Beljonne, David

Boyen, Hans-Gerd

Conings, Bert

Grozema, Ferdinand C

Gélvez-Rueda, Maria C

Herckens, Roald

Lutsen, Laurence

Marchal, Nadège

Quarti, Claudio

Van Gompel, Wouter

Van Hecke, Kristof

Vanderzande, Dirk

Vandewal, Koen

Ghent University Academic Bibliography

roald.herckens@uhasselt.be | wouter.vangompel@uhasselt.be · www.uhasselt.beExtending the functionality of low-dimensional hybrid perovskitesthrough the incorporation of charge-transfer complexesWouter Van Gompela, Nadège Marchalb, María C. Gélvez-Ruedac, Koen Vandewald, Kristof VanHeckee, Hans-Gerd Boyend, Bert Coningsd, Roald Herckensa, Laurence Lutsend, Claudio Quartib,Ferdinand C. Grozemac, David Beljonneb, Dirk Vanderzandea,daHybrid Materials Design, Institute for Materials Research (IMO-IMOMEC), Hasselt University, Martelarenlaan 42, 3500 Hasselt, BelgiumbLaboratory for Chemistry of Novel Materials, University of Mons, Place du Parc, 20, B-7000 Mons, BelgiumcOptoelectronic Materials Section, Department of Chemical Engineering, Delft University of Technology, Van der Maasweg 9, 2629 HZ Delft, The NetherlandsdInstitute for Materials Research (IMO-IMOMEC), Hasselt University, Wetenschapspark 1, 3590 Diepenbeek, BelgiumeXStruct, Department of Chemistry, Ghent University, Krijgslaan 281-S3, B-9000 Ghent, BelgiumAcknowledgements ReferencesIntroductionwout .va gompel@uhasselt.be · Hasselt Univ rsity · https://www.uhasselt.be/HyMaD   ConclusionsWe showed that charge-transfer complexes (CTCs) can be incorporated into the organic layer of a 1D hybrid through self-assembly. The band gap of the 1D hybrid containing the CTC(~ 1.0 eV) is significantly red-shifted compared to the band gap of the equivalent free organic charge-transfer complex (~ 1.3 eV). Through ab initio modelling it is shown that this shift inband gap can mainly be explained by a templating effect of the inorganic lattice, which changes the stacking of the donor and acceptor molecules in the hybrid compared to the freecharge-transfer complex. The valence band edge (VBE) and conduction band edge (CBE) of the hybrid are respectively dominated by pyrene occupied orbitals and TCNQ empty orbitals.However, occupied states of the inorganic lattice are located in very close energy proximity to the VBE. The 1D hybrid possesses a higher photoconductivity than the free organic CTC.This hybrid represents the first of a new class of hybrids containing CTCs with the potential for a high compositional versatility and a wide range of optical and electronic properties.ConceptW.T.M.V.G. is an SB PhD fellow at FWO (Number 1S17516N), R. H. is a special research fund (BOF) doctoral (PhD) student atUHasselt/IMO. K. V. H. thanks the Hercules Foundation and the special research fund (BOF)–UGent for funding. The research leadingto these results in the TUDelft has received funding from the European Research Council Horizon 2020. The work from the Universityof Mons was supported by a 50-50 PhD funding for N.M. from the University of Mons, by the Interuniversity Attraction Pole program ofthe Belgian Referal Science Policy Office (PAI 6/27) and FNRS-F.R.S. Computational resources have been provided by theConsortium des Equipements de Calcul Intensif (CECI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS)and by the Walloon Region. C.Q. and D.B. are FNRS postdoctoral researcher and research director, respectively. Bart Ruttens andJan D'Haen (IMO-IMOMEC) are acknowledged for PXRD measurements.Low-dimensional hybrid perovskites are emerging as a promising class of materials for use in optoelectronic applications. A significant advantage of the low-dimensional hybrids over the currently more extensively studied 3D hybrid perovskites, is the greater compositional flexibility of the organic layer. The structuralconstraints on the organic cation are much more limited for low-dimensional hybrids compared to their 3D counterparts and a large variety of possible moleculesremains unexplored. An additional way to introduce functionality is through the use of intercalation. In this way, molecules that do not contain an ammoniumtethering group can be incorporated into the organic layer of the hybrids. Mitzi et al. intercalated hexafluorobenzene molecules into phenethylammonium based 2Dlayered perovskites using the fluoroaryl-aryl interactions.1 More recently, Smith et al. intercalated molecular iodine into hexylammonium based 2D layeredperovskites in order to decrease the electronic confinement in the layered perovskite.2We incorporate donor:acceptor charge-transfer complexes into the organic layer of low-dimensional hybrids.3,4 The organic layer of these hybrids contains donormolecules with an ammonium tethering group. Through self-assembly, small electron acceptor molecules intercalate into the organic layer. The structural, opticaland charge-transport properties of the hybrid are compared to the properties of the free organic donor:acceptor charge-transfer complex.1. D. B. Mitzi, D. R. Medeiros and P. R. L. Malenfant, Inorg. Chem., 2002, 41, 2134–2145.2. M. D. Smith, L. Pedesseau, M. Kepenekian, I. C. Smith, C. Katan, J. Even and H. I. Karunadasa, Chem. Sci., 2017, 8, 1960–1968.3. W. T. M. Van Gompel, R. Herckens, K. Van Hecke, B. Ruttens, J. D'Haen, L. Lutsen, D. Vanderzande, Chem. Commun., 2019, 55, 2481-2484.4. N. Marchal, W. T. M. Van Gompel, M. C. Gélvez-Rueda, K. Vandewal, K. Van Hecke, H.-G. Boyen, B. Conings, R. Herckens, L. Lutsen, C.Quarti, F. C. Grozema, D. Vanderzande, D. Beljonne, Chemistry of Materials, under revision.donor:acceptor                    PbI6 octahedracharge-transfer complexHybrid: (donor-CnH2n-NH3:acceptor)PbI3Comparison1D hybrid containing CT complex CT complex           Results750 1000 1250 1500PDS signal ~ absorbed photonswavelength (nm) (PyrC4:TCNQ 1:1)PbI3 crystal (pyrene:TCNQ 1:1) crystalVBECBEBGPDOS

Extending the functionality of low-dimensional hybrid perovskites through the incorporation of charge-transfer complexes

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Extending the functionality of low-dimensional hybrid perovskites through the incorporation of charge-transfer complexes

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