Morphology, photophysics and optoelectronics of P3HT nanoparticles and TiO2 nanorods composite

2017 ◽  
Vol 31 (16-19) ◽  
pp. 1744053 ◽  
Author(s):  
Wei-Long Xu ◽  
Hongchun Yuan ◽  
Jin Xiao ◽  
Chao Xiong ◽  
Xifang Zhu

Morphology and photophysics of polymers are critical to the performance of organic optoelectronics. In this work, poly(3-thiophene) (P3HT) nanoparticles were successfully fabricated by the miniemulsion and reprecipitation methods. The P3HT nanoparticles demonstrated uniform distribution with the domain size of [Formula: see text][Formula: see text]40 nm. The photophysics of P3HT nanoparticles was investigated by absorption and steady-state and time-resolved PL spectroscopy. P3HT nanoparticles showed more ordered and longer conjugation length than pristine P3HT. At the same time, P3HT nanoparticles showed aggregate species which are favorable for interchain charge transfer. The organic/inorganic hybrid photodetectors based on P3HT and TiO2 nanorods were fabricated. The superior performance of the photodetector based on P3HT nanoparticle and TiO2 nanorods comes from the efficient charge transfer and large donor/acceptor interface.

Author(s):  
Haofan Yang ◽  
Xiaobo Li ◽  
Reiner Sebastian Sprick ◽  
Andrew I. Cooper

A library of 237 organic binary/ternary nanohybrids consisting of conjugated polymers donors and both fullerene and non-fullerene molecular acceptors was prepared and screened for sacrificial photocatalytic hydrogen evolution. These donor-acceptor nanohybrids (DANHs) showed significantly enhanced hydrogen evolution rates compared with the parent donor or acceptor compounds. DANHs of <a></a><a>a polycarbazole</a>-based donor combined with a methanofullerene acceptor (PCDTBT/PC<sub>60</sub>BM) showed a high hydrogen evolution rate of 105.2 mmol g<sup>-1</sup> h<sup>-1</sup> under visible light (λ > 420 nm). This DANH photocatalyst produced 5.9 times more hydrogen than a sulfone-containing polymer (P10) under the same conditions, which is one of the most efficient organic photocatalysts reported so far. An apparent quantum yield of hydrogen evolution of 3.0 % at 595 nm was measured for this DANH. The photocatalytic activity of the DANHs, which in optimized cases reached 179.0 mmol g<sup>-1</sup> h<sup>-1</sup>, is attributed to efficient charge transfer at the polymer donor/molecular acceptor interface. We also show that ternary donor<sub>A</sub>-donor<sub>B</sub>-acceptor nanohybrids can give higher activities than binary donor-acceptor hybrids in some cases.


2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Ture F. Hinrichsen ◽  
Christopher C. S. Chan ◽  
Chao Ma ◽  
David Paleček ◽  
Alexander Gillett ◽  
...  

Abstract Organic solar cells based on non-fullerene acceptors can show high charge generation yields despite near-zero donor–acceptor energy offsets to drive charge separation and overcome the mutual Coulomb attraction between electron and hole. Here, we use time-resolved optical spectroscopy to show that free charges in these systems are generated by thermally activated dissociation of interfacial charge-transfer states that occurs over hundreds of picoseconds at room temperature, three orders of magnitude slower than comparable fullerene-based systems. Upon free electron–hole encounters at later times, both charge-transfer states and emissive excitons are regenerated, thus setting up an equilibrium between excitons, charge-transfer states and free charges. Our results suggest that the formation of long-lived and disorder-free charge-transfer states in these systems enables them to operate closely to quasi-thermodynamic conditions with no requirement for energy offsets to drive interfacial charge separation and achieve suppressed non-radiative recombination.


RSC Advances ◽  
2016 ◽  
Vol 6 (62) ◽  
pp. 57293-57305 ◽  
Author(s):  
Jian-Yong Liu ◽  
Xue-Ni Hou ◽  
Ye Tian ◽  
Lizhi Jiang ◽  
Shuiquan Deng ◽  
...  

The bis(triphenylamine)–BODIPY–C60 artificial photosynthetic system has been prepared and studied for its photoinduced transfer processes in polar and nonpolar solvents using various steady-state and time-resolved spectroscopic techniques.


Author(s):  
TORSTEN OEKERMANN ◽  
DERCK SCHLETTWEIN ◽  
NILS I. JAEGER ◽  
DIETER WÖHRLE

The influence of electron-withdrawing substituents on the photoelectrochemical properties of phthalocyanines is shown in a comparison between hexadecafluorophthalocyaninatozinc(II) ( F 16 PcZn ) and the unsubstituted phthalocyaninatozinc(II) ( PcZn ). The role of surface states in the photoelectrochemistry of both materials has been investigated by time-resolved photocurrent measurements in the millisecond range. The charging and discharging of surface states could clearly be seen as spikes at the beginning and the end of illumination. Surface states were filled with photogenerated electrons at PcZn and with photogenerated holes at F 16 PcZn . In the steady state under illumination only cathodic photocurrents were detected at PcZn , while at F 16 PcZn both cathodic and anodic photocurrents were observed. An adsorption step of electroactive species prior to the charge transfer was derived from the dependence of the steady state photocurrents on the electrolyte concentration for both materials. The concentration dependence of the charging and discharging currents, however, showed that charge transfer from surface states to the electrolyte occurs at PcZn , while at F 16 PcZn the surface states only represent recombination centres.


2003 ◽  
Vol 81 (6) ◽  
pp. 567-574
Author(s):  
Dustin Levy ◽  
Bradley R Arnold

Time-resolved linear dichroism spectroscopy has been used to study the influence of solvent on the charge transfer complex formed between hexamethylbenzene and 1,2,4,5-tetracyanobenzene. It was shown that cyano-substituted solvents induce a 1500 cm–1 increase in the charge transfer transition energies relative to those observed in chlorinated solvents. Furthermore, the angle between the charge transfer absorption transition moments and the photochemically produced radical anion absorption transition moment, after relaxation, has been measured for this complex in several solvents. A simple model was used to correlate the angles measured using time-resolved linear dichroism spectroscopy with the extent of localized excitation mixed into the charge transfer transitions. These measurements reveal that different charge transfer transitions borrow intensity from the localized excitation to different extents. By using different excitation wavelengths, the partitioning of the borrowed intensity among the charge transfer transitions of this complex could be evaluated for the first time.Key words: 1,2,4,5-tetracyanobenzene, hexamethylbenzene, donor–acceptor complex, photoinduced electron transfer, photoselection.


2021 ◽  
Author(s):  
Can Li ◽  
Ruotian Chen ◽  
Zefeng Ren ◽  
Yu Liang ◽  
Thomas Dittrich ◽  
...  

Abstract Water-splitting reactions using photocatalyst particles are promising routes for solar fuel production1-4. Photoinduced charge transfer from a photocatalyst to catalytic surface sites is key in ensuring photocatalytic efficiency5; however, it is challenging to understand this process, which spans a wide spatiotemporal range from nanometers to micrometers and from femtoseconds to seconds6-8. Although the steady-state charge distribution on single photocatalyst particles has been mapped using microscopic techniques9-11 and the averaged charge transfer dynamics in photocatalyst aggregations have been revealed via time-resolved spectroscopy12,13, spatiotemporally evolving charge transfer processes in single photocatalyst particles cannot be tracked, and the mechanism of charge transfer is unknown. Here, we report spatiotemporally resolved surface photovoltage measurements on Cu2O photocatalyst particles to map complete charge transfer processes throughout the femtosecond to second time scale at the single-particle level. We found that photogenerated electrons are transferred to the catalytic surface ballistically on a sub-picosecond timescale and are retained at this location for the duration, whereas photogenerated holes are transferred to a spatially separated surface and stabilized via selective trapping on a microsecond timescale. We demonstrate that these ballistic electron transfer and anisotropic trapping regimes, which challenge the classical perception of the drift–diffusion model, contribute to efficient charge separation in photocatalysis and improve the photocatalytic performance. We anticipate our findings to demonstrate the universality of other photoelectronic devices and facilitate the rational design of photocatalysts.


2019 ◽  
Author(s):  
Haofan Yang ◽  
Xiaobo Li ◽  
Reiner Sebastian Sprick ◽  
Andrew I. Cooper

A library of 237 organic binary/ternary nanohybrids consisting of conjugated polymers donors and both fullerene and non-fullerene molecular acceptors was prepared and screened for sacrificial photocatalytic hydrogen evolution. These donor-acceptor nanohybrids (DANHs) showed significantly enhanced hydrogen evolution rates compared with the parent donor or acceptor compounds. DANHs of <a></a><a>a polycarbazole</a>-based donor combined with a methanofullerene acceptor (PCDTBT/PC<sub>60</sub>BM) showed a high hydrogen evolution rate of 105.2 mmol g<sup>-1</sup> h<sup>-1</sup> under visible light (λ > 420 nm). This DANH photocatalyst produced 5.9 times more hydrogen than a sulfone-containing polymer (P10) under the same conditions, which is one of the most efficient organic photocatalysts reported so far. An apparent quantum yield of hydrogen evolution of 3.0 % at 595 nm was measured for this DANH. The photocatalytic activity of the DANHs, which in optimized cases reached 179.0 mmol g<sup>-1</sup> h<sup>-1</sup>, is attributed to efficient charge transfer at the polymer donor/molecular acceptor interface. We also show that ternary donor<sub>A</sub>-donor<sub>B</sub>-acceptor nanohybrids can give higher activities than binary donor-acceptor hybrids in some cases.


2020 ◽  
Vol 44 (11) ◽  
pp. 4376-4385 ◽  
Author(s):  
Pooja Daga ◽  
Prakash Majee ◽  
Debal Kanti Singha ◽  
Priyanka Manna ◽  
Sayani Hui ◽  
...  

A Co(ii)-based metal–organic compound exhibits luminescence turn-on by Al3+ and quenching by Fe3+ due to the formation of charge-transfer complexes/adducts.


2020 ◽  
Vol 21 (12) ◽  
pp. 4366
Author(s):  
Mario Gutiérrez ◽  
Lucie Duplouy-Armani ◽  
Lorenzo Angiolini ◽  
Mercedes Pintado-Sierra ◽  
Félix Sánchez ◽  
...  

The design of improved organic linkers for the further engineering of smarter metal–organic framework (MOF) materials has become a paramount task for a wide number of material scientists. In this report, a luminescent double-functionalized push–pull (electron donor–acceptor) archetype organic molecule, dimethyl 4-amino-8-cyanonaphthalene-2,6-dicarboxylate (Me2CANADC), has been synthesized and characterized. The optical steady-state properties of Me2CANADC are strongly influenced by the surrounding environment as a direct consequence of its strong charge transfer (CT) character. The relaxation from its first electronically excited singlet state follows a double pathway: (1) on one side deactivating from its local excited (LE) state in the sub-picosecond or picosecond time domain, and (2) on the other side undergoing an ultrafast intramolecular charge transfer (ICT) reaction that is slowing down in viscous solvents. The deactivation to the ground state of these species with CT character is the origin of the Me2CANADC luminescence, and they present solvent-dependent lifetime values ranging from 8 to 18 ns. The slow photodynamics of Me2CANADC unveils the coexistence of a non-emissive triplet excited state and the formation of a long-lived charge separated state (2 µs). These observations highlight the promising optical properties of Me2CANADC linker, opening a window for the design of new functional MOFs with huge potential to be applied in the fields of luminescent sensing and optoelectronics.


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