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Photovoltaic Device Comprising Perovskites Photovoltaische Vorrichtung Mit Perowskiten Dispositif Photovoltaïque Comprenant Des Pérovskites

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Photovoltaic Device Comprising Perovskites Photovoltaische Vorrichtung Mit Perowskiten Dispositif Photovoltaïque Comprenant Des Pérovskites (19) TZZ Z_T (11) EP 2 850 669 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: H01L 51/46 (2006.01) H01L 51/42 (2006.01) 24.02.2016 Bulletin 2016/08 H01G 9/20 (2006.01) (21) Application number: 13723945.5 (86) International application number: PCT/GB2013/051310 (22) Date of filing: 20.05.2013 (87) International publication number: WO 2013/171520 (21.11.2013 Gazette 2013/47) (54) PHOTOVOLTAIC DEVICE COMPRISING PEROVSKITES PHOTOVOLTAISCHE VORRICHTUNG MIT PEROWSKITEN DISPOSITIF PHOTOVOLTAÏQUE COMPRENANT DES PÉROVSKITES (84) Designated Contracting States: • AKIHIRO KOJIMA ET AL: "Organometal Halide AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Perovskites as Visible-Light Sensitizers for GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Photovoltaic Cells", JOURNAL OF THE PL PT RO RS SE SI SK SM TR AMERICAN CHEMICALSOCIETY, vol. 131, no. 17, 6 May 2009 (2009-05-06), pages 6050-6051, (30) Priority: 18.05.2012 GB 201208785 XP055045648, ISSN: 0002-7863, DOI: 13.06.2012 GB 201210487 10.1021/ja809598r • ZHANGL ET AL: "Dye-sensitized solar cells made (43) Date of publication of application: from BaTiO3-coated TiO2 nanoporous 25.03.2015 Bulletin 2015/13 electrodes", JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY, A: CHEMISTRY, (60) Divisional application: ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 197, 15198087.7 no.2-3, 25 June 2008(2008-06-25), pages 260-265, XP022649448, ISSN: 1010-6030, DOI: (73) Proprietor: Isis Innovation Limited 10.1016/J.JPHOTOCHEM.2008.01.002 [retrieved Oxford Oxfordshire OX2 7SG (GB) on 2008-01-12] • M. M. LEE ET AL: "Efficient Hybrid Solar Cells (72) Inventors: Based on Meso-Superstructured Organometal • SNAITH, Henry Halide Perovskites", SCIENCE, vol. 338, no. 6107, Oxford 4 October 2012 (2012-10-04), pages 643-647, Oxfordshire OX1 3PU (GB) XP055071972, ISSN: 0036-8075, DOI: • LEE, Michael 10.1126/science.1228604 Oxford • KITAZAWA N ET AL: "Optical properties of Oxfordshire OX1 3PU (GB) CH3NH3PbX3 (X = halogen) and their mixed-halide crystals", JOURNAL OF (74) Representative: Silcock, Peter James MATERIALS SCIENCE, KLUWER ACADEMIC J A Kemp PUBLISHERS, BO, vol. 37, no. 17, 1 September 14 South Square 2002 (2002-09-01), pages 3585-3587, Gray’s Inn XP019209691, ISSN: 1573-4803, DOI: London WC1R 5JJ (GB) 10.1023/A:1016584519829 • DAVID B. MITZI: "Synthesis, Structure, and (56) References cited: Properties of Organic-Inorganic Perovskites and WO-A1-2011/030117 WO-A2-2011/110869 Related Materials", PROGRESS IN INORGANIC US-A1- 2008 202 583 US-A1- 2010 294 350 CHEMISTRY,vol. 48, 1 January 1999 (1999-01-01), pages 1-121, XP055072062, Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 850 669 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 850 669 B1 • Liisa J. Antila ET AL: "ALD Grown Aluminum • KAY A ET AL: "ARTIFICIAL PHOTOSYNTHESIS. Oxide Submonolayers in Dye-Sensitized Solar 2. INVESTIGATIONS ON THE MECHANISM OF Cells: The Effect on Interfacial Electron Transfer PHOTOSENSITIZATIONOF NANOCRYSTALLINE andPerformance", Journal of Physical Chemistry TIO2 SOLAR CELLS BY CHLOROPHYLL C, vol. 115, no. 33, 22 July 2011 (2011-07-22), DERIVATIVES", JOURNAL OF PHYSICAL pages 16720-16729, XP055021948, ISSN: CHEMISTRY, AMERICAN CHEMICAL SOCIETY, 1932-7447, DOI: 10.1021/jp204886n US, vol. 98, no. 3, 20 January 1994 (1994-01-20), • Katherine E. Roelofs ET AL: "Effect of Al 2 O 3 pages 952-959, XP001149471, ISSN: 0022-3654, Recombination Barrier Layers Deposited by DOI: 10.1021/J100054A035 Atomic Layer Deposition in Solid-State CdS • Sara E. Koops ET AL: "Parameters Influencing Quantum Dot-Sensitized Solar Cells", Journal of the Efficiency of Electron Injection in Physical Chemistry C, vol. 117, no. 11, 25 Dye-Sensitized Solar Cells", Journal of the February 2013 (2013-02-25), pages 5584-5592, American Chemical Society, vol. 131, no. 13, 12 XP055148586, ISSN: 1932-7447, DOI: March 2009 (2009-03-12), pages 4808-4818, 10.1021/jp311846r XP055211184, ISSN: 0002-7863, DOI: • CHING LIN ET AL: ’Enhanced performance of 10.1021/ja8091278 dye-sensitized solar cells by an Al2O3 • Douglas R. Pernik ET AL: "Tracking the charge-recombination barrier formed by Adsorption and Electron Injection Rates of CdSe low-temperature atomic layer deposition’ Quantum Dots on TiO 2 : Linked versus Direct JOURNAL OF MATERIALS CHEMISTRY vol. 19, Attachment", Journal of Physical Chemistry C, no. 19, 01 January 2009, pages 2999 - 3003, vol. 115, no. 27, 14 July 2011 (2011-07-14), pages XP055148593 DOI: 10.1039/b819337a ISSN: 13511-13519, XP055048977, ISSN: 1932-7447, 0959-9428 DOI: 10.1021/jp203055d • PEACOCK P W ET AL: "Band offsets and • Jin-Wook Lee ET AL: "Quantum-Dot-Sensitized Schottky barrier heights of high dielectric Solar Cell with Unprecedentedly High constant oxides", JOURNAL OF APPLIED Photocurrent", Scientific Reports, vol. 3, 10 PHYSICS, AMERICAN INSTITUTE OF PHYSICS, January 2013 (2013-01-10), pages 1-8, US, vol. 92, no. 8, 15 October 2002 (2002-10-15), XP055211185, DOI: 10.1038/srep01050 pages4712-4721, XP012057483, ISSN: 0021-8979, • PALOMARES E ET AL: "Slow charge DOI: 10.1063/1.1506388 recombination in dye-sensitised solar cells • Henry J. Snaith ET AL: "Charge Generation and (DSSC) using Al2O3 coated nanoporous TiO2 Photovoltaic Operation of Solid-State films", CHEMICAL COMMUNICATIONS > Dye-Sensitized Solar Cells Incorporating a High CHEMICAL COMMUNICATIONS - CHEMCOM; Extinction Coefficient Indolene-Based [6015D], ROYAL SOCIETY OF CHEMISTRY, GB, Sensitizer", Advanced Functional Materials, vol. no. 14, 21 July 2002 (2002-07-21), pages 19, no. 11, 9 June 2009 (2009-06-09), pages 1464-1465, XP002283754, ISSN: 1359-7345, DOI: 1810-1818, XP055211182, ISSN: 1616-301X, DOI: 10.1039/B202515A 10.1002/adfm.200801751 • Michael D. Brown ET AL: "Surface Energy Relay Remarks: Between Cosensitized Molecules in Solid-State Thefile contains technical information submitted after Dye-Sensitized Solar Cells", Journal of Physical the application was filed and not included in this Chemistry C, vol. 115, no. 46, 17 October 2011 specification (2011-10-17), pages 23204-23208, XP055211183, ISSN: 1932-7447, DOI: 10.1021/jp207075z • KOOPS ET AL: "Transient emission studies of electron injection in dye sensitised solar cells", INORGANICACHIMICA ACTA, ELSEVIERBV, NL, vol. 361, no. 3, 20 December 2007 (2007-12-20), pages 663-670, XP022397484, ISSN: 0020-1693, DOI: 10.1016/J.ICA.2007.05.021 2 EP 2 850 669 B1 Description FIELD OF THE INVENTION 5 [0001] The invention relates to photovoltaic devices. BACKGROUND TO THE INVENTION [0002] Over recent years, the field of optoelectronic devices has developed rapidly, generating new and improved 10 devices that go some way to meeting the ever increasing global demand for low-carbon emissions. However, this demand cannot be met with the devices currently available. The issues with the currently-available technology are illustrated below, using the area of photovoltaic devices. [0003] The leading emerging technologies pushing to realise the ultimate goal of low cost solar power generation are dye-sensitized and organic photovoltaics. Dye-sensitized solar cells are composed of a mesoporous n-type metal oxide 15 photoanode, sensitized with organic or metal complex dye and infiltrated with a redox active electrolyte. [O’Regan, B. and M. Gratzel (1991). "A Low-Cost, High-Efficiency Solar-Cell Based On Dye-Sensitized Colloidal TiO2 Films." Nature 353(6346): 737-740.] They currently have certified power conversion efficiencies of 11.4% [Martin A. Green et al. Prog. Photovolt: Res. Appl. 2011; 19:565-572] and highest reported efficiencies are 12.3% [Aswani Yella, et al. Science 334, 629 (2011)]. The current embodiment of organic solar cells, is a nanostructured composite of a light absorbing and hole- 20 transporting polymer blended with a fullerene derivative acting as the n-type semiconductor and electron acceptor [Yu, G., J. Gao, et al. (1995) Science 270(5243): 1789-1791 and Halls, J. J. M., C. A. Walsh, et al. (1995) Nature 376(6540): 498-500]. The most efficient organic solar cells are now just over 10% [Green, M. A., K. Emery, et al. (2012). "Solar cell efficiency tables (version 39)." Progress in Photovoltaics 20(1): 12-20]. Beyond organic materials and dyes, there has been growing activity in the development of solution processable inorganic semiconductors for thin-film solar cells. 25 Specific interest has emerged in colloidal quantum dots, which now have verified efficiencies of over 5%, [Tang, J, et al. Nature Materials 10, 765-771 (2011)] and in cheaply processable thin film semiconductors grown from solution such as copper zinc tin sulphide selenide (CZTSS) which has generated a lot of excitement recently by breaking the 10% efficiency barrier in a low cost fabrication route. [Green, M. A., K. Emery, et al. (2012). "Solar cell efficiency tables (vers ion 39)." Progress in Photovoltaics 20(1): 12-20] The main issue currently with CZTSS system is that it is processed with 30 hydrazine, a highly explosive reducing agent [Teodor K. Todorov et al. Adv. Matter 2010, 22, E156-E159]. [0004] For a solar cell to be efficient, the first requirement is that it absorbs most of the sun light over the visible to near infrared region (300 to 900nm), and converts the light effectively to charge. Beyond this however, the charge needs to be collected at a high voltage in order to do useful work, and it is the generation of a high voltage with suitable current that is the most challenging aspect for the emerging solar technologies.
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