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1.
Efficient Iron Phosphide Catalyst as a Counter Electrode in Dye-Sensitized Solar Cells : article
Abdullah Yildiz, Takwa Chouki, Aycan Atli, Moussab Harb, Sammy W Verbruggen, Rajeshreddy Ninakanti, Saim Emin, 2021, original scientific article

Abstract: Developing an efficient material as a counter electrode (CE) with excellent catalytic activity, intrinsic stability, and low cost is essential for the commercial application of dye-sensitized solar cells (DSSCs). Transition metal phosphides have been demonstrated as outstanding multifunctional catalysts in a broad range of energy conversion technologies. Here, we exploited different phases of iron phosphide as CEs in DSSCs with an I–/I3–-based electrolyte. Solvothermal synthesis using a triphenylphosphine precursor as a phosphorus source allows to grow a Fe2P phase at 300 °C and a FeP phase at 350 °C. The obtained iron phosphide catalysts were coated on fluorine-doped tin oxide substrates and heat-treated at 450 °C under an inert gas atmosphere. The solar-to-current conversion efficiency of the solar cells assembled with the Fe2P material reached 3.96 ± 0.06%, which is comparable to the device assembled with a platinum (Pt) CE. DFT calculations support the experimental observations and explain the fundamental origin behind the improved performance of Fe2P compared to FeP. These results indicate that the Fe2P catalyst exhibits excellent performance along with desired stability to be deployed as an efficient Pt-free alternative in DSSCs.
Keywords: Iron phosphide, catalyst, counter electrode, dye-sensitized solar cell, solvothermal synthesis
Published in RUNG: 06.02.2023; Views: 1299; Downloads: 0
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2.
PHOTO-EXCITATION ENERGY INFLUENCE ON THE PHOTOCONDUCTIVITY OF ORGANIC SEMICONDUCTORS
Nadiia Pastukhova, 2018, doctoral dissertation

Abstract: In this work, we experimentally studied the influence of photoexcitation energy influence on the charge transport in organic semiconductors. Organic semiconductors were small molecules like corannulene, perylene and pentacene derivatives, polymers such as polythiophene and benzothiophene derivatives, and graphene, along with combinations of these materials in heterojunctions or composites. The first part of this study is focused on the photoexcitation energy influence on the transient photoconductivity of non-crystalline curved π-conjugated corannulene layers. The enhanced photoconductivity, in the energy range where optical absorption is absent, is deduced from theoretical predictions of corannulene gas-phase excited state spectra. Theoretical analysis reveals a consistent contribution involving transitions to Super Atomic Molecular Orbitals (SAMOs), a unique set of diffuse orbitals typical of curved π-conjugated molecules. More, the photoconductivity of the curved corannulene was compared to the π-conjugated planar N,N′-1H,1H- perfluorobutyldicyanoperylene-carboxydi-imide (PDIF-CN2), where the photoexcitation energy dependence of photocurrent closely follows the optical absorption spectrum. We next characterized charge transport in poly(3-hexylthiophene) (P3HT) layers deposited from solution. Our results indicate that time-of-flight (TOF) mobility depends on the photoexcitation energy. It is 0.4× 10 −3 cm 2 /Vs at 2.3 eV (530 nm) and doubles at 4.8 eV (260 nm). TOF mobility was compared to field-effect (FET) mobility of P3HT field-effect transistors (OFETs). The FET mobility was similar to the 2.3 eV excitation TOF mobility. In order to improve charge mobility, graphene nanoparticles were blended within a P3HT solution before the deposition. We found that the mobility significantly improves upon the addition of graphene nanoparticles of a weight ratio as low as 0.2 %. FET mobility increases with graphene concentration up to a value of 2.3× 10 −2 cm 2 /Vs at 3.2 %. The results demonstrate that phase segregation starts to influence charge transport at graphene concentration of 0.8 % and above. Hence, the graphene cannot form a bridged conduction channel between electrodes, which would cancel the semiconducting effect of the polymer composite. An alternative approach to enhance mobility is to optimize the molecular ordering of organic semiconductors. For that purpose, we studied an innovative nanomesh device. Free-standing nanomesh devices were used to form nanojunctions of N,N′- iiDioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires and crystalline bis(triisopropylsilylethinyl)pentacene (TIPS-PEN). We characterized the photocurrent response time of this novel nanomesh scaffold device. The photoresponse time depends on the photon energy. It is between 4.5 − 5.6 ns at 500 nm excitation wavelength and between 6.7 − 7.7 ns at 700 nm excitation wavelength. In addition, we found that thermal annealing reduces charge carrier trapping in crystalline nanowires. This confirms that the structural defects are crucial to obtaining high photon-to-charge conversion efficiency and subsequent transport from pn junction in heterostructured materials. Structural defects also influence the power conversion efficiency of organic heterostructured photovoltaics (OPVs). Anticipating that polymers with different backbone lengths produce different level of structural defects, we examined charge transport dependence on the molecular weight of poly[4,8-bis(5-(2- ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2- ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl] (PTB7-Th) from 50 kDa to 300 kDa. We found p-type hopping transport in PTB7-Th, characterized by 0.1 – 3× 10 −2 cm 2 /Vs mobility, which increases with temperature and electric field. The polymer molecular weight exhibits a non-trivial influence on charge transport. FET mobility in the saturation regime increases with molecular weight. A similar trend is observed in TOF mobility and FET mobility in the linear regime, except for the 100kDa polymer, which manifests in the highest mobility due to reduced charge trapping. The lowest trapping at the dielectric interface of OFET is observed at 200 kDa. In addition, the 200 kDa polymer exhibits the lowest activation energy of the charge transport. Although the 100 kDa polymer indicates the highest mobility, OPVs using the 200 kDa polymer exhibit the best performance in terms of power conversion efficiency.
Keywords: organic semiconductors, optical absorption spectroscopy, time-of-flight photoconductivity, transient photocurrent spectroscopy, organic thin film transistors, atomic force microscopy, superatomic molecular orbitals, pn heterojunction, organic nanowires, graphene, composites, charge mobility, charge trapping, temperature dependence, photodetector, photovoltaic, solar cell, organic electronics
Published in RUNG: 08.10.2018; Views: 5892; Downloads: 166
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