monovalent-cation-doping-ch3nh3pbi3-for-efficient-perovskite-solar

Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical ...

University of Cambridge

The synthesis, characterization, and device studies of poly(benzobisoxazole imide)s containing perylene or naphthalene units in an alternating fashion with the oxazole unit are described. Photoinduced energy transfer and charge separation were studied in methanesulfonic acid (MSA) solution via absorption, excitation, and steady-state fluorescence studies. Excitation of the bisoxazole moiety resulted in enhanced emission from the perylene bisimide unit as a result of FRET (Förster resonance energy transfer). The influence of the imide substitution into the linear chain of poly(benzobisoxazole) (PBO) on its solid-state packing was examined by wide-angle X-ray diffraction (WXRD) analysis. Bottom contact field effect transistors (FET) based on thermally annealed polymer films were fabricated and studied. The polymers showed n-type charge transport and current modulation with an on/off ratio greater than 10(2). It was observed that the FETs consisting of the random copolymer of bisoxazole containing both perylene as well as naphthalene bisimide units had higher performance parameters such as better mobility (μ(e)) and I(on)/I(off) ratio compared to those of the pristine systems.

n-Type field effect transistors based on rigid rod and liquid crystalline alternating copoly(benzobisoxazole) imides containing perylene and/or naphthalene.

We present here the physicochemical characterization of a series of D-A-D type molecules which comprise benzooxadiazole (BDO) and benzothiadiazole (BDT) core symmetrically linked to two aromatic-heterols (furan (F), thiophene (T) and selenophene (Se)) at 4 and 7-positions. The molecular structures of four compounds 2 (T-BDO-T), 3 (Se-BDO-Se), 5 (T-BDT-T), and 6 (Se-BDT-Se) were determined by single-crystal X-ray diffraction. The combination of chalcogen atoms of benzochalcogenadiazole and chalcogenophene in D-A-D molecules has significant impact on their molecular packing in crystal structures. Structural analyses and theoretical calculations showed that all the molecules are nearly planar. Crystal structures of 2, 3, 5, and 6 showed significant short range interactions such as π···π, CH···π, S···π, Se···π, N···H, O···H, S···H, Se···H, S···O, and Se···N interactions, which influence crystal packing and orientation of the capped aromatic-heterol rings with respect to the central BDO or BDT unit. The π-stacking interactions have been observed via intermolecular overlap of the donor with acceptor units of the adjacent molecules which facilitate the charge transport process. Good thermal stability and solubility in common organic solvents make them good candidate for flexible electronics. Interestingly, the molecules 2, 3, and 6 have the propensity to form ordered crystallites when sheared during the drying process in the thin films. Devices based on these solution processable all organic FETs demonstrated hole mobility as high as 0.08 cm(2) V(-1) s(-1) and Ion/Ioff ratio of 10(4).

Solution processable benzooxadiazole and benzothiadiazole based D-A-D molecules with chalcogenophene: field effect transistor study and structure property relationship.

A new thiophene-based salphen-type ligand, 1, and its Cu(II) and Zn(II) complexes, 1·Cu and 1·Zn·MeOH, were designed and synthesized. These metal organic complexes (MOCs), with ultra-close π-stacking interactions were explored as a novel class of active materials for organic field effect transistors (OFETs). The top-contact bottom gated OFETs fabricated from solution-processed thin films of 1·Cu and 1·Zn·MeOH exhibited excellent p-type mobilities (up to 0.7 and 1.5 cm(2) V(-1) s(-1), respectively).

Zn(II) and Cu(II) complexes of a new thiophene-based salphen-type ligand: solution-processable high-performance field-effect transistor materials.

While the mechanism of self-assembly of π-conjugated molecules has been well studied to gain control over the structure and functionality of supramolecular polymers, the intermolecular interactions underpinning it are poorly understood. Here, we study the mechanism of self-assembly of perylene bisimide derivatives possessing dipolar carbonate groups as linkers. It was observed that the combination of carbonate linkers and cholesterol/dihydrocholesterol self-assembling moieties led to a cooperative mechanism of self-assembly. Atomistic molecular dynamics simulations of an assembly in explicit solvent strongly suggest that the dipole-dipole interaction between the carbonate groups imparts a macro-dipolar character to the assembly. This is confirmed experimentally through the observation of a significant polarization in the bulk phase for molecules following a cooperative mechanism. The cooperativity is attributed to the presence of dipole-dipole interaction in the assembly. Thus, anisotropic long-range intermolecular interactions such as dipole-dipole interaction can serve as a way to obtain cooperative self-assembly and aid in rationalizing and predicting the mechanisms in various synthetic supramolecular polymers.

Dipole-moment-driven cooperative supramolecular polymerization.

The possibility of designing programmable thin-film supramolecular structures with spontaneous polarization widens the utility of facile supramolecular chemistry. Although a range of low molecular mass molecular single crystals has been shown to exhibit ferroelectric polarization, demonstration of stimuli-responsive, thin-film, solution-processable supramolecular ferroelectric materials is rare. We introduce aromatic π-electron donor-acceptor molecular systems responsive to multiple stimuli that undergo supramolecular chiral mixed-stack charge-transfer (CT) coassembly through the tweezer-inclusion-sandwich process supported by hydrogen-bonding interactions. The structural synergy originating from hydrogen-bonding and chiral CT interactions resulted in the development of spontaneous unidirectional macroscopic polarization in the crystalline nanofibrous hydrogel network, under ambient conditions. Moreover, the tunability of these interactions with optical, mechanical, thermal, and electrical stimuli allowed the design of multistate thin-film memory devices. Our design strategy of the supramolecular motif is expected to help the development of new molecular engineering strategies for designing potentially useful smart multicomponent organic electronics.

Multi-Stimuli-Responsive Charge-Transfer Hydrogel for Room-Temperature Organic Ferroelectric Thin-Film Devices.

We report on the optimization of the interfacial properties of titania in mesoscopic CH3NH3PbI3 solar cells. Modification of the mesoporous TiO2 film by TiCl4 treatment substantially reduced the surface traps, as is evident from the sharpness of the absorption edge with a significant reduction in Urbach energy (from 320 to 140 meV) determined from photothermal deflection spectroscopy, and led to an order of magnitude enhancement in the bulk electron mobility and corresponding decrease in the transport activation energy (from 170 to 90 meV) within a device. After optimization of the photoanode-perovskite interface using various sizes of TiO2 nanoparticles, the best photovoltaic efficiency of 16.3% was achieved with the mesoporous TiO2 composed of 36 nm sized nanoparticles. The improvement in device performance can be attributed to the enhanced charge collection efficiency that is driven by improved charge transport in the mesoporous TiO2 layer. Also, the decreased recombination at the TiO2-perovskite interface and better perovskite coverage play important roles.

Impact of a Mesoporous Titania-Perovskite Interface on the Performance of Hybrid Organic-Inorganic Perovskite Solar Cells.

n-channel organic semiconductors are prone to oxidation upon exposed to ambient conditions. Herein, we report design and synthesis of diketopyrrolopyrrole (DPP)-based oligomers for ambipolar organic thin-film transistors (OFETs) with excellent air and bias stability at ambient conditions. The cyclic voltammetry measurements reveal exceptional electrochemical stability during the redox cycle of oligomers. Structural properties including aggregation, crystallinity, and morphology in thin film were investigated by UV-visible spectroscopy, atomic force microscopy (AFM), thin-film X-ray diffraction (XRD), and grazing incidence small-angle X-ray scattering (GISAXS) measurements. AFM reveals morphological changes induced by different processing conditions whereas GISAXS measurements show an increase in the population of face-on oriented crystallites in films subjected to a combination of solvent and thermal treatments. These measurements also highlight the significance of chalcogen atom from sulfur to selenium on the photophysical, optical, electronic, and solid-state properties of DPP-DPP oligomers. Charge carrier mobilities of the oligomers were investigated by fabricating top-gate bottom-contact (TG-BC) thin-film transistors by annealing the thin films under various conditions. Combined solvent and thermal annealing of DPP-DPP oligomer thin films results in consistent electron mobilities as high as ∼0.2 cm(2) V(-1) s(-1) with an on/off ratio exceeding 10(4). Field-effect behavior was retained for up to ∼4 weeks, which illustrates remarkable air and bias stability. This work paves the way toward the development of n-channel DPP-DPP-based oligomers exhibiting retention of field-effect behavior with superior stability at ambient conditions.

Air-Stable n-channel Diketopyrrolopyrrole-Diketopyrrolopyrrole Oligomers for High Performance Ambipolar Organic Transistors.

Reliable and ultrasensitive detection of mercury ions is of paramount importance for toxicology assessment, environmental protection, and human health. Herein, we present a novel optoelectronic approach based on nanoarchitectonics of small-molecule templated DNA system that consists of an adenine (A)-conjugated small organic semiconductor (BNA) and deoxyribo-oligothymidine (dTn). This mutually templated dynamic chiral coassembly system (BNAn-dTn) with tunable chiroptical, morphological, and electrical properties is tapped in to enable ultrasensitive and selective detection of inorganic and organometallic mercury in water. We observe a rapid transformation of the BNAn-dTn coassembly into a metallo-DNA duplex [dT-Hg-dT]n in the presence of mercury, which is utilized for a chiro-optical and conductivity-based rapid and subnanomolar sensitivity (≥0.1 nM, 0.02 ppb) to mercury ions in water (∼100 times lower than United States Environmental Protection Agency tolerance limit). This ultrasensitive detection of inorganic and organometallic mercury is driven by a novel chemical design principle that allows strong mercury thymine interaction. This study is anticipated to inspire the development of future templated DNA nanotechnology-based optoelectronic devices for the rapid and ultrasensitive detection of numerous other toxic analytes.

Nanoarchitectonics of Small Molecule and DNA for Ultrasensitive Detection of Mercury.

Fundamental understanding of the charge transport physics of hybrid lead halide perovskite semiconductors is important for advancing their use in high-performance optoelectronics. We use field-effect transistors (FETs) to probe the charge transport mechanism in thin films of methylammonium lead iodide (MAPbI3). We show that through optimization of thin-film microstructure and source-drain contact modifications, it is possible to significantly minimize instability and hysteresis in FET characteristics and demonstrate an electron field-effect mobility (μFET) of 0.5 cm(2)/Vs at room temperature. Temperature-dependent transport studies revealed a negative coefficient of mobility with three different temperature regimes. On the basis of electrical and spectroscopic studies, we attribute the three different regimes to transport limited by ion migration due to point defects associated with grain boundaries, polarization disorder of the MA(+) cations, and thermal vibrations of the lead halide inorganic cages.

Article	Year
n-Type field effect transistors based on rigid rod and liquid crystalline alternating copoly(benzobisoxazole) imides containing perylene and/or naphthalene. The journal of physical chemistry. B\| PubMed ID: 21090774	2010
Solution processable benzooxadiazole and benzothiadiazole based D-A-D molecules with chalcogenophene: field effect transistor study and structure property relationship. ACS applied materials & interfaces\| PubMed ID: 24237045	2013
Zn(II) and Cu(II) complexes of a new thiophene-based salphen-type ligand: solution-processable high-performance field-effect transistor materials. Chemical communications (Cambridge, England)\| PubMed ID: 24848721	2014
Dipole-moment-driven cooperative supramolecular polymerization. Journal of the American Chemical Society\| PubMed ID: 25756951	2015
Multi-Stimuli-Responsive Charge-Transfer Hydrogel for Room-Temperature Organic Ferroelectric Thin-Film Devices. Journal of the American Chemical Society\| PubMed ID: 27305598	2016
Impact of a Mesoporous Titania-Perovskite Interface on the Performance of Hybrid Organic-Inorganic Perovskite Solar Cells. The journal of physical chemistry letters\| PubMed ID: 27472458	2016
Air-Stable n-channel Diketopyrrolopyrrole-Diketopyrrolopyrrole Oligomers for High Performance Ambipolar Organic Transistors. ACS applied materials & interfaces\| PubMed ID: 27592516	2016
Nanoarchitectonics of Small Molecule and DNA for Ultrasensitive Detection of Mercury. ACS applied materials & interfaces\| PubMed ID: 27753489	2016
Understanding charge transport in lead iodide perovskite thin-film field-effect transistors. Science advances\| PubMed ID: 28138550	2017

Satyaprasad P. Senanayak

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