The carrier collection efficiency (ηc) and energy conversion efficiency (ηe) of polymer photovoltaic cells were improved by blending of the semiconducting polymer with C60 or its functionalized derivatives. Composite films of poly(2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) and fullerenes exhibit ηc of about 29 percent of electrons per photon and ηe of about 2.9 percent, efficiencies that are better by more than two orders of magnitude than those that have been achieved with devices made with pure MEH-PPV. The efficient charge separation results from photoinduced electron transfer from the MEH-PPV (as donor) to C60 (as acceptor); the high collection efficiency results from a bicontinuous network of internal donor-acceptor heterojunctions.
Sensing from the ultraviolet-visible to the infrared is critical for a variety of industrial and scientific applications. Today, gallium nitride-, silicon-, and indium gallium arsenide--based detectors are used for different sub-bands within the ultraviolet to near-infrared wavelength range. We demonstrate polymer photodetectors with broad spectral response (300 to 1450 nanometers) fabricated by using a small-band-gap semiconducting polymer blended with a fullerene derivative. Operating at room temperature, the polymer photodetectors exhibit detectivities greater than 10(12) cm Hz(1/2)/W and a linear dynamic range over 100 decibels. The self-assembled nanomorphology and device architecture result in high photodetectivity over this wide spectral range and reduce the dark current (and noise) to values well below dark currents obtained in narrow-band photodetectors made with inorganic semiconductors.
A device configuration for light emission from electroactive polymers is described. In these light-emitting electrochemical cells, a p-n junction diode is created in situ through simultaneous p-type and n-type electrochemical doping on opposite sides of a thin film of conjugated polymer that contains added electrolyte to provide the necessary counterions for doping. Light-emitting devices based on conjugated polymers have been fabricated that operate by the proposed electrochemical oxidation-reduction mechanism. Blue, green, and orange emission have been obtained with turn-on voltages close to the band gap of the emissive material.
Some conjugated polymers have luminescence properties that are potentially useful for applications such as light-emitting diodes, whose performance is ultimately limited by the maximum quantum efficiency theoretically attainable for electroluminescence, ,. If the lowest-energy excited states are strongly bound excitons (electron-hole pairs in singlet or triplet spin states), this theoretical upper limit is only 25% of the corresponding quantum efficiency for photoluminescence: an electron in the π-band and a hole (or missing electron) in the π-band can form a triplet with spin multiplicity of three, or a singlet with spin multiplicity of one, but only the singlet will decay radiatively. But if the electron-hole binding energy is sufficiently weak, the ratio of the maximum quantum efficiencies for electroluminescence and photoluminescence can theoretically approach unity. Here we report a value of ∼50% for the ratio of these efficiencies (electroluminescence:photoluminescence) in polymer light-emitting diodes, attained by blending electron transport materials with the conjugated polymer to improve the injection of electrons. This value significantly exceeds the theoretical limit for strongly bound singlet and triplet excitons, assuming they comprise the lowest-energy excited states. Our results imply that the exciton binding energy is weak, or that singlet bound states are formed with higher probability than triplets.
The photosensitivity of semiconducting polymers can be enhanced by blending donor and acceptor polymers to optimize photoinduced charge separation. We describe a novel phase-separated polymer blend (composite) made with poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene], MEH-PPV, as donor and cyano-PPV, CN-PPV, as acceptor. The photoluminescence and electroluminescence of both component polymers are quenched in the blend, indicative of rapid and efficient separation of photogenerated electron-hole pairs with electrons on the acceptor and holes on the donor. Diodes made with such a composite semiconducting polymer as the photosensitive medium show promising photovoltaic characteristics with carrier collection efficiency of 5% electrons/photon and energy conversion efficiency of 0.9%, ∼20 times larger than in diodes made with pure MEH-PPV and ∼100 times larger than in diodes made with CN-PPV. The photosensitivity and the quantum yield increase with reverse bias voltage, to 0.3 A/W and 80% electrons/photon respectively at −10 V, comparable to results obtained from photodiodes made with inorganic semiconductors.
Solid-state polymer light-emitting electrochemical cells have been fabricated using thin films of blends of poly(1,4-phenylenevinylene) and poly(ethylene oxide) complexed with lithium trifluoromethanesulfonate. The cells contain three layers: the polymer film (as the emissive layer) and indium-tin oxide and aluminum films as the two contact electrodes. When externally biased, the conjugated polymers are p-doped and n-doped on opposite sides of the polymer layer, and a light-emitting p-n junction is formed in between. The admixed polymer electrolyte provides the counterions and the ionic conductivity necessary for doping. The p-n junction is dynamic and reversible, with an internal built-in potential close to the band gap of the redox-active conjugated polymer (2.4 eV for PPV). Green light emitted from the p-n junction was observed with a turn-on voltage of about 2.4 V. The devices reached 8 cd/m(2) at 3 V and 100 cd/m(2) at 4 V, with an external quantum efficiency of 0.3-0.4% photons/electron. The response speed of these cells was around 1 s, depending on the diffusion of ions. Once the light-emitting junction had been formed, the subsequent operation had fast response (microsecond scale or faster) and was no longer diffusion-controlled.
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