title: Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals.
abstract: Controllable doping of semiconductors is a fundamental technological requirement for electronic and optoelectronic devices. As intrinsic semiconductors, hybrid perovskites have so far been a phenomenal success in photovoltaics. The inability to dope these materials heterovalently (or aliovalently) has greatly limited their wider utilizations in electronics. Here we show an efficient in situ chemical route that achieves the controlled incorporation of trivalent cations (Bi(3+), Au(3+), or In(3+)) by exploiting the retrograde solubility behavior of perovskites. We term the new method dopant incorporation in the retrograde regime. We achieve Bi(3+) incorporation that leads to bandgap tuning (∼300 meV), 10(4) fold enhancement in electrical conductivity, and a change in the sign of majority charge carriers from positive to negative. This work demonstrates the successful incorporation of dopants into perovskite crystals while preserving the host lattice structure, opening new avenues to tailor the electronic and optoelectronic properties of this rapidly emerging class of solution-processed semiconductors.
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.|Department of Chemistry, Faculty of Science, Mansoura University , Mansoura, 35516, Egypt.
authors.forename: Ahmed L
authors.initials: AL
authors.lastname: Abdelhady
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Makhsud I
authors.initials: MI
authors.lastname: Saidaminov
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Banavoth
authors.initials: B
authors.lastname: Murali
authors.affiliation: Department of Electrical and Computer Engineering, University of Toronto , Toronto, Ontario M5S 3G4, Canada.
authors.forename: Valerio
authors.initials: V
authors.lastname: Adinolfi
authors.affiliation: Department of Electrical and Computer Engineering, University of Toronto , Toronto, Ontario M5S 3G4, Canada.
authors.forename: Oleksandr
authors.initials: O
authors.lastname: Voznyy
authors.affiliation: SABIC Corporate Research and Innovation Center, King Abdullah University of Science and Technology (KAUST) , Thuwal, 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Khabiboulakh
authors.initials: K
authors.lastname: Katsiev
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Erkki
authors.initials: E
authors.lastname: Alarousu
authors.affiliation: Department of Electrical and Computer Engineering, University of Toronto , Toronto, Ontario M5S 3G4, Canada.
authors.forename: Riccardo
authors.initials: R
authors.lastname: Comin
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Ibrahim
authors.initials: I
authors.lastname: Dursun
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Lutfan
authors.initials: L
authors.lastname: Sinatra
authors.affiliation: Department of Electrical and Computer Engineering, University of Toronto , Toronto, Ontario M5S 3G4, Canada.
authors.forename: Edward H
authors.initials: EH
authors.lastname: Sargent
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Omar F
authors.initials: OF
authors.lastname: Mohammed
authors.affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Osman M
authors.initials: OM
authors.lastname: Bakr