Biomimetic Dye Aggregate Solar Cells PDF
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Springer Theses Recognizing Outstanding Ph.D. Research Peter L. Marek Biomimetic Dye Aggregate Solar Cells Springer Theses Recognizing Outstanding Ph.D. Research For furthervolumes: http://www.springer.com/series/8790 Aims and Scope The series ‘‘Springer Theses’’ brings together a selection of the very best Ph.D. theses from around the world and across the physical sciences. Nominated and endorsed by two recognized specialists, each published volume has been selected for its scientific excellence and the high impact of its contents for the pertinent fieldofresearch.Forgreateraccessibilitytonon-specialists,thepublishedversions includeanextendedintroduction,aswellasaforewordbythestudent’ssupervisor explaining the special relevance of the work for the field. As a whole, the series will provide a valuable resource both for newcomers to the research fields described, and for other scientists seeking detailed background information on specialquestions.Finally,itprovidesanaccrediteddocumentationofthevaluable contributions made by today’s younger generation of scientists. Theses are accepted into the series by invited nomination only and must fulfill all of the following criteria • They must be written in good English. • ThetopicshouldfallwithintheconfinesofChemistry,Physics,EarthSciences, Engineering andrelatedinterdisciplinaryfieldssuchasMaterials, Nanoscience, Chemical Engineering, Complex Systems and Biophysics. • The work reported in the thesis must represent a significant scientific advance. • Ifthethesisincludespreviouslypublishedmaterial,permissiontoreproducethis must be gained from the respective copyright holder. • They must have been examined and passed during the 12 months prior to nomination. • Each thesis should include a foreword by the supervisor outlining the signifi- cance of its content. • The theses should have a clearly defined structure including an introduction accessible to scientists not expert in that particular field. Peter L. Marek Biomimetic Dye Aggregate Solar Cells Doctoral Thesis accepted by the Technical University of Darmstadt, Germany 123 Author Supervisors Dr. PeterL. Marek Prof.Dr. TeodorSilviu Balaban Instituteof Nanotechnology Chirosciences Team Karlsruhe Instituteof Technology Aix-Marseille Université Karlsruhe Marseille Germany France Prof.Dr.-Ing. HorstHahn InstituteforMaterials Science Technical University Darmstadt Darmstadt Germany ISSN 2190-5053 ISSN 2190-5061 (electronic) ISBN 978-3-319-00635-2 ISBN 978-3-319-00636-9 (eBook) DOI 10.1007/978-3-319-00636-9 SpringerChamHeidelbergNewYorkDordrechtLondon LibraryofCongressControlNumber:2013938756 (cid:2)SpringerInternationalPublishingSwitzerland2013 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodology now known or hereafter developed. Exempted from this legal reservation are brief excerpts in connection with reviews or scholarly analysis or material supplied specifically for the purposeofbeingenteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthe work. Duplication of this publication or parts thereof is permitted only under the provisions of theCopyright Law of the Publisher’s location, in its current version, and permission for use must always be obtained from Springer. Permissions for use may be obtained through RightsLink at the CopyrightClearanceCenter.ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Parts of this thesis have been published in the following journal articles: [1] Marek,P;Balaban,T.S.,BiomimetischeSolarzellen,Nachr.Chem.,2006,54, 1072-1077. [2] Balaban, T.S.; Marek, P.; Hedderich, R., Solarzellen zur künstlichen Photo- synthese nutzen Nanopartikel nach dem Vorbild grüner Schwefelbakterien, Nanotechnik, 2006, 6. [3] Huijser, A.; Marek, P.L.; Savenije, T.J.; Siebbeles, L.D.A.; Scherer, T.; Hauschild, R.; Szmytkowski, J.; Kalt, H.; Hahn, H.; Balaban, T.S., Photo- sensitization of TiO and SnO by Artificial Self-Assembling Mimics of the 2 2 Natural Chlorosomal Bacteriochlorophylls, J. Phys. Chem. C, 2007, 111, 11726-11733. [4] Marek,P.L.;Sieger,H.;Scherer,T.;Hahn,H.;Balaban,T.S.,Self-Assembled Chromophores Within Mesoporous Nanocrystalline TiO , Towards Biomi- 2 metic Solar Cells, J. Nanosci. Nanotechnol., 2009, 9, 3708-3713. [5] Marek, P.L.; Hahn, H.; Balaban, T.S., On the way to biomimetic dye aggre- gate solar cells, Energy Environ. Sci. 2011, 4, 2366-2378. [6] Chappaz-Gillot, C.; Marek, P.L.; Blaive, B.J.; Canard, G.; Bürck, J.; Garab, G.;Hahn,H.;Jávorfi,T.;Kelemen,L.;Krupke,R.;Mössinger,D.;Ormos,P.; Reddy,C.M.;Roussel,C.;Steinbach,G.;Szabó,M.;Ulrich,A.S.;Vanthuyne, N.; Vijayaraghavan, A.; Zupcanova, A.; Balaban, T.S., Anisotropic Organi- zationandMicroscopicManipulationofSelf-AssemblingSyntheticPorphyrin Microrods That Mimic Chlorosomes: Bacterial Light-Harvesting Systems, J. Am. Chem. Soc.2012, 134, 944-954. Supervisor’s Foreword PeterL.MarekperformedresearchattheInstituteforNanotechnology(INT,please see the list of Acronyms after the References) within the former Research Center (Forschungszentrum) Karlsruhe (FZK), now part of the Karlsruhe Institute of Technology (KIT) after unification with the University of Karlsruhe. He came to INT,firstforaDiplomaThesis,whichhesubmittedtotheTechnischeUniversität Darmstadt (TUD) and which was granted the highest mark. Encouraged by his mentorinDarmstadt,Prof.Dr.-Ing.HorstHahn,theManagingDirectoroftheINT, he joined the Balaban research group which was in the Department of Supramo- lecular Chemistry under the directorship of Prof. Dr., Dr. h. c. mult., Jean-Marie Lehn. Generous funding for assuring Peter’s doctoral fellowship was provided by theFZK,whiletheDeutscheForschungsgemeinschaft(DFG)providedextramural funding for equipment and consumables through the Center for Functional Nano- structures (CFN) at the UniversityofKarlsruhe. Our group at INT was performing mostly synthetic work on self-assembling chromophores which were the first fully synthetic molecules to mimic a very efficient natural light harvesting system of bacteriochlorophylls [1]. These are cousins of the very common plant chlorophylls, the most abundant pigments on earth. Peter, as trained material scientist at the TUD, embarked on an adventure which ended successfully with his Ph.D. defense, again judged with the highest mark,andwiththepresentthesis,whichyouasreaderareholdingorreadingona screen, and which was under the joint supervision by Balaban and Hahn. Peter’s research goal was to build solar cells which could function efficiently also under dim light, following the architectural principles of early photosynthetic bacteria. ThisbiomimeticapproachtosolarcellswasanovelendeavorspecifictoINTand FZK [2]. Peter brought to INT complementary knowledge and skills. While we providedthemoleculesthroughmulti-stepsyntheticsequences,Peterstudiedtheir self-assembly by several different nanoscopic and spectroscopic techniques, providing unprecedented insight into their morphologies and their incorporation into solar cells. Peter is a team player with an extremely friendly personality and withwhomunravelingunknownphenomenawasexcitingandstimulating.Hehas theabilitytoasktherightquestions,whichsometimescanbemoreimportantthan searching for their answers. vii viii Supervisor’sForeword The thesis is well written and, in my opinion, proves interdisciplinarity and a profoundknowledgeofsolarcellswithampleliteraturecitations.Thepresentation is augmented by a very useful collection of procedures to build dye-sensitized solar cells either with liquid electrolytes or as all-solid state. Peter had the per- severance to surpass multiple obstacles, which in the end might affect the overall performance and long-time stability of solar cells. He is also an inventor and an admirer of bionics, which is a field imitating Nature from an engineer’s per- spective[3].Whensomethingdidnotwork,helookedforthereasonsandtriedto understand, improve, and surmount the difficulties. An example is the device shown in Fig. 6.4, which he designed and built in collaboration with specialists from the machine workshop of the FZK. This device allows electrical contacting for 16 solar cells assembled in parallel, on one and the same substrate, but which couldhavebeendifferentlytreatedordoped.Theproblemweinitiallyencountered atthe LinzInstituteforOrganicSolarCells, wasthatuponcontacting, inorder to characterize solar cell performance, we short-circuited the sometimes brittle deposits [4]. Peter recognized this mechanical problem and brilliantly circum- vented it. He was one of the most frequent users of the scanning electron microscopes at INT, as their log books show. The reader can convince herself/ himself of the quality of Peter’s images and his skill at finding the right infor- mation. Sifting through thousands of images, out of which only a selected few have been in the end incorporated into publications or this thesis, was a huge effort, requiring discipline, a rigorous archiving system, and expert computer technologies. In collaboration with the group of Prof. Laurens Siebbeles and Dr. Tom SavenijeattheTechnicalUniversityinDelft,TheNetherlands,wecouldmeasure by time-resolved microwave conductivity the exciton diffusion in wide band gap semiconductors such as nanocrystalline titanium dioxide [5]. A thorough under- standing of the electron injection from the excited singlet state of chromophores, which behave collectively in such self-assemblies, into the conduction band of titania, was essential for optimizing cell dimensions and their nanomorphology. Furthermore, Peter could in collaboration with Dr. Ralph Krupke from INT per- form an unprecedented pulsed dielectrophoretic deposition of self-assembled chromophores onto microstructured electrodes [6]. This work, while in the reviewingprocess,receivedaveryfavorablereportstatingthatwhileforphysicists it is quite common to have multiple authorship, chemists are often reluctant to publish work with more than 20 authors. Peter is the second author of this J. Am. Chem. Soc. paper, with 21 co-authors, but with equal contribution with the first author Cyril Chappaz-Gillot, who was a Ph.D. Student in Marseille, where Silviu Balaban now heads the Chirosciences Department of the Institute of Molecular SciencesofMarseille(iSm2).Cyril,asyntheticchemisteducatedatthe‘‘Centrale Marseille,’’ earned the prize for the best fundamental science Ph.D. thesis of the C’NanointheregionProvenceAlpesCôted’AzurinFrance.Itisonlyfittingthat Peter, whohadthehindsighttowritehisPh.D.ThesisinEnglish, earnsthehonor topublishaSpringerThesis.MentionshouldbemadethatPeter wasawardedthe Supervisor’sForeword ix prizeforthebestoralpresentation‘‘OntheWaytowardsBiomimeticSolarCells’’ at the conference NanoSmat in Porto (Portugal) in 2007. Peter often made presentations for high-school students on solar cells, some- times with practical demonstrations of sensitizing titania with wild berry fruit juices.Hisvividtalksalwayslefta‘‘begeistert’’audience.Ifwedonotstartnowto educatethenextgenerationofpotentialresearchersonhowtosolvetheconversion of the rather dilute solar energy to concentrated electricity or fuels, by mid- century,ourcivilizationwillfaceahugeenergyproblem,especiallyifpopulation- rich Asian or Latin American countries reach the standard lifestyle of Europe, NorthAmericaorAustraliaandNewZealand.AswrittenbyVicenzoBalzani,the creator of the Bologna School on Photochemistry at Giacomo Ciamician’s Uni- versity: ‘‘The efficient production of solar fuels would represent the most impor- tant breakthrough of modern science’’ [7]. One anecdotal recollection from Peter’s early days at INT, was when one morning he very boldly put on a brilliant white new lab coat, upon my insisting that he perform a column chromatography on his ‘workhorse compound P2,’ as entitled in this thesis, which was formerly repeatedly synthesized by Anil Bhise, Dennis Mössinger, Chilla Malla Reddy, and more recently by Cyril. After explaining how chromatography works, showing Peter how the four rotary evaporators were functioning and where P2 was migrating on his column, I left himalonefortherestoftheday.Intheevening,aradiantPeter,inadirtylabcoat, completelyexhausted,showedmethepowderedcompoundinaflaskunderargon. He acknowledged this had been physically, his most exhausting day at INT. The result of my brutal throwing a non-swimmer into the pool and waiting for him to discover how to swim, which in Peter’s case translated into demanding from a non-trained chemist to prepare his object of study, was that Peter gained a deep respect for his beloved compound. It often happens that interdisciplinary work between chemists and physicists or materials scientists is hampered, less than by eachcommunity’sjargonorusageofdifferentunitsforenergythanbythefactthat physicists are using complicated instruments which need tuning, and several monthsofassemblyuntilexperimentscanbemeaningfullyperformed.Oncesuch a sophisticated experiment is up-and-running, physicists are in need of samples. Biologists, Biochemists or Nature are favored sample sources, in addition to commercial suppliers. However, it is often the chemist, who has an exact knowledge of how to handle the compound he synthesized, sometimes also in month-long synthetic sequences. The chemist knows his solvents and how to ultrapurifythese.Hecanavoidadventitiousimpurities,suchaseitherthestabilizer of the commercial solvent, or the phthalate plasticizer from the plastic cap of his vialthatcandrasticallyquenchphotoexcitedstates.Theperfectmarriageiswhena pure sample, inan ultra-pure medium, is putina well-tunedinstrument,allowing new knowledge to be gained, reproducibly. Peter learned this, probably the hard way,andjustasinTangohetooktwostepsback,twostepsinfront,buthavingfun most of the time. Another remark I would like to reiterate here from a previous Account [8] is that ‘‘Man-made devices are often better than natural ones for performance and x Supervisor’sForeword robustness.Typicalexamplesarewheelsandcogwheels,forwhichthereexistsno natural counterpart, but when coupled to an engine allow much higher velocities than any natural joint designed for movement. However, for light-harvesting one still awaits solutions. Learning from Nature’s architectural principles might help ustodeviseefficientdeviceswithrobustpigmentsallowingfunctioningatelevated temperatures (over 80 (cid:3)C in the deserts), for long periods (desirable are over 20 years of serviceless functioning), or under low-light illumination conditions.’’ Peter’s work, described in the following pages, is an effort in this direction. Hopefully,thisworkwillstimulateotherstojoininwhatwethinkisaworthwhile and stringently needed endeavor. Fromanotherpaperco-authoredwithPeterandHorstIcitehere:‘‘Organicand hybrid solar cell research is still an emerging field and is in a development stage where organic light emitting diodes were a decade ago. The problems then encountered with the stability of displays have been solved in the course of the past few years so that flat displays based on organics are now commonplace. We considerthatsimilarbreakthroughscanbeachievedforthesolarcellfield.Ideally, hybrid solar cells functioning with over 10 % power conversion efficiencies also under dim or diffuse illumination conditions should be attainable’’ [9]. Finally, citing from Giacomo Ciamician’s (father of photochemistry and a bionic’s pioneer) landmark Science paper in 1912: ‘‘On the arid lands there will spring up industrial colonies without smoke and without smokestacks; forests of glass tubes will extend over the plants and glass buildings will rise everywhere; inside of these will take place the photochemical process that hitherto have been the guarded secret of the plants, but that will have been mastered by human industry which will know how to make them bear even more abundant fruit than nature, for nature is not in a hurry and mankind is’’ [10]. Acknowledgment: Dr. Tobias Wassermann from Springer is thanked for his initiativeregardingPeter’sthesis,forhiscarefulproofreading,andpatienceforthe final manuscript. Marseille, April 2013 Prof. Dr. Teodor Silviu Balaban References 1. Balaban TS, Bhise AD, Fischer M, Linke-Schaetzel M, Roussel C, Vanthuyne N (2003) Controllingchiralityandopticalpropertiesofartificialantennasystemswithself-assembling porphyrins. Angew Chem Int Ed 42:2139–2144; 115:2189–2194 (Frontispiece illustration). doi:10.1002/anie.200250465 2.BhiseAD(2004)Abiomimeticapproachforsynthesizingartificiallight-harvestingsystems usingself-assembly,WissenschaftlicheBerichte,FZKA7174,ForschungszentrumKarslruhe in der Helmholtz-Gemeinschaft, 2005, ISSN 0947-8620. Ph.D. Defense on December 14, 2004
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