The achievement of organic semiconductors with both high mobility and strong fluorescence emission remains a challenge. High mobility requires molecules which pack densely and periodically, while serious fluorescence quenching typically occurs when fluorescent materials begin to aggregate (aggregation-induced quenching (AIQ)). Indeed, classical materials with strong fluorescent emission always exhibit low mobility, for example, tris(8-hydroxyquinoline) aluminium (ALQ) and phenylenevinylene-based polymers with mobility only 10-6-10-5 cm2V-1s-1, and benchmark organic semiconductors with high mobility demonstrate very weak emission, for example, rubrene exhibits a quantum yield﹤1% in crystalline state and pentacene shows very weak fluorescence in the solid state. However, organic semiconductors with high mobility and strong fluorescence are necessary for the achievement of high efficiency organic light-emitting transistors (OLETs) and electrically pumped organic lasers. Therefore, it is necessary for developing high mobility emissive organic/polymeric semiconductors towards a fast mover for the organic optoelectronic integrated devices and circuits.
We demonstrate a polymer photodetector with spectral response from 300nm to 1450nm by using a
narrow-band-gap semiconducting polymer blended with a fullerene derivative. Operating in room temperature, the polymer
photodetectors exhibit detectivity greater than 1013Jones (1Jones =1cm Hz1/2/W) from the UV well into the near-infrared
out to 1150nm and greater than 1012Jones from 1150nm to 1450nm. The linear dynamic range is over 100dB. To our
knowledge, there is no inorganic material system (not even Si-Ge alloys) capable of such high performance
photodetectivty over such a wide spectral range.
We report the fabrication and measurement of solar cells with 6% power conversion efficiency using the alternating copolymer,
poly[N-9''-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole), PCDTBT, in
bulk heterojunction (BHJ) composites with the fullerene derivative [6,6]-phenyl C70-butyric acid methyl ester (PC70BM).
The PCDTBT/PC70BM solar cells exhibit the best performance of any BHJ system studied to date; Jsc = 10.6 mA/cm2,
Voc = 0.88 V, FF = 0.66 and ηe = 6.1% under air mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm2. The internal
quantum efficiency (IQE) is close to 100%, implying that essentially every absorbed photon results in a separated pair of
charge carriers and that all photogenerated carriers are collected at the electrodes.
Conducting and semiconducting polymers are important materials in the development of printed, flexible, large area
electronics such as flat panel displays and photovoltaic cells. There has been rapid progress in developing conjugated
polymers with high transport mobility required for high performance field effect transistors (FETs), beginning with
mobilities around 10-5cm2/Vs to a recent report of 1cm2/Vs for poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno
[3,2-b]thiophene) (PBTTT). In this work, the electrical properties of PBTTT are studied at high charge densities both as the
semiconductor layer in FETs and in electrochemically doped films to determine the transport mechanism. We show that
data obtained using a wide range of parameters (temperature, gate-induced carrier density, source-drain voltage and
doping level) scale onto the universal curve predicted for transport in the Luttinger Liquid description of the onedimensional
"metal", where fermions along the 1D chain collectively behave as bosons, and where charge and spin are
decoupled.
By introducing a titanium oxide (TiOx) layer between the active layer and the aluminum cathode in polymer based
electronic devices, we have demonstrated devices with excellent air stability and with enhanced performance. The TiOx
layer acts as a shielding and scavenging layer which prevents the intrusion of oxygen and humidity into the
electronically active polymers, thereby improving the lifetime of unpackaged devices exposed to air by nearly two orders
of magnitude. We have also fabricated polymer tandem solar cells with a power conversion efficiency of 6.5%, with
each layer processed from solution. A transparent TiOx layer is used to separate and connect the front cell and the back
cell. The TiOx layer serves as an electron transport and collecting layer for the first cell and as a stable foundation that
enables the fabrication of the second cell to complete the tandem cell architecture. We use an inverted structure with the
low band-gap polymer/fullerene composite as the charge separating layer in the front cell and the high band-gap polymer
composite as the charge separating layer in the back cell.
Organic and polymer light-emitting diodes (OLEDs/PLEDs) that emit white light are of interest and potential importance for use in active matrix displays (with color filters) and because they might eventually be used for solid-state lighting. In such applications, large-area devices and low-cost of manufacturing will be major issues. We demonstrated that high performance multilayer white emitting PLEDs can be fabricated by using a blend of luminescent semiconducting polymers and organometallic complexes as the emission layer, and water-soluble (or ethanol-soluble) polymers/small molecules (for example, PVK-SO3Li) as the hole injection/transport layer (HIL/HTL) and water-soluble (or ethanol-soluble) polymers/small molecules (for example, t-Bu-PBD-SO3Na) as the electron injection/transport layer (EIL/HTL). Each layer is spin-cast sequentially from solutions. Illumination quality light is obtained with stable Commission Internationale d'Eclairage coordinates, stable color temperatures, and stable high color rendering indices, all close to those of "pure" white. The multilayer white-emitting PLEDs exhibit luminous efficiency of 21 cd/A, power efficiency of 6 lm/W at a current density of 23 mA/cm2 with luminance of 5.5 x 104 cd/m2 at 16 V. By using water-soluble (ethanol-soluble) polymers/small molecules as HIL/HTL and polymers/small molecules as EIL/ETL, the interfacial mixing problem is solved (the emissive polymer layer is soluble in organic solvents, but not in water/ ethanol). As a result, this device architecture and process technology can potentially be used for printing large-area multiplayer light sources and for other applications in "plastic" electronics. More important, the promise of producing large areas of high quality white light with low-cost manufacturing technology makes the white multilayer white-emitting PLEDs attractive for the development of solid state light sources.
The overall power conversion efficiency of organic solar cells depends on many factors, some of which such as photon absorption, charge carrier photogeneration, separation and transport are intrinsic properties of the active material. The use of low-bandgap conjugated polymers in polymer/fullerene bulk heterojunctions improves the spectral overlap between the polymer absorption and the solar irradiance spectrum, and is therefore a promising route toward increased light harvesting and higher power conversion efficiency of polymer photovoltaics. We present our studies on the optical and charge transport properties of a novel low-bandgap conjugated polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)], PCPDTBT, with an optical energy gap of Eg=1.46 eV. The combination of steady-state and transient photoconductivity with photoinduced absorption measurements has allowed us to investigate the charge carrier photogeneration and charge transport mechanisms in pristine PCPDTBT and PCPDTBT:PCBM interpenetrating networks, and to compare them to the P3HT and P3HT:PCBM model systems. The picture of the photophysics of PCPDTBT:PCBM emerging from these studies is very similar to that of P3HT:PCBM blends. We discuss the potential of PCPDTBT as a new material for high efficiency polymer solar cells.
Polymer field-effect transistors with a field-effect mobility of μ ≈0.3 cm2/V.s have been demonstrated using
regioregular poly(3-hexylthiophene) (rr-P3HT). Devices were fabricated by dip-coating the semiconducting polymer
followed by annealing at 150°C for 10 minutes. The heat annealed devices exhibit an increased field-effect mobility
compared with the as-prepared devices. Morphology studies and analysis of the channel resistance demonstrate that the
annealing process increases the crystallinity of rr-P3HT and improves the contact between the electrodes and the P3HT
films, thereby increasing the field effect mobility of the films. Based on the results obtained from unipolar FETs using rr-
P3HT, we have also applied postproduction heat treatment to ambipolar polymer FETs fabricated with rr-P3HT and C61-
butyric acid methyl ester (PCBM). Devices were fabricated using aluminum (Al) source and drain electrodes to achieve
an equivalent injection for the both holes and electrons. As the case of P3HT unipolar FETs, the thermal annealing
method also improves the film morphology, crystallinity, and the contact properties between Al and active layer, thereby
resulting in excellent ambipolar characteristics with the hole mobility of 1.7×10-3 cm2/V.s and the electron mobility of
2.0×10-3 cm2/V.s.
Ambipolar light-emitting field-effect transistors are fabricated with two different metals for the top-contact source and
drain electrodes; a low-work-function metal defining the channel for the source electrode and a high-work-function
metal defining the channel for the drain electrode. A thin film of polypropylene-co-1-butene on SiNx is used as the gate
dielectric on an n++-Si wafer, which functioned as the substrate and the gate electrode. Transport data show ambipolar
behavior. Recombination of electrons and holes results in a narrow zone of light emission within the channel. The
location of the emission zone is controlled by the gate bias.
New architectural polymer photovoltaic cells approaching 5% power conversion efficiency have been fabricated using titanium oxide (TiOx) as an optical spacer. Solar cells with a TiOx layer (deposited by a sol-gel process) between the active layer and the electron collecting aluminum electrode exhibit approximately 50% enhancement in power conversion efficiency compared to similar devices without the optical spacer. The TiOx layer increases the efficiency by modifying the spatial distribution of the light intensity inside the device, thereby creating more photogenerated charge carriers in the bulk heterojunction layer.
By applying the specific fabrication conditions such as postproduction annealing at 150oC for 30 minutes, polymer solar cells with 5% power conversion efficiency are demonstrated. These devices exhibit remarkable thermal stability. We attribute the improved performance to changes in the bulk heterojunction material induced by thermal annealing. The improved nanoscale morphology, the increased crystallinity of the semiconducting polymer, and the improved contact to the electron collecting electrode facilitate charge generation, charge transport to, and charge collection at the electrodes, thereby enhancing the device efficiency by lowering the series resistance of the polymer solar cells. Also new architectural polymer solar cells with 5% power conversion efficiency have been fabricated using titanium oxide (TiOx) as an optical spacer. Solar cells with a TiOx layer (deposited by a sol-gel process) between the active layer and the electron collecting aluminum electrode exhibit approximately 50% enhancement in power conversion efficiency compared to similar devices without the optical spacer. The TiOx layer increases the efficiency by modifying the spatial distribution of the light intensity inside the device, thereby creating more photogenerated charge carriers in the bulk heterojunction layer.
White emission from polymer light-emitting diodes (PLEDs) is demonstrated by spin-casting polymer blends from solution containing poly(9,9-dioctylfluorenyl-2.7-diyl) (PFO) and tris (2,5-bis-2'-(9',9'-dihexylfluorene) pyridine) iridium (III), Ir(HFP)3. The white electrophosphorescence PLEDs exhibit luminance of 1.2 x 104 cd/m2 at 17 volts and luminous efficiency of 4.3 cd/A at current density of 5.2 mA/cm2. Because a single semiconducting polymer, PFO, was used as the common host for red, green and blue emission, the color coordinates, the color temperatures and the color rendering indices of the white emission are insensitive to the brightness, applied voltage and applied current density.
High performance electrophosphorescent light emitting diodes (LEDs) were demonstrated by using conjugated polymers, poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO), PFO end-capped with hole-transporting moieties (HTM), PFO-HTM, and PFO end-capped with electron-transporting moieties (ETM), PFO-ETM, as the hosts and the organometallic emitter, tris-[2,5-bis-2'-(9,9'-dihexylfluorene) iridium] [Ir(HFP)3] as the guest. Electrophosphorescent LEDs fabricated from PFO, PFO-HTM, and PFO-ETM as the hosts emit red light with turn-on voltage around 5V, luminances (L) of 2040 cd/m2, 1937 cd/m2 and 2487 cd/m2 at 290 mA/cm2 (16 V), and luminance efficiencies (LE) of 1.40 cd/A, 1.38 cd/A and 1.80 cd/A at 4.5 mA/cm2 for PFO, PFO-HTM, and PFO-ETM, respectively. The results demonstrate that high performance electrophosphorescence can be obtained from conjugated polymer-based LEDs that are fabricated by processing the active materials directly from solution.
The electrical properties of polymeric thin film transisitors (P-TFTs) based on poly(9,9-dioctylfluorene-co-bithiophene) alternating copolymer (F8T2) have been studied. Device performance was compared for amorphous silicon nitride deposited by LPCVD and PECVD techniques, aluminum oxide deposited by sputtering, titanium oxide deposited by sputtering, and thermal silicon oxide gate dielectrics. A heavily n-type doped crystalline silicon wafer coated with the desired gate dielectric was used. Photolithographic patterning of source/drain electrodes directly on top of the F8T2 layer is also discussed. The main conclusion from this work is that traps within the F8T2 define the conduction process within the device.
Ultrafast photoinduced absorption by infrared-active vibrational modes (IRAV) is used to detect charged photo- excitations (polarons) in solid films of conjugated luminescent polymers. Experiments, carried out in zero applied electric field, show that polarons are generated within 100 fs with quantum efficiencies of approximately 10%. The ultrafast photoinduced IRAV Absorption, the weak pump-wavelength dependence, and the linear dependence of charge density on pump intensity indicate that both charged polarons and neutral excitons are independently generated even at the earliest times. Measurements of the excitation profile of the transient and steady-state photoconductivity of poly(phenylene vinylene) and its soluble derivatives over a wide spectral range up to h(upsilon) = 6.2 eV indicate an apparent increase in the photoconductivity at h(upsilon) > 3- 4 eV that arises from external currents generated by electron photoemission (PE). After quenching the PE by addition of CO2+SF6 (90%:10%) into the sample chamber, the bulk photoconductivity is nearly independent of photon energy in all polymers studied, in a good agreement with the IRAV spectra. The single threshold for photoconductivity is spectrally close to the onset of (pi) - (pi) * absorption, behavior that is inconsistent with a large exciton binding energy.
Polymer photovoltaic cells and photodetectors have passed their infancy and become mature technologies. The energy conversion efficiency of polymer photovoltaic cells have been improved to over 4.1% (500 nm, 10 mW/cm2). Such high efficiency polymer photovoltaic cells are promising for many applications including e-papers, e-books and smart- windows. The development of polymer photodetectors is even faster. The performance parameters have been improved to the level meeting all specifications for practical applications. The polymer photodetectors are of high photosensitivity (approximately 0.2 - 0.3 A/Watt in visible and UV), low dark current (0.1 - 1 nA/cm2), large dynamic range (> 8 orders of magnitude), linear intensity dependence, low noise level and fast response time (to nanosecond time domain). These devices show long shelf and operation lives. The advantages of low manufacturing cost, large detection area, and easy hybridization and integration with other electronic or optical components make the polymer photodetectors promising for a variety of applications including chemical/biomedical analysis, full-color digital image sensing and high energy radiation detection.
In this presentation, we discuss recent progress on polymer photovoltaic cells and polymer photodetectors. By improving the fill-factor of polymer photovoltaic cells, the energy conversion efficiency was improved significantly to over 4 percent. Such high efficiency polymer photovoltaic cells are promising for many applications including e-papers, e-books and smart-windows. Polymer photodetectors with similar device configuration show high photosensitivity, low dark current, large dynamic range, linear intensity dependence, low noise level and fast response time. These parameters are comparable to or even better than their inorganic counterparts. The advantages of low manufacturing cost, large detection area, and easy hybridization and integration with other electronic or optical components make them promising for a variety of applications including chemical/biomedical analysis, full-color digital image sensing and high energy radiation detection.
We demonstrate ultrafast (100 fs) carrier generation in poly(phenylene vinylene), PPV, and poly[2-methoxy-5-(2- ethyl-hexyloxy)-(phenylene vinylene)], MEH-PPV, by using femtosecond transient spectroscopy in the mid-IR in order to probe the infrared active vibrational active (IRAV) modes. The 10% carrier generation quantum efficiency in MEH-PPV with no electric field applied, implies primary photogeneration of charge carriers. The recombination dynamics in PPV and MEH-PPV indicate that the carrier lifetime is sensitive to the strength of the interchain interaction.
Sub-picosecond spectroscopy and ultrafast pump-probe experiments spectrally and temporally resolve the Forster energy transfer in blends from larger gap host to the smaller gap guest organic materials. The dynamics of the stimulated emission and photoinduced absorption of the polymer blends indicate that 10 - 20 ps are required for complete energy transfer. The Forster interaction ranges suggested by quantitative measurements of energy transfer rates are compared with the theoretical values as calculated from the spectral overlap. We discuss the effect of the excited state delocalization. The energy transfer dynamics in small organic molecule blends have a longer time scale (1 ns), corresponding to the much longer lifetimes of the organic dyes.
We present a new approach for achieving spatial frequency filtering in the analog domain. Our device, the Thin Film Analog Image Processor (TAIP), is a hybrid structure that combines the strengths of analog VLSI technology with the simplicity of a conducting polymer film. The TAIP consists of a silicon chip with a square array of metal pads corresponding to the image pixels, onto which a conducting polymer film is applied to create lateral interaction between pixels. Analog image data (0 - 2 Volts) is multiplexed into the array, and the image is processed with up to 72 dB of resolution. The TAIP arrays are capable of performing either high or low pass spatial frequency filtering, operations that become computationally intensive for large images in the digital domain. Multiple arrays can be combined to create tunable bandpass spatial frequency filters that are capable of extracting features from complex images. Two array formats have been fabricated, 60 X 80 and 320 X 240, each capable of 60 Hz operation with a power consumption of approximately 100 mW.
High performance photonic and electronic devices fabricate from conjugated polymers have been demonstrated, including light emitting diodes, photovoltaic cells, photodiodes, optocouplers, and thin film transistors. In some cases, performance parameters have been improved to levels comparable to or better than their inorganic counterparts.Notably absent from this list of semiconducting polymer devices is the polymer laser diode. As the first important step in exploring the feasibility of such laser diodes, optically pumped stimulated emission, gain, and lasing have recently been observed in over a dozen different semiconducting polymers representing a variety of molecular structures with emission wavelengths spanning the visible spectrum. Because of their strong absorption, high density of chromophores, and Stokes-shifted luminescence, luminescent semiconducting polymers have potential as low- threshold laser media and as active media in InGaN/polymer hybrid light emitting devices. We give details on an ongoing effort on optically pumped lasers using microcavities and distributed feedback (DFB) and suggest two routes toward fabricating laser diodes using semiconducting polymers. Initial results show that the lasing threshold for DFB laser is one order of magnitude lower than that of a microcavity laser using the same polymer under similar optical pumping conditions.
The recent emergence of semiconducting (pi) -conjugated polymers as solid-state laser materials has been made possible by the availability of numerous high photoluminescence efficiency polymers with emission wavelengths spanning the visible spectrum. As the first important step in exploring the feasibility of electrically pumped polymer laser diodes, we have demonstrated photopumped gain narrowing in submicron thick films, neat and undiluted, of photoluminescent conjugated polymers. The dramatic collapse of the emission line width (to as little as 7 nm) occurs at very low pump energy thresholds (approximately 10 (mu) J/cm2 per 10 ns pulse). Gain narrowing is found in over a dozen different polymers representing a variety of molecular structures and is explained in terms of amplified spontaneous emission in planar waveguides which allow the distance traveled by emitted photons to exceed the short intrinsic gain lengths. The short gain lengths arise from the high density of chromophores, the large density of states associated with the (pi) -(pi) * transition in quasi-one-dimensional systems, and the Stokes shift which minimizes self- absorption. Prospects for producing electrically pumped solid-state polymer diode lasers using this class of materials are discussed in the context of the low-threshold gain narrowing in submicron thick films.
We present experimental evidence that orientation of the polymer chains in semiconducting polymer films leads to lower thresholds for gain narrowing. Two different materials have been investigated: neat films of poly(p-phenylene vinylene) (PPV) and blends of poly(2-methoxy-5-(2'- ethyl-hexyloxy)-1-4-phenylenevinylene) (MEH-PPV) in polyethylene (PE). Gain narrowing is not observed in non- oriented films in either of the two materials. However, free-standing films of PPV drawn to a ratio of (7:1) showed gain narrowing at threshold one order of magnitude lower than typically found for non-oriented films of soluble PPV derivatives. For the MEH-PPV blends, gain narrowing is observed in diluted films with concentrations of the active polymer of approximately 1 percent. The thresholds for these dilute, but chain extended and highly oriented free standing films are comparable to those obtained in neat thin film waveguides of the same material. These result are correlated with the microstructure of the films, as investigated by x- ray diffraction.
Charge-transfer polymers are a new class of nonlinear optical materials which can be used for generating femtosecond holographic gratings. Using semiconducting polymers sensitizes with varying concentrations of C60, holographic gratings were recorded by individual ultrafast laser pulses; the diffraction efficiency and time decay of the gratings were measured using non-degenerate four-wave mixing. Using a figure of merit for dynamic data processing, the temporal diffraction efficiency, this new class of materials exhibits between two and 12 orders of magnitude higher response than previous reports. The charge transfer range at polymer/C60 interfaces was further studied using transient absorption spectroscopy. The fact that charge-transfer occurs in the picosecond-time scale in bilayer structures implies that diffusion of localized excitations to the interface is not the dominant mechanism; the charge transfer range to be 80 angstrom and interpret that range as resulting from quantum delocalization of the photoexcitations.
We report steady-state photoinduced absorption (PIA) and photoinduced reflectance (PIR) in films of MEH-PPV and BCHA- PPV blended with fullerene-based acceptors. Absorption from the metastable charge-transferred state is probed by PIA; the modulated absorption spectrum causes changes in the real part of the index of refraction, (Delta) n, which can be measured directly by PIR. The charge transfer gives rise to pronounced features in (Delta) n, including vibrational structure in the mid- and near-IR. Our measurements over a wide spectral range allow quantitative comparison of (Delta) n obtained from PIR with that obtained from Kramers- Kronig transformation of the PIA data. We find good agreement throughout the IR, indicating that our method for measuring (Delta) n is useful as an analytical tool for optical characterization and for prediction of optical spectral ranges for nonlinear optical response.
Blending organic semiconductors with different electron affinities results in an interpenetrating bi-continuous network of internal donor/acceptor (D/A) heterojunctions. These nano-scale D/A junctions show efficient charge separation and charge transfer. The interpenetrating bi- continuous networks of the donor and the acceptor phases also allow the separated carriers to be collected effectively at the anode and cathode contacts. Typical materials used for the donor phase are conjugated polymers (MEH-PPV). Typical materials used for the acceptor phase are conjugated polymer CN-PPV or fullerene molecules. These photosensitive materials are soluble to common organic solvents, and are processable at room temperature. Photodiodes and photovoltaic cells are fabricated with high quantum efficiencies. The carrier collection efficiency and energy conversion efficiency of MEH-PPV:C60 photovoltaic cells are approximately 29 percent electrons/photon and approximately 3 percent under illumination of 20 mW/cm2 at 430 nm, two orders of magnitude higher than that in devices with MEH-PPV alone. The photosensitivity and the quantum yields increase to 0.26 A/W and approximately 75 percent electrons/photon at reverse bias of -2V, even higher than those in UV-enhanced Si photodiodes at the same wavelength. Large size photodetectors and image sensors have been fabricated with these materials.
Optical quality organic blend films were developed with high photosensitivity. These materials are composed with conjugated polymers, P3OT, or poly(2-methoxy-5-(2-ethyl- hexyloxy)-1,4-phenylene vinylene), MEH-PPV) and fullerene molecules. These blends are soluble to common organic solvents, and are processable at room temperature. Thin film devices in sandwich configurations were fabricated with high quantum efficiency. The carrier collection efficiency and energy conversion efficiency in the MEH-PPV:C60 photovoltaic cells are approximately 29 percent electrons/photons and 2.9 percent respectively, better by more than two orders of magnitude than devices made with MEH-PPV alone. The photosensitivity are even higher with reverse bias, approximately 0.2A/W-0.3A/W in visible region at a few volts. These numbers are comparable to photodiodes made with inorganic semiconductors.
We report photoinduced absorption and photoinduced reflectance spectra of poly(3-octyl thiophene)- methanofullerene films. The data allow direct evaluation of the corresponding changes in the complex refractive index, (Delta) N equals (Delta) n((omega) )+i(Delta) (kappa) ((omega) ), of the films. As a results of the efficient photoinduced intermolecular charge transfer, the magnitudes of (Delta) n((omega) ) and (Delta) (kappa) ((omega) ) are significantly enhanced over those in either of the component materials, with (Delta) n and (Delta) (kappa) approximately equals 10-2 in the infrared at laser pump intensity of only 50mW/cm2. Moreover, the photoinduced absorption shows new features at 1.2 eV and 1.6 eV, both of which are associated with excited state absorptions of the methanofullerene anion. The implications of these photoinduced changes in the index resulting from photoexcitations are discussed in terms of potential optoelectronic and nonlinear optical applications of these materials, indicating that conducting polymer/methanofullerene films are promising as high- performance nonlinear optical materials.
Holographic recording has been demonstrated in conducting polymer/C60 blends. These materials allow ultrafast holographic recording and the ability to tailor the decay dynamics of the recorded hologram. Diffraction efficiencies up to 1.6 percent have been measured in these materials for gratings recorded with individual laser pulses. Results are presented that demonstrate that an improved signal-to-noise ratio is obtained when holographic detection is used to observe the dynamics of photo-induced absorption.
An array of polymer grid triodes (PGTs) connected through a common grid functions as a 'plastic retina' which provides local contrast gain control for image enhancement. This device, made from layers of conducting polymers, functions as an active resistive network that performs center-surround filtering. The PGT array with common grid is a continuous analog of the discrete approach of Mead, with a variety of fabrication advantages and with a significant saving of 'real estate' within the unit cell of each pixel.
Nonlinear optical absorption in solid films of poly(3-octyl thiophene) (P3OT) sensitized with methanofullerene was investigated for wavelengths from 620 to 960 nm. The nonlinear absorption is enhanced over that in either of the component materials by more than two orders of magnitude at 760 nm. The large nonlinearity results from efficient photoinduced intermolecular charge transfer from P3OT to methanofullerene, followed by absorption in the charge separated excited state. P3OT/fullerene films are promising as optical limiters; the transmission clamps at an average fluence of approximately 0.1 J/cm2.
In this review we discus the photophysical properties of the supramolecular composites of two (pi) -electron semiconductors; e.g. conjugated polymers as electron donors and Buckminsterfullerene as electron acceptor. Conjugated, polymeric semiconductors have been found to be effective donors upon photoexcitation of the valence band electrons across the bandgap into the conduction band. The Buckminsterfullerene, C60 is a powerful acceptor moeity upon photoexcitation. Thus, the supramolecular composite of these two conjugated materials exhibit an ultrafast, reversible, metastable photoinduced electron transfer and charge separation. This process, similar to the primary steps of photosynthesis, has been utilized in conjugated polymer/C60 based heterojunction as well as Schottky type devices for effective conversion of the solar photon energy into electricity. Other related applications of the above mentioned photophysics include photolithographic and xerographic processes. Furthermore, quantum well like heterostructures based on organic donor-acceptor layers are proposed to exhibit interesting photoinduced phenomena. Non-linear optical (NLO) properties of these composites are reported in comparative studies with the components alone. The results show a strong enhancement of the NLO coefficients in the composite materials compared to the conjugated polymer as well as C60 alone.
Evidence for ultrafast photoinduced electron transfer from semiconducting polymers to C60 is presented. Upon photoexcitation across the (pi) -(pi) * gap of the conjugated polymer, an electron transfer from the polymer to C60 is initiated. We find that the forward charge transfer occurs in the subpicosecond time domain, and that the charge transferred state is metastable. The ultrafast electron transfer implies that the intrinsic quantum efficiency for photogenerating charged species is close to unity. Hence C60 can serve as an ideal photosensitizing agent for conjugated polymers, as confirmed by picosecond photoconductivity measurements. Steady state photoinduced absorption shows features of the absorption of the C60 anion and the polymer cation, confirming the mechanism of charge transfer from the polymer host to C60.
We present a comparative study of the steady state photo-induced absorption of conducting polymers mixed with Buckminsterfullerene, C60. For conjugated polymers with nondegenerate ground state as donors, electron transfer takes place prior to either radiative or nonradiative recombination of (pi) -electron photoexcitations on the conducting polymer. In the case of a conjugated polymer with degenerate ground state as donor, the structural relaxation associated with the formation of charged solitons is faster, and no indications of photoinduced charge transfer are observed.
We present the results of picosecond time-resolved luminescence studies of poly(2-methoxy,5- (2'-ethyl-hexyloxy)-p-phenylene-vinylene),MEH-PPV, in four forms: a pure film, in solution, in an ultra-high molecular weight polyethylene (UHMW-PE) gel, and a MEH-PPV/UHMW- PE blend. The luminescence has a characteristic lifetime of 200 - 300 ps at 293 K and 500 - 700 ps at 80 K. The decay times are approximately the same for the four forms of the material we studied. Calculated lifetimes longer than those measured and the observed temperature dependence imply that the luminescence is quenched by non-radiative processes. Fitting and luminescence versus pump intensity are used to determine possible mechanisms.
Experimental evidence of electron transfer from photo-excited conjugated polymers onto C60 is reported. Photoinduced optical absorption, photoinduced electron spin resonance, and quenching of the photoluminescence in conducting polymers interacting with C60 imply that charge transfer from the excited state of the conducting polymer to C60 occurs on a picosecond time scale. The charge-separated state in composite films is metastable at low temperatures. Rectifying bilayer heterojunctions (diodes) have been fabricated using semiconducting polymers and C60; rectification ratios in the current vs. voltage characteristics exceed 104. When illuminated, the devices act as photodiodes and exhibit photovoltaic response as a result of photoinduced charge separation across the heterojunction interface from the semiconducting polymer (donor) onto the C60 (acceptor). The photodiode and photovoltaic responses are characterized. The results are discussed in terms of opportunities for solar energy conversion, for photodiode detector devices, and for a variety of other applications which use photoinduced intermolecular charge separation.
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