Neil C. Greenham

MEASUREMENT OF ABSOLUTE PHOTOLUMINESCENCE QUANTUM EFFICIENCIES IN CONJUGATED POLYMERS

Abstract Measurements of absolute photoluminescence (PL) efficiencies have been performed for solid films of several conjugated polymers commonly used for electroluminescence. In poly( p -phenylenevinylene) (PPV), a PL efficiency of 0.27 is measured in samples which show an initial PL decay time-constant of 320 ps. These values indicate that photoexcitation in PPV produces intra-chain singlet excitons with a high quantum yield. The PL efficiencies of derivatives of PPV have been investigated, and efficiencies in excess of 0.4 have been measured for cyano-substituted PPVs.

Poly(p‐phenylenevinylene) light‐emitting diodes: Enhanced electroluminescent efficiency through charge carrier confinement

We have fabricated light‐emitting diodes with poly(p‐phenylenevinylene) as the emissive layer, and with an electron‐transporting layer formed from a solid state dispersion of 2‐(4‐biphenylyl)‐5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole in poly(methyl methacrylate), placed between this and the negative electrode. These structures show typically a tenfold improvement in efficiency in the low‐voltage regime and an eightfold improvement in the high‐voltage regime over devices without the electron‐transporting layer. Typical efficiencies are about 0.8% photons/electron. We consider that the role of the electron‐transport layer is to confine holes to the emissive layer.

Electroluminescence emission pattern of organic light-emitting diodes: Implications for device efficiency calculations

The electroluminescence (EL) pattern emitted through the surface and edge of the glass substrate of two efficient polymer light-emitting diodes (LEDs) has been characterized. The surface emission is nearly Lambertian, while the edge emission comprises discrete substrate reflection and leaky waveguide modes. A simple “half-space” optical model that accounts for optical interference effects of the metal cathode–reflector is developed to extract the location and orientation of the emitting dipoles from these patterns. Numerical simulations for a range of polymer and metal refractive indices show that the surface out-coupling efficiency ξ of the internally generated photons can be greater than the 0.5 n−2 relation (where n is the refractive index of the emitter layer) valid for isotropic emitters that are not subjected to optical interference effects. When the emitting dipoles are optimally located for maximum rate of surface emission, the model predicts ξ to vary as 0.75 n−2 for the isotropic case, and as 1....

Efficient Light-Emitting Diodes Based on Nanocrystalline Perovskite in a Dielectric Polymer Matrix

Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

Vertically segregated hybrid blends for photovoltaic devices with improved efficiency

Solution-processed photovoltaic devices based on blends of conjugated polymers and inorganic semiconductor tetrapods show high efficiencies due to the good electron transport perpendicular to the plane of the film. Here, we show that by using a high-boiling-point solvent, 1,2,4-trichlorobenzene, instead of chloroform for spin-coating, we can typically obtain a threefold increase in solar power conversion efficiency in devices based on CdSe tetrapods and the poly(p-phenylenvinylene) derivative OC1C10-PPV. The optimized devices show AM1.5 solar power conversion efficiencies of typically 2.1% with some devices as high as 2.8%. The results can be explained by the occurrence of vertical phase separation which leads to an optimal structure for charge collection. Evidence for this structure is obtained by environmental scanning electron microscopy, photocurrent action spectra measurements, time-resolved photoluminescence, and spectroscopic measurements of exciton dissociation and charge-carrier recombination.

Dual electron donor/electron acceptor character of a conjugated polymer in efficient photovoltaic diodes

The authors report efficient photovoltaic diodes which use poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2″-diyl) (F8TBT) both as electron acceptor, in blends with poly(3-hexylthiophene), and as hole acceptor, in blends with (6,6)-phenyl C61-butyric acid methyl ester. In both cases external quantum efficiencies of over 25% are achieved, with a power conversion efficiency of 1.8% under simulated sunlight for optimized F8TBT/poly(3-hexylthiophene) devices. The ambipolar nature of F8TBT is also demonstrated by the operation of light-emitting F8TBT transistors. The equivalent p- and n-type operation in this conjugated polymer represent an important extension of the range of useful n-type materials which may be developed.

Highly Efficient Perovskite Nanocrystal Light‐Emitting Diodes Enabled by a Universal Crosslinking Method

The preparation of highly efficient perovskite nanocrystal light-emitting diodes is shown. A new trimethylaluminum vapor-based crosslinking method to render the nanocrystal films insoluble is applied. The resulting near-complete nanocrystal film coverage, coupled with the natural confinement of injected charges within the perovskite crystals, facilitates electron-hole capture and give rise to a remarkable electroluminescence yield of 5.7%.

The origin of the open-circuit voltage in polyfluorene-based photovoltaic devices

The influence of device structure on the open-circuit voltage of polyfluorene-based photovoltaic devices has been investigated. Bilayers of hole- and electron-accepting polyfluorenes have been fabricated using an aqueous “float-off” lamination technique and subsequently incorporated into organic photovoltaic devices with a range of cathodes and anodes. A scaling of the open-circuit voltage with electrode work function difference has been observed with an additional intensity- dependent contribution from the active layer within the device. This additional contribution is attributed to photoinduced generation of carriers, whereby accumulation of charge at the polymer–polymer heterojunction results in a dipole across the interface and gives rise to a diffusion current that must be counterbalanced by a drift current at open circuit.

A microscopic model for the behavior of nanostructured organic photovoltaic devices

We present a Monte Carlo model of carrier separation and recombination in nanostructured organic photovoltaic (OPV) devices which takes into account all electrostatic interactions, energetic disorder, and polaronic effects. This permits a detailed analysis of the strong morphology dependence of carrier collection efficiency. We find that performance is determined both by the orientation of the heterojunction relative to the external electric field as well as by carrier confinement due to polymer intermixing. The model predicts that an idealized interdigitated structure could achieve overall efficiencies twice as high as blends. The model also reproduces the weakly sublinear intensity dependence of short-circuit photocurrent (ISC) seen in experiment. We show that this is not the result of space-charge effects but of bimolecular recombination. Disconnected islands of polymer in coarser blends result in bimolecular recombination even at low intensities and should therefore be minimized. By including a micros...

Charge Recombination in Organic Photovoltaic Devices with High Open-Circuit Voltages

A detailed charge recombination mechanism is presented for organic photovoltaic devices with a high open-circuit voltage. In a binary blend comprised of polyfluorene copolymers, the performance-limiting process is found to be the efficient recombination of tightly bound charge pairs into neutral triplet excitons. We arrive at this conclusion using optical transient absorption (TA) spectroscopy with visible and IR probes and over seven decades of time resolution. By resolving the polarization of the TA signal, we track the movement of polaronic states generated at the heterojunction not only in time but also in space. It is found that the photogenerated charge pairs are remarkably immobile at the heterojunction during their lifetime. The charge pairs are shown to be subject to efficient intersystem crossing and terminally recombine into F8BT triplet excitons within approximately 40 ns. Long-range charge separation competes rather unfavorably with intersystem crossing--75% of all charge pairs decay into triplet excitons. Triplet exciton states are thermodynamically accessible in polymer solar cells with high open circuit voltage, and we therefore suggest this loss mechanism to be general. We discuss guidelines for the design of the next generation of organic photovoltaic materials where separating the metastable interfacial charge pairs within approximately 40 ns is paramount.