We present a comprehensive review on the optical properties in pristine low bandgap copolymers, namely PTB7 and PDTP–DFBT, which are used as electron donors in copolymer/phenyl C71 butyric acid methyl ester blends for high efficiency solar cell devices. The copolymer backbone chain comprises of donor (D) and acceptor (A) moieties, which lower the band gap to the near-IR spectral region. Unlike traditional π-conjugated polymers in which the primary photoexcitations are singlet excitons (SE), in D–A copolymers we find at short times coexistence of two primary photoexcitation species, namely SE and triplet–triplet (TT) pairs, which are directly photogenerated upon photon absorption from the ground state within 300 fs, our transient time resolution. Using the transient magnetophotoinduced absorption (t-MPA) spectroscopy, we reveal the spin coupling between the SE and TT spin states from their correlated t-MPA responses. In addition, we show that the TT species dissociates into two individual triplet excitons (TE) in the picosecond time scale; however, the two-geminate TEs are entangled and maintain their spin coherence into the microsecond time domain.
We report on the photophysical properties of a soluble thienylene-vinylene π-conjugated polymer, namely imide poly-thienylene vinylene. Ultrafast pump probe spectroscopy reveals that a broad photoinduced absorption (PA) band is immediately photogenerated along with a narrower PA from the photoinduced singlet excitons. The broad PA is susceptible to magnetic field and thus is assigned to a correlated triple pair state. This feature shows a long lifetime persisting into the μs time domain, in contrast to the singlet exciton PA, which quickly decays on a 10-ps timescale. The steady-state PA spectrum is identical to the transient PA spectrum of the triplet pair state but shows a magnetic field response that is typical to isolated triplet excitons.
Recent advances in spin response of organic semiconductors include long polaron spin coherence time measured
by optically detected magnetic resonance (ODMR); substantive room-temperature magneto-electroluminescence
and magneto-conductance obtained in organic light emitting diodes (OLED); and spin-polarized carrier injection
from ferromagnetic electrodes in organic spin valves (OSV). Although the hyperfine interaction (HFI) has been
foreseen to play an important role in organic spin response, clear experimental evidence has been lacking. Using
the chemical versatility advantage of the organics, we studied and compared spin responses in films, OLED and
OSV devices based on π-conjugated polymers made of protonated, H-, and deuterated, D-hydrogen having a
weaker HFI strength. We demonstrate that the HFI plays a crucial role in all three spin responses. OLEDs and
films based on the D-polymers show substantial narrower magneto-electroluminescence, magneto-conductivity
and ODMR responses; whereas due to the longer spin diffusion, OSV devices based on D-polymers show
substantially larger magnetoresistance that reaches ~330% at small bias voltage and low temperatures.
In this work we study the internal electric field (Vint) present in devices based on an intrinsically semiconducting
polymer. Intermediate layers between the indium-tin-oxide and Al electrodes and the photoactive layer are
able to influence and alter this electric field. The two commonly used intermediate layers, namely poly(3,4-
ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) and LiF, are subject of this study.
Their influence is studied with Electroabsorption (EA) spectroscopy as well as transient photocurrent measurements
under applied bias. While PEDOT:PSS has no significant influence on Vint, introducing LiF increases
Vint close to the bandgap of the studied semiconducting polymer. However, using PEDOT:PSS directly influences
the spectral EA response. The interface between PEDOT:PSS and the conjugated polymer is studied by
impedance spectroscopy. We interpret the results in terms of the presence of charges at the interface.
We have studied the electroabsorption (EA) of self-assembled organic heterostructures (PPV/SPS)n consisting of alternate layers of poly(p-phenylenevinylene) (PPV) and `spacer' layers of poly(styrene-4-sulfonate), SPS. The heterostructures were prepared utilizing a layer-by-layer self-assembly technique using the precursor pre-polymer, followed by heat treatment to convert the pre-polymer into the conjugated polymer. For comparison, we have also studied the electroabsorption of a device made of spin-coated PPV. The thickness of the spacer layer, as determined by X-ray reflectivity, is varied from approximately equals 5 angstroms to 45 angstroms where the average thickness of the active PPV layers are maintained coarsely constant, 16 +/- 3 angstroms for the ten layers of each device. In all our measurements here the applied electric field is perpendicular to the plane of the films. The EA spectra of self-assembled films is significantly blue-shifted with increasing thickness of the spacer in the bilayers. The spectral width of the main peak in the EA spectrum for all the heterostructures is significantly broadened with respect to that of the spin- coated PPV, but it is almost independent of the spacer thickness. It exhibits a quadratic dependence on the applied electric field but no spectral shift with increasing field strength. The blue shift of the EA spectra is consistent with the blue shift in the absorption spectra as demonstrated in this work and in previous studies. The EA results, and particularly the blue-shifted spectra in the self-assembled films, are tentatively attributed to confinement effects, reduction of the PPV centrosymmetry and to an increase of the in-plane disorder of the active PPV layers.
The Raman active vibrational modes in (pi) -conjugated polymers are known to have different frequencies in different types of experiments. The best known examples are the resonant Raman scattering (RRS) and doping or photoinduced absorption infrared active vibrations (IRAV) measurements, in which the same modes appear at different energies. Other examples are the phonon side bands, accompanying the polarons, bipolarons, and solitons absorption bands, in which the same modes give rise to different side band energies. In this work we discuss RRS and IRAV measurements and correlate their experimentally observed frequencies with the relevant electronic state that is active in this type of experiment. We show that the IRAV frequencies are lower than those of RRS since the relevant energy levels of charged solitons and/or polarons are closer to the ground state than the optically allowed 1Bu state of the neutral polymer. Thus a new insight into the meaning of the `pinning' potential, which is associated with the lowest frequency IRAV mode is obtained.
The preparation and optical characterization of a novel PPV derivative displaying reversible tunable photophysical and electrophysical properties, poly-(5-vinylene-5'- (vinylene-1,4-phenylene)-2,2'-bipyridine), p-BVP, (1), is reported and its application in the preparation of tunable organic electroluminescent devices is described. The photophysical properties of the new polymer, such as its absorption, emission and electroluminescence are sensitive to the present of even minute traces of vapors of different acids and bases such as ammonia, formic acid and haloacids. The acid/base vapor induced optical changes are reversible and can be repeated many times without any significant degradation of the optical and mechanical properties of the films. Intermediate spectra can be generated simply by controlling the exposure time of the films to acidic or basic vapors. Similar effects were observed for two other polymers, poly-(5-vinylene-5'-tri(vinylene-1,4- phenylene)-2,2'-bipyridine), p-BTVP, (2), and its random analog p-BRTVP, (3). The tunability of the photo- and electrophysical properties of the polymers originates probably from structures changes associated with protonation-deprotonation processes and aggregation phenomena.
We have studied acceptor substituted poly(3-butyl)thiophene in an attempt to examine the role of acceptor molecules as intrinsic charge traps under light excitations by measuring the transient photoconductivity response following pulse excitation. The specially synthesized acceptor molecule is a chemically prepared high electron affinity (HEA) monomer, 1- (4-nitrophenyl)-2-(3-thienyl) ethene. In the co-polymers prepared with this acceptor monomer we have observed a simultaneous decrease of the sub-nanosecond photoconductivity and increase of the slow component is attributed to a bimolecular recombination process. A new photoinduced current rectifier based on an all-organic donor-acceptor bilayer substituted polythiophene derivative is described. Under visible and UV illumination, a p-n junction is formed leading to current rectification. Maximum photo-rectified current is obtained at approximately 400 nm, with a sharp decrease at shorter wavelengths. This sharp decrease indicates that photons with energy higher than 3.1 eV quench the light activation of this bilayer device.
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