvi@jyu.fi) on 2024-06-04T08:42:15Z\r\nNo. of bitstreams: 0", "language": "en", "element": "description", "qualifier": "provenance", "schema": "dc"}, {"key": "dc.description.provenance", "value": "Made available in DSpace on 2024-06-04T08:42:15Z (GMT). No. of bitstreams: 0\r\n Previous issue date: 2013", "language": "en", "element": "description", "qualifier": "provenance", "schema": "dc"}, {"key": "dc.format.mimetype", "value": "application/pdf", "language": null, "element": "format", "qualifier": "mimetype", "schema": "dc"}, {"key": "dc.language.iso", "value": "eng", "language": null, "element": "language", "qualifier": "iso", "schema": "dc"}, {"key": "dc.relation.ispartofseries", "value": "Research report / Department of Chemistry, University of Jyv\u00e4skyl\u00e4", "language": null, "element": "relation", "qualifier": "ispartofseries", "schema": "dc"}, {"key": "dc.relation.haspart", "value": "<b>Artikkeli I:</b> Antila, L., Myllyperki\u00f6, P., Mustalahti, S., Lehtivuori, H., & Korppi-Tommola, J. (2014). Injection and Ultrafast Regeneration in Dye-Sensitized Solar Cells. <i>Journal of Physical Chemistry C, 118(15), 7772-7780.</i> DOI: <a href=\"https://doi.org/10.1021/jp4124277\"target=\"_blank\"> 10.1021/jp4124277</a>", "language": "", "element": "relation", "qualifier": "haspart", "schema": "dc"}, {"key": "dc.relation.haspart", "value": "<b>Artikkeli II:</b> Antila, L., Heikkil\u00e4, M. J., Lehtovuori, V., Kemell, M., Myllyperki\u00f6, P., Leskel\u00e4, M., & Korppi-Tommola, J. (2010). Suppression of forward electron injection from Ru(dcbpy)2(NCS)2 to nanocrystalline TiO2 film as a result of interfacial Al2O3 barrier layer prepared with atomic layer deposition. <i>Journal of Physical Chemistry Letters, 1, 536-539.</i> DOI: <a href=\"https://doi.org/10.1021/jz9003075\"target=\"_blank\"> 10.1021/jz9003075</a>", "language": "", "element": "relation", "qualifier": "haspart", "schema": "dc"}, {"key": "dc.relation.haspart", "value": "<b>Artikkeli III:</b> Antila, L., Heikkil\u00e4, M. J., M\u00e4kinen, V., Humalam\u00e4ki, N., Laitinen, M., Linko, V., Jalkanen, P., Toppari, J., Aumanen, V., Kemell, M., Myllyperki\u00f6, P., Honkala, K., H\u00e4kkinen, H., Leskel\u00e4, M., & Korppi-Tommola, J. (2011). ALD Grown Aluminum Oxide Submonolayers in Dye-Sensitized Solar Cells: The Effect on Interfacial Electron Transfer and Performance. <i>The Journal of Physical Chemistry C, 115(33), 16720-16729. </i> DOI: <a href=\"https://doi.org/10.1021/jp204886n\"target=\"_blank\"> 10.1021/jp204886n </a>", "language": "", "element": "relation", "qualifier": "haspart", "schema": "dc"}, {"key": "dc.rights", "value": "In Copyright", "language": null, "element": "rights", "qualifier": null, "schema": "dc"}, {"key": "dc.title", "value": "Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells", "language": null, "element": "title", "qualifier": null, "schema": "dc"}, {"key": "dc.type", "value": "doctoral thesis", "language": null, "element": "type", "qualifier": null, "schema": "dc"}, {"key": "dc.identifier.urn", "value": "URN:ISBN:978-952-86-0223-1", "language": null, "element": "identifier", "qualifier": "urn", "schema": "dc"}, {"key": "dc.contributor.faculty", "value": "Faculty of Mathematics and Science", "language": "en", "element": "contributor", "qualifier": "faculty", "schema": "dc"}, {"key": "dc.contributor.faculty", "value": "Matemaattis-luonnontieteellinen tiedekunta", "language": "fi", "element": "contributor", "qualifier": "faculty", "schema": "dc"}, {"key": "dc.contributor.organization", "value": "University of Jyv\u00e4skyl\u00e4", "language": "en", "element": "contributor", "qualifier": "organization", "schema": "dc"}, {"key": "dc.contributor.organization", "value": "Jyv\u00e4skyl\u00e4n yliopisto", "language": "fi", "element": "contributor", "qualifier": "organization", "schema": "dc"}, {"key": "dc.type.coar", "value": "http://purl.org/coar/resource_type/c_db06", "language": null, "element": "type", "qualifier": "coar", "schema": "dc"}, {"key": "dc.relation.issn", "value": "0357-346X", "language": null, "element": "relation", "qualifier": "issn", "schema": "dc"}, {"key": "dc.relation.numberinseries", "value": "no 171.", "language": null, "element": "relation", "qualifier": "numberinseries", "schema": "dc"}, {"key": "dc.rights.accesslevel", "value": "openAccess", "language": null, "element": "rights", "qualifier": "accesslevel", "schema": "dc"}, {"key": "dc.type.publication", "value": "doctoralThesis", "language": null, "element": "type", "qualifier": "publication", "schema": "dc"}, {"key": "dc.format.content", "value": "fulltext", "language": null, "element": "format", "qualifier": "content", "schema": "dc"}, {"key": "dc.rights.url", "value": "https://rightsstatements.org/page/InC/1.0/", "language": null, "element": "rights", "qualifier": "url", "schema": "dc"}, {"key": "dc.date.digitised", "value": "2024", "language": null, "element": "date", "qualifier": "digitised", "schema": "dc"}, {"key": "dc.type.okm", "value": "G4", "language": null, "element": "type", "qualifier": "okm", "schema": "dc"}]
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spellingShingle Antila, Liisa Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells
title Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells
title_full Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells
title_fullStr Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells
title_full_unstemmed Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells
title_short Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells
title_sort spectroscopic studies of electron transfer reactions at the photoactive electrode of dye sensitized solar cells
title_txtP Spectroscopic studies of electron transfer reactions at the photoactive electrode of dye-sensitized solar cells
url https://jyx.jyu.fi/handle/123456789/95477 http://www.urn.fi/URN:ISBN:978-952-86-0223-1
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