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2.
Molecules ; 26(4)2021 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-33672710

RESUMO

The presence of excited-states and charge-separated species was identified through UV and visible laser pump and visible/near-infrared probe femtosecond transient absorption spectroscopy in spin coated films of poly[N-9″-heptadecanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) nanoparticles and mesoparticles. Optical gain in the mesoparticle films is observed after excitation at both 400 and 610 nm. In the mesoparticle film, charge generation after UV excitation appears after around 50 ps, but little is observed after visible pump excitation. In the nanoparticle film, as for a uniform film of the pure polymer, charge formation was efficiently induced by UV excitation pump, while excitation of the low energetic absorption states (at 610 nm) induces in the nanoparticle film a large optical gain region reducing the charge formation efficiency. It is proposed that the different intermolecular interactions and molecular order within the nanoparticles and mesoparticles are responsible for their markedly different photophysical behavior. These results therefore demonstrate the possibility of a hitherto unexplored route to stimulated emission in a conjugated polymer that has relatively undemanding film preparation requirements.


Assuntos
Carbazóis/química , Nanopartículas/química , Polímeros/química , Compostos de Enxofre/química , Semicondutores
3.
Nanomaterials (Basel) ; 12(1)2021 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-35010034

RESUMO

The use of water-processable nanoparticles (WPNPs) is an emerging strategy for the processing of organic semiconducting materials into aqueous medium, dramatically reducing the use of chlorinated solvents and enabling the control of the nanomorphology in OPV active layers. We studied amphiphilic rod-coil block copolymers (BCPs) with a different chemical structure and length of the hydrophilic coil blocks. Using the BCPs blended with a fullerene acceptor material, we fabricated NP-OPV devices with a sustainable approach. The goal of this work is to clarify how the morphology of the nanodomains of the two active materials is addressed by the hydrophilic coil molecular structures, and in turn how the design of the materials affects the device performances. Exploiting a peculiar application of TEM, EFTEM microscopy on WPNPs, with the contribution of AFM and spectroscopic techniques, we correlate the coil structure with the device performances, demonstrating the pivotal influence of the chemical design over material properties. BCP5, bearing a coil block of five repeating units of 4-vinilpyridine (4VP), leads to working devices with efficiency comparable to the solution-processed ones for the multiple PCBM-rich cores morphology displayed by the blend WPNPs. Otherwise, BCP2 and BCP15, with 2 and 15 repeating units of 4VP, respectively, show a single large PCBM-rich core; the insertion of styrene units into the coil block of BCP100 is detrimental for the device efficiency, even if it produces an intermixed structure.

4.
Phys Chem Chem Phys ; 22(45): 26583-26591, 2020 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-33201972

RESUMO

Using ultrafast spectroscopy, we investigate the photophysics of water-processable nanoparticles composed of a block copolymer electron donor and a fullerene derivative electron acceptor. The block copolymers are based on a poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] rod, which is covalently linked with 2 or 100 hydrophilic coil units. In both samples the photogenerated excitons in the blend nanoparticles migrate in tens of ps to a donor/acceptor interface to be separated into free charges. However, transient absorption spectroscopy indicates that increasing the coil length from 2 to 100 units results in the formation of long living charge transfer states which reduce the charge generation efficiency. Our results shed light on the impact of rod-coil copolymer coil length on the blend nanoparticle morphology and provide essential information for the design of amphiphilic rod-coil block copolymers to increase the photovoltaic performances of water-processable organic solar cell active layers.

5.
Chem Sci ; 11(29): 7599-7608, 2020 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-33033610

RESUMO

The development of purely organic materials showing multicolor fluorescent and phosphorescent behaviour represents a formidable challenge in view of practical applications. Herein the rich photophysical behaviour of 3-(pyridin-2-yl)triimidazotriazine (TT-Py) organic molecule, comprising excitation-dependent fluorescence and phosphorescence under ambient conditions in both blended films and the crystalline phase, is investigated by means of steady state, time resolved and ultrafast spectroscopies and interpreted on the basis of X-ray diffraction studies and DFT/TDDFT calculations. In particular, by proper excitation wavelength, dual fluorescence and dual phosphorescence of molecular origin can be observed together with low energy phosphorescences resulting from aggregate species. It is demonstrated that the multiple emission properties originate from the copresence, in the investigated system, of an extended polycyclic nitrogen-rich moiety (TT), strongly rigidified by π-π stacking interactions and short C-H···N hydrogen bonds, and a fragment (Py) having partial conformational freedom.

6.
Molecules ; 26(1)2020 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-33396319

RESUMO

The 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based molecules have emerged as interesting material for optoelectronic applications. The facile structural modification of BODIPY core provides an opportunity to fine-tune its photophysical and optoelectronic properties thanks to the presence of eight reactive sites which allows for the developing of a large number of functionalized derivatives for various applications. This review will focus on BODIPY application as solid-state active material in solar cells and in photonic devices. It has been divided into two sections dedicated to the two different applications. This review provides a concise and precise description of the experimental results, their interpretation as well as the conclusions that can be drawn. The main current research outcomes are summarized to guide the readers towards the full exploitation of the use of this material in optoelectronic applications.


Assuntos
Compostos de Boro/química , Corantes Fluorescentes/química , Óptica e Fotônica , Fótons , Energia Solar
7.
Molecules ; 25(1)2019 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-31878329

RESUMO

The development of high performance optically pumped organic lasers operating in the deep blue still remains a big challenge. In this paper, we have investigated the photophysics and the optical gain characteristics of a novel fluorene oligomer functionalized by four triphenylamine (TPA) groups. By ultrafast spectroscopy we found a large gain spectral region from 420 to 500 nm with a maximum gain cross-section of 1.5 × 10-16 cm2 which makes this molecule a good candidate for photonic applications. Amplified Spontaneous Emission measurements (ASE) under 150 fs and 3 ns pump pulses have revealed a narrow emission at 450 nm with a threshold of 5.5 µJcm-2 and 21 µJcm-2 respectively. Our results evidence that this new fluorene molecule is an interesting material for photonic applications, indeed the inclusion of TPA as a lateral substituent leads to a high gain and consequently to a low threshold blue organic ASE.


Assuntos
Compostos de Anilina/química , Fluorenos/química , Luz , Luminescência , Sondas Moleculares/química , Fatores de Tempo
8.
Front Chem ; 7: 409, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31263691

RESUMO

The photophysics of water and propan-1-ol suspensions of poly [N-9"-heptadecanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2',1',3'- benzothiadiazole)] (PCDTBT) nanoparticles and mesoparticles has been studied by ultrafast spectroscopy. High molar mass polymer (HMM > 20 kg/mol) forms nanoparticles with around 50 nm diameter via mini-emulsion post-polymerization, while low molar mass (LMM < 5 kg/mol) polymer prepared by dispersion polymerization results in particles with a diameter of almost one order of magnitude larger (450 ± 50 nm). In this study, the presence of excited-states and charge separated species was identified through UV pump and visible/near-infrared probe femtosecond transient absorption spectroscopy. A different behavior for the HMM nanoparticles has been identified compared to the LMM mesoparticles. The nanoparticles exhibit typical features of an energetically disordered conjugated polymer with a broad density of states, allowing for delayed spectral relaxation of excited states, while the mesoparticles show a J-aggregate-like behavior where interchain interactions are less efficient. Stimulated emission in the red-near infrared region has been found in the mesoparticles which indicates that they present a more energetically ordered system.

9.
Sci Rep ; 9(1): 7370, 2019 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-31089241

RESUMO

Polythiophenes are the most widely utilized semiconducting polymers in organic electronics, but they are scarcely exploited in photonics due to their high photo-induced absorption caused by interchain polaron pairs, which prevents the establishment of a window of net optical gain. Here we study the photophysics of poly(3-hexylthiophene) configured with different degrees of supramolecular ordering, spin-coated thin films and templated nanowires, and find marked differences in their optical properties. Transient absorption measurements evidence a partially-polarized stimulated emission band in the nanowire samples, in contrast with the photo-induced absorption band observed in spin-coated thin films. In combination with theoretical modeling, our experimental results reveal the origin of the primary photoexcitations dominating the dynamics for different supramolecular ordering, with singlet excitons in the nanostructured samples superseding the presence of polaron pairs, which are present in the disordered films. Our approach demonstrates a viable strategy to direct optical properties through structural control, and the observation of optical gain opens the possibility to the use of polythiophene nanostructures as building blocks of organic optical amplifiers and active photonic devices.

10.
J Phys Chem Lett ; 8(3): 547-552, 2017 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-28045534

RESUMO

One-dimensional J aggregates present narrow and intense absorption and emission spectra that are interesting for photonics applications. Matrix immobilization of the aggregates, as required for most device architectures, has recently been shown to induce a non-Gaussian (Lévy type) defect distribution with heavy tails, expected to influence exciton relaxation. Here we perform two-dimensional electronic spectroscopy (2DES) in one-dimensional J aggregates of the cyanine dye TDBC, immobilized in a gel matrix, and we quantitatively model 2DES maps by nonlinear optimization coupled to quantum mechanical calculations of the transient excitonic response. We find that immobilization causes strong non-Gaussian off-diagonal disorder, leading to a segmentation of the chains. Intersegmental exciton transfer is found to proceed on the picosecond time scale, causing a long-lasting excitation memory. These findings can be used to inform the design of optoelectronic devices based on J aggregates as they allow for control of exciton properties by disorder management.

11.
Faraday Discuss ; 196: 143-161, 2017 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-27901153

RESUMO

We report the design, synthesis, molecular optical properties, and solid state emissive behaviour of a series of novel compounds, which, similar to the archetypal AIE luminogen tetraphenylethene, are formed of a central olefin stator and decorated with either three or four rotors. These rotors, being either electron-rich substituted benzenes, or electron-withdrawing functional groups (esters, ketones, cyano groups) confer a "push-pull" character to the overall molecular structure. Building on both new and already published contributions, a comprehensive picture of the properties and the potential of these compounds is provided.

12.
Opt Lett ; 41(10): 2245-8, 2016 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-27176973

RESUMO

We investigate experimentally the interaction between amplified spontaneous emission (ASE) and a soliton, which are both generated in a dye-doped nematic liquid crystal (LC) cell. A light beam is injected through an optical fiber slid into the cell to form a soliton beam. ASE is then automatically collected by this self-induced waveguide and efficiently coupled into the same optical fiber, in the backward direction. We demonstrate that the presence of the soliton improves the ASE collection by one order of magnitude. We also show that the ASE is highly polarized in the plane of the LC cell and that the ASE spectrum depends on the pump stripe orientation with respect to the LC director. The origin of the spectral anisotropy of the gain curves is determined with the help of femtosecond pump-probe spectroscopy.

13.
ACS Appl Mater Interfaces ; 6(15): 11997-2004, 2014 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-25007400

RESUMO

A new nanostructured α-Fe2O3 photoelectrode synthesized through plasma-enhanced chemical vapor deposition (PE-CVD) is presented. The α-Fe2O3 films consist of nanoplatelets with (001) crystallographic planes strongly oriented perpendicular to the conductive glass surface. This hematite morphology was never obtained before and is strictly linked to the method being used for its production. Structural, electronic, and photocurrent measurements are employed to disclose the nanoscale features of the photoanodes and their relationships with the generated photocurrent. α-Fe2O3 films have a hierarchical morphology consisting of nanobranches (width ∼10 nm, length ∼50 nm) that self-organize in plume-like nanoplatelets (350-700 nm in length). The amount of precursor used in the PE-CVD process mainly affects the nanoplatelets dimension, the platelets density, the roughness, and the photoelectrochemical (PEC) activity. The highest photocurrent (j = 1.39 mA/cm(2) at 1.55 VRHE) is shown by the photoanodes with the best balance between the platelets density and roughness. The so obtained hematite hierarchical morphology assures good photocurrent performance and appears to be an ideal platform for the construction of customized multilayer architecture for PEC water splitting.

14.
Chem Commun (Camb) ; 49(100): 11761-3, 2013 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-24205511

RESUMO

We report a new approach to improve the gain characteristics of a red-emitting based molecule. The insertion of the active dye between two polymeric arms prevents the inter-molecular interactions deleterious for the gain. By means of the ultra-fast pump-probe technique we found an efficient energy transfer between the polymer and dye. High gain in the nanosecond timescale regime has been proved.

15.
Phys Chem Chem Phys ; 14(39): 13646-50, 2012 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-22964896

RESUMO

In a smart solution-processable luminescent poly(norbornene)/oxazine-1 (Ox1) intercalated fluoromica nanohybrid, the supramolecular organization of the Ox1 dyes can be tuned at the nanoscale level and a deep red emission band switched on by inducing a phase segregation of aligned molecules within the fluoromica layered scaffold. By combining low-temperature photoluminescence and ultrafast pump-probe spectroscopy we prove that the nanoconstrained Ox1 molecules are organized in a J-type packing and we highlight the critical factor that controls such a supramolecular dye arrangement.


Assuntos
Corantes Fluorescentes/química , Nanoestruturas/química , Oxazinas/química , Plásticos/química , Luminescência , Soluções , Análise Espectral , Temperatura
16.
Nanoscale ; 4(7): 2219-26, 2012 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-22358178

RESUMO

This article is devoted to the exploration of the benefits of a new ultrafast confocal pump-probe technique, able to study the photophysics of different structured materials with nanoscale resolution. This tool offers many advantages over standard stationary microscopy techniques because it directly interrogates excited state dynamics in molecules, providing access to both radiative and non-radiative deactivation processes at a local scale. In this paper we present a few different examples of its application to organic semiconductor systems. The first two are focussed on the study of the photophysics of phase-separated polymer blends: (i) a blue-emitting polyfluorene (PFO) in an inert matrix of PMMA and (ii) an electron donor polythiophene (P3HT) mixed with an electron acceptor fullerene derivative (PCBM). The experimental results on these samples demonstrate the capability of the technique to unveil peculiar interfacial dynamics at the border region between phase-segregated domains, which would be otherwise averaged out using conventional pump-probe spectroscopy. The third example is the study of the photophysics of isolated mesoscopic crystals of the PCBM molecule. Our ultrafast microscope could evidence the presence of two distinctive regions within the crystals. In particular, we could pinpoint for the first time areas within the crystals showing photobleaching/stimulated emission signals from a charge-transfer state.


Assuntos
Nanocompostos/química , Nanocompostos/ultraestrutura , Análise Espectral/métodos , Fluorenos/química , Fulerenos/química , Microscopia Confocal/instrumentação , Microscopia Confocal/métodos , Modelos Biológicos , Nanoestruturas/química , Óptica e Fotônica , Compostos Orgânicos/química , Polimetil Metacrilato/química , Fatores de Tempo
19.
Appl Opt ; 48(31): G114-8, 2009 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-19881630

RESUMO

We report on innovative application of microchannels with access holes fabricated by femtosecond laser irradiation followed by chemical etching. This technique allows us to demonstrate a novel approach to the achievement of organic photonic devices in which the properties of a conjugated polymer in solution are exploited in a microfluidic configuration to produce an easy-to-integrate photonic device. Filling the microchannel with a diluted polyfluorene solution, we exploit the unique properties of isolated polymeric chains such as ultrafast gain switching (switching response time of 150 fs) with a 100% on-off ratio. In addition, by dispersing nanoparticles in the polymeric solution we are able to achieve random lasing in the microchannel.

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