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Improving the performance of doped p-conjugated polymers for use in organic light-emitting diodes
(2000)
Light-induced softening of azobenzene dye-doped polymer films probed with quartz crystal resonators
(2000)
Photoaddressable alignment layers for fluorescent polymers in polarized electroluminescence devices
(2002)
Chiroptcial properties of poly(p-phenyleneethynylene) copolymers in thin films : large g-values
(2002)
Suppression of the keto-emission in polyfluorene light-emitting diodes : Experiments and models
(2004)
The spectral characteristics of polyfluorene (PF)-based light-emitting diodes (LEDs) containing a defined low concentration of either keto-defects or of the polymer poly(9.9-octylfuorene-co-benzothiadiazole) (F8BT) are preseneted. Both types of blend layers were tested in different device configurations with respect to the relative and absolute intensities of green blue emission components. It is shown that blending hole-transporting molecules into the emission layer at low concentration or incorporation of a suitable hole-transport layer reduces the green emission contribution in the electroluminescence (EL) spectrum of the PF:F8BT blend, which is similar to what is observed for the keto- containing PF layer. We conclude that the keto-defects in PF homopolymer layers mainly constitute weakly emissive electron traps, in agreement with the results of quantum-mechanical calculations
We demonstrate efficient single-layer polymer phosphorescent light-emitting devices based on a green-emitting iridium complex and a polymer host co-doped with electron-transporting and hole-transporting molecules. These devices can be operated at relatively low voltages, resulting in a power conversion efficiency of up to 24 lm/W at luminous efficiencies exceeding 30 cd/A. The overall performances of these devices suggest that efficient electrophosphorescent devices with acceptable operating voltages can be achieved in very simple device structures fabricated by spin coating. (C) 2004 American Institute of Physics
Optically induced mass transport studied by scanning near-field optical- and atomic force microscopy
(2004)
Some functionalised thin organic films show a very unusual property, namely the light induced material transport. This effect enables to generate three-dimensional structures on surfaces of azobenzene containing films only caused by special optical excitation. The physical mechanisms underlying this phenomenon have not yet been fully understood, and in addition, the dimensions of structures created in that way are macroscopic because of the optical techniques and the wavelength of the used light. In order to gain deeper insight into the physical fundamentals of this phenomenon and to open possibilities for applications it is necessary to create and study structures not only in a macroscopic but also in nanometer range. We first report about experiments to generate optically induced nano structures even down to 100 nm size. The optical stimulation was therefore made by a Scanning Near-field Optical Microscope (SNOM). Secondly, physical conditions inside optically generated surface relief gratings were studied by measuring mechanical properties with high lateral resolution via pulse force mode and force distance curves of an AFM
The optical, structural, and electrical properties of thin layers made from poly(3-hexylthiophene) (P3HT) samples of different molecular weights are presented. As reported in a previous paper by Kline et al., Adv. Mater 2003, 15, 1519, the mobilities of these layers are a strong function of the molecular weight, with the largest mobility found for the largest molecular weight. Atomic force microscopy studies reveal a complex polycrystalline morphology which changes considerably upon annealing. X-ray studies show the occurrence of a layered phase for all P3HT fractions, especially after annealing at 1.50 degreesC . However, there is no clear correlation between the differences in the transport properties and the data from structural investigations. In order to reveal the processes limiting the mobility in these layers, the transistor properties were investigated as a function of temperature. The mobility decreases continuously with increasing temperatures; with the same trend pronounced thermochromic effects of the P3HT films occur. Apparently, the polymer chains adopt a more twisted, disordered conformation at higher temperatures, leading to interchain transport barriers. We conclude that the backbone conformation of the majority of the bulk material rather than the crystallinity of the layer is the most crucial parameter controlling the charge transport in these P3HT layers. This interpretation is supported by the significant blue-shift of the solid-state absorption spectra with decreasing molecular weight, which is indicative of a larger distortion of the P3HT backbone in the low-molecular weight P3HT layers
A commercially available Ir complex has been employed for the preparation of highly efficient (see Figure) single-layer phosphorescent polymer light,emitting diodes by use of appropriate thermal treatment and proper adjustment of the layer composition. These devices exhibit essentially no dependence of the driving field on the concentration of the Ir complex, suggesting that the build-up of space-charge in the layer is insignificant
Aggregation of chromophores in the solid state commonly causes undesirable red shifts in the emission spectra and/or emission quenching. To overcome this problem, we have prepared soluble perylenetetracarboxidiimide dyes in which the chromophores are effectively shielded by polyphenylene dendrimers attached in the bay positions. Models show that attachment of the shielding units in the bay position should provide more efficient shielding than attaching them via the imide moieties. The dendrimers possess excellent film-forming properties due to alkyl substituents on their peripheries. The lack of a red shift in emission upon going from solution to the solid state indicates the dendrons suppress interaction of the emissive cores, leading to pure red-orange emission. Single-layer LEDs produce red-orange emission with relatively low efficiency especially for the higher generation dendrons, which is attributed to poor charge conduction. LEDs using blends of the dendrimers and the undendronized dye as a model compound in PVK have been investigated, and a model to extract relative charge injection rates through the dendritic scaffold from the spectral contributions in the EL spectra is developed
Alkoxy-substituted CN-containing phenylene-vinylene-alt-phenylene-ethynylene hybrid polymers (CN-PPV-PPE), 3a, 3b, and 7a, were obtained from luminophoric dialdehydes 1 by step growth polymerization via Knoevenagel reaction as high molecular-weight materials. Corresponding CN-free polymers 3c and 7b and an ethynylene-free polymer 5 with similar side chains were synthesized for the purpose of comparison. The chemical structures of the polymers were confirmed by IR, H-1 and C-13 NMR, and elemental analysis. Thermal characterization was conducted by means of thermogravimetric analysis and differential scanning calorimetry. Morphology was investigated by means of optical microscopy and small-angle light scattering. The final morphologies are determined by the molecular characteristics (side chains volume fraction, backbone stiffness) of the studied polymers. All the CN-containing polymers 3b, 5, and 7a exhibit higher fluorescence quantum yield in solid state (50 to 60%), but lower quantum yields (12-40%) in dilute chloroform solution, in total contrast to CN-free polymers 3c, 3d, and 7b. Identical optical, E-g(opt), and electrochemical band gap energies, E- g(ec), were obtained for 3b, 3c and 3d with intrinsic self-assembly ability, whereas a discrepancy, DeltaE(g), was observed in the cases of the fully substituted polymers 5, 7a, and 7b, whose values are dependent on the level of backbone stiffness and length of the side groups combined with the presence or absence of CN units. The incorporation of CN units in 3b and 7a lowers their respective LUMO level by 220 and 350 meV compared to their corresponding CN-free counterparts 3c and 7b, suggesting an improvement of the electron-accepting strength. Polymers 3b and 7a are efficient electron acceptors suitable for photovoltaic application. The experiments indicate that 3b is a better electron acceptor when used together with M3EH-PPV, but transport properties seem to be better for 7a. With 3b, high external quantum efficiencies of up to 23%, an open circuit voltage of up to 1.52 V, and a white light energy efficiency of 0.65% could be realized in bilayer solar cell devices. LED-devices of configuration ITO/PEDOT:PSS/polymer/Ca/Al from 3b, 3c, 7a, and 7b showed low turn-on voltages between 2 and 2.5 V. The CN-free polymers 3c and 7b exhibit far better EL parameters than their corresponding CN containing counterparts 3b and 7a
All parameters describing the charge carrier dynamics in a poly(phenylene vinylene)-based photorefractive (PR) composite relevant to PR grating dynamics were determined using photoconductivity studies under various illumination conditions. In particular, the values of the coefficients for trap filling and recombination of charges with ionized sensitizer molecules could be extracted independently. It is concluded that the PR growth time without preillumination is mostly determined by the competition between deep trap filling and recombination with ionized sensitizer molecules. Further, the pronounced increase in PR speed upon homogeneous preillumination (gating) as reported recently is quantitatively explained by deep trap filling
Materials for polymer electronics applications semiconducting polymer thin films and nanoparticles
(2004)
The paper presents two different approaches to nanostructured semiconducting polymer materials: (i) the generation of aqueous semiconducting polymer dispersions (semiconducting polymer nanospheres SPNs) and their processing into dense films and layers, and (ii) the synthesis of novel semiconducting polyfluorene-block-polyaniline (PF-b-PANI) block copolymers composed of conjugated blocks of different redox potentials which form nanosized morphologies in the solid state
The delayed luminescence and phosphorescence of ladder-type methyl-poly(para-phenylene) (MeLPPP) doped with benzil at a concentration of 20% by weight has been measured. The introduction of benzil leads to a dramatic reduction of the polymer singlet emission. At the same time, a new band with maximum at 611 nm appears, corresponding to the phosphorescence of MeLPPP. The phosphorescence decay on the short time scale is close to an exponential law with a time decay of 15 ms. This indicates that benzil can efficiently sensitize the phosphorescence of the polymer. In addition, a broad and featureless emission is observed in the delayed luminescence spectra of benzil-doped MeLPPP, which is attributed to an exciplex formed between the polymer host and the dopant. We further observe that the delayed fluorescence is enhanced by the addition of benzil. It is concluded that the delayed fluorescence of benzil-doped MeLPPP is mainly due to the annihilation of triplet excitons on the polymer. Finally, efficient triplet-triplet energy transfer from the benzil-doped polymer to the red-emitting phosphorescent dye Pt(II)octaethylporphyrin is established. (C) 2004 American Institute of Physics
Polymer solar cell devices with nanostructured blend layers have been fabricated using single- and dual- component polymer nanospheres. Starting from an electron-donating and an electron-accepting polyfluorene derivative, PFB and F8BT, dissolved in suitable organic solvents, dispersions of solid particles with mean diameters of ca. 50 nm, containing either the pure polymer components or a mixture of PFB and F8BT in each particle, were prepared with the miniemulsion process. Photovoltaic devices based on these particles have been studied with respect to the correlation between external quantum efficiency and layer composition. It is shown that the properties of devices containing a blend of single-component PFB and F8BT particles differ significantly from those of solar cells based on blend particles, even for the same layer composition. Various factors determining the quantum efficiency in both kinds of devices are identified and discussed, taking into account the spectroscopic properties of the particles. An external quantum efficiency of ca. 4% is measured for a device made from polymer blend nanoparticles containing PFB:F8BT at a weight ratio of 1:2 in each individual nanosphere. This is among the highest values reported so far for photovoltaic cells using this material combination
Energy transfer in a ladder-type methyl-poly(para-phenylene) doped by Pt(II)octaethylporphyrin
(2004)
The luminescence of a ladder-type methyl-poly(para-phenylene) (MeLPPP) doped by platinum-porphyrin dye PtOEP covering the concentration 10(-3) to 5% by weight has been measured employing cw and transient techniques. Upon excitating into the range of absorption of the host strong phosphorescence of the dopant is observed. Possible ways of populating of the dopant triplet state are considered. It is shown that the main channel is singlet-singlet energy transfer among chromophor groups of the polymer followed by Forster-type transfer to the guest and subsequent intersystem crossing. (C) 2003 Elsevier B.V. All rights reserved
The performance of highly soluble regioregular poly[ (3-hexylthiophene)-co-(3-octylthiophetie)] (P3HTOT) as a semiconducting material in organic field-effect transistors (OFETs) is presented in comparison to that of the corresponding homopolymers. Transistors made from as-prepared layers of P3HTOT exhibit a mobility of ca. 7 x 10(-3) cm(2) V-1 s(-1), which is comparable to the performance of transistors made from as-prepared poly(3-hexylthiophene) (P3HT) and almost 6 times larger than the mobility of transistors prepared with poly(3-octylthiophene) (P3OT). On the other hand, the solubility parameter delta(p) of P3HTOT is close to that of the highly soluble P3OT. Moreover, compared to a physical blend of poly(3-hexylthiophene) and poly(3-octylthiophene), the mobility of P3HTOT devices is almost twice as large and the performance does not degrade upon annealing at elevated temperatures. Therefore, the copolymer approach outlined here may be one promising step toward an optimum balance between a Sufficient processability of the polymers from common organic solvents, a high solid state order, and applicable OFET performances
The effect of oxygen plasma treatment and/or silanization with hexamethyldisilazane (HMDS) on the surface chemistry and the morphology of the SiO2-gate insulator were studied with respect to the performance of organic field effect transistors. Using X-ray photoelectron spectroscopy (XPS), it is shown that silanization leads to the growth of a polysiloxane interfacial layer and that longer silanization times increase the thickness of this layer. Most important, silanization reduces the signal from surface contaminations such as oxidized hydrocarbon molecules. In fact, the lowest concentration of these contaminations was found after a combined oxygen plasma/silanization treatment. The results of these investigations were correlated with the characteristic device parameters of polymer field effect transistors with poly(3-hexylthiophene)s as the semiconducting layer. We found that the field effect mobility correlates with the concentration of contaminations as measured by XPS. We, finally, demonstrate that silanization significantly improves the operational stability of the device in air compared to the untreated devices
Thermodynamic theory of light-induced material transport in amorphous azobenzene polymer films
(2005)
It was discovered 10 years ago that the exposure of an initially flat layer of an azobenzene-containing polymer to an inhomogeneous light pattern leads to the formation of surface relief structures, accompanied by a mass transport over several micrometers. However, the driving force of this process is still unclear. We propose a new thermodynamic approach that explains a number of experimental findings including the light-induced deformation of free-standing films and the formation of surface relief gratings for main inscription geometries. Our basic assumption is that under homogeneous illumination, an initially isotropic sample should stretch itself along the polarization direction to compensate the entropy decrease produced by the photoinduced reorientation of azobenzene chromophores. The magnitude of the elastic stress, estimated by taking the derivative of the free energy over the sample deformation, is shown to be sufficient to induce plastic deformation of the polymer film. Orientational distributions of chromophores predicted by our model are compared with those deduced from Raman intensity measurements
Photoinduced changes in the mechanical and dielectric properties of azobenzene polymer films were measured utilizing the method of electromechanical spectroscopy. The measurements revealed a strong correlation between the time- dependent behavior of the plate compliance and the dielectric constant under irradiation. Actinic light causes a light softening of the film that also manifests itself in the increase of the dielectric constant, whereas ultraviolet irradiation results in an initial plasticization of the film followed by its hardening. The latter is accompanied by decrease of the dielectric constant. A semiquantitative model based on the kinetics of the photoisomerization process in azobenzene polymers is proposed. We assume that both visible and ultraviolet irradiation increase the free volume in the layer due to photoisomerization. Additionally, ultraviolet light increases the modulus of the polymer matrix due to the presence of a high density of azobenzene moieties in the cis state. These assumptions allowed us to reproduce the time- dependent behavior of the bulk compliance as well as the dielectric constant at different irradiation intensities, for both visible and ultraviolet light, with only two adjustable parameters
It is well known that the performance of solar cells based on a blend of hole-accepting and electron-accepting conjugated polymers as the active material depend crucially on the length scale of the resulting phase separated morphology. However, a direct control of this morphology is difficult if the layer is prepared from an organic solvent. To circumvent this difficulty, recently a universal method to fabricate defined nano-structured blend layer using nanoparticles dispersed in water was demonstrated. These nanoparticles were prepared with the miniemulsion method, which allows for the preparation of semiconducting polymer nanospheres (SPNs) with diameters in the range of 30 to 300 nanometres. Since the process starts from the active material dissolved in a common solvent, it can be applied to the fabrication of nanoparticles of blends of polymers with oligomers or even with inorganic materials. We present here for the first time scanning near field optical microscopy (SNOM) investigations on these novel nanostructured polymer layers. We show that by spin-coating a mixture of two different dispersions a nanoparticle monolayer with a statistically distribution of the nanoparticles can be obtained. Mixing conjugated polymer nanoparticles with some inert particles like polystyrene beads may allow for the preparation of nano-sized light emitters
An increase in random molecular vibrations of a solid owing to heating above the melting point leads to a decrease in its long-range order and a loss of structural symmetry. Therefore conventional liquids are isotropic media. Here we report on a light-induced isothermal transition of a polymer film from an isotropic solid to an anisotropic liquid state in which the degree of mechanical anisotropy can be controlled by light. Whereas during irradiation by circular polarized light the film behaves as an isotropic viscoelastic fluid, it shows considerable fluidity only in the direction parallel to the light field vector under linear polarized light. The fluidization phenomenon is related to photoinduced motion of azobenzene-functionalized molecular units, which can be effectively activated only when their transition dipole moments are oriented close to the direction of the light polarization. We also describe here how the photofluidization allows nanoscopic elements of matter to be precisely manipulated
This contribution reports the combined influences of odd-even effects and the specific positioning of alkoxy side chains OR1 = (OCn+H-10(2(n+10)+1)) and OR2 = (OCnH2n+1) (with n = 6, 7, 8, 9) on the phenylene-ethynylene and phenylene- vinylene segments, respectively, on the optical properties of hybrid polymers P(n+10)/n of general repeating unit: -Ph-C equivalent to C-Ph-C equivalent to C-Ph-CH=CH-Ph-CH=CH-. For the polymeric materials, visual color impression varies alternatively between orange red (P16/6 and P18/8) and yellow (P17/7 and P19/9) according to the odd and even features of the alkoxy side chains, where odd or even relates to the total number of sp(3)-hybridized atoms within the side chains. This side chain related effect is ascribed to both absorptive and emissive behaviors of the polymers on the basis of photophysical investigations in the bulk. Almost identical thin film absorption spectra were obtained for all four materials; however, the photoluminescence of the odd polymers, P16/6 (lambda(f) = 556 nm) and P18/ 8 (lambda(f) = 614 nm), was red-shifted relative to that of their even counterparts (lambda(f) = 535 nm). Further, the P18/8 maximum at 614 nm can be readily assigned to excimer emission, as evidenced by the largest Stokes shift (5600 cm(- 1)), largest fwhmf-value (3700 cm(-1))(,) and the lowest Phi(f)-value of 24%. The strong pi-pi interchain interaction in P18/8, due to loose alkoxy side chains packing, does not only favor fluorescence quenching but also enable an effective inter- as well as intra-molecular recombination of the generated positive and negative polarons in electrolurninescence, which explains the good EL properties of this polymer irrespective of the solvent used. A voltage-dependent blue shift of the EL spectra of up to 100 nm was observed for P18/8 devices prepared from aromatic solvents. This red to green EL shift as observed with increasing voltage is assigned to conformational changes of the polymer chains with increasing temperature
Diyne-containing poly(p-phenylene-vinylene)s, 4a-d, of general chemical structure-(Ph-C&3bond; C-C&3bond; C-Ph- CH&3bond; CH-Ph-CH&3bond; CH-)(n), obtained through polycondensation reactions of 1,4-bis(4-formyl-2,5-dioctyloxyphenyl)- buta-1,3-diyne (2) with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 3a-d, are the subject of this report. The polymers exhibit great disparity in their degree of polymerization, n, which might be ascribed to side-chain-related differences in reactivity of the reactive species during the polycondensation process and which led to n-dependent absorption (solution and solid state) and emission (solution) behaviors of the polymers. Polarizing optical microscopy and differential scanning calorimetry are employed to probe their thermal behavior. The structure is investigated by means of wide-angle X-ray diffraction for both isotropic and macroscopically oriented samples. Comparison of photophysical (experimental and theoretical) and electrochemical properties of the polymers with those of their yne- containing counterparts 6a-d [-(Ph-C&3bond; C-Ph-CH&3bond; CH-Ph-CH&3bond; CH-)(n)] has been carried out. Similar photophysical behavior was observed for both types of polymers despite the difference in backbone conjugation pattern. The introduction of a second yne unit in 4 lowers the HOMO and LUMO levels, thereby enhancing the electron affinity of polymers 4 compared to polymers 6. The "wider opening" introduced by the second yne unit facilitates moreover the movement of charges during the electrochemical processes leading to minimal discrepancy, Delta E-g between the optical and electrochemical band gap energies. Polymers 6, in contrast, show significant side-chain-dependent Delta E-g values. Low turn-on voltages between 2 and 3 V and maximal luminous efficiencies between 0.32 and 1.25 cd/A were obtained from LED devices of configuration ITO/PEDOT:PSS/polymer 4/Ca/Al
The luminescence of a ladder-type methyl-poly(para-phenylene) (MeLPPP) doped with platinum-porphyrin dye PtOEP covering the concentration 10(-3)-5% by weight has been measured employing cw and transient techniques. Upon excitation into the range of absorption of the host, strong phosphorescence of the dopant is observed. Possible ways of populating the dopant triplet state are considered. (c) 2004 Elsevier B.V. All rights reserved
We report on polymer blend solar cells with an external quantum efficiency of more than 30% and a hi-h overall energy conversion efficiency (ECE) under white light illumination (100 mW/cm(2)) Of Lip to 1.7% using a blend of M3EH- PPV (poly [2,5-dimethoxy-1,4-phenylene-1,2-ethenylene-2-methoxy-5(2-ethylhexyloxy)-(1,4-pheiiylene-1,2-ethenylene)]) and CN-ether-PPV (poly[oxa-1,4-phenylene-1,2(1-cyano)ethenylene-2,5-dioctyloxy-1,4-phenylene-1,2-(2-cyano)ethellyiene-1,4- phenylene]). We attribute these high efficiencies to the formation of a vertically composition graded structure during spin coating Photoluminescence measurements performed on the blend layers indicated the formation of exciplexes between both types of polymers, which we propose to be one factor preventing even higher efficiencies
Polymeric electrophosphorescent LEDs with internal quantum efficiencies approaching unity have been fabricated. Such performance levels are previously unknown for OLEDs. The key to this success is redox chemically doped oxetane- crosslinkable hole-transporting layers with multilayer capability (see figure). They improve hole injection and act as electron-blocking layers, without the need to include exciton-or hole-blocking layers
We have recently shown that efficient polymer solar cells can be fabricated by using a weakly soluble derivative of poly-p-vinylene (M3EH-PPV) as the electron donor. Here we present studies on bilayer devices using organic electron acceptors with varying LUMO levels and M3EH-PPV. It is found that the open-circuit voltage scales linearly with the LUMO level of the acceptor, reaching values as high as 1.5 V when cyano-substituted poly(p-phenyleneethynylene)-alt- poly(p-phenylenevinylene) copolymers are used. Further, we discovered that for an increasing number of triple bonds in the repeat unit of the acceptor polymer the device performance decreases with increasing thickness of the acceptor layer. Also, the quantum efficiency was smaller when using polymers with higher LUMO levels. Thus, further effort is needed to design optimum acceptor polymers for devices exhibiting large open-circuit voltage and high quantum efficiency
Photo-induced deformations in azobenzene-containing side-chain polymers : molecular dynamics study
(2006)
We perform molecular dynamics simulations of azobenzene containing side-chain liquid crystalline polymer subject to an external model field that mimicks the reorientations of the azobenzenes upon irradiation with polarized light. The smectic phase of the polymer is studied with the field applied parallel to the nematic director, forcing the trans isomers to reorient perpendicularly to the field (the direction of which can be assosiated with the light polarization). The coupling between the reorientation of azobenzenes and mechanical deformation of the sample is found to depend on the field strength. In a weak field the original smectic order is melted gradually with no apparent change in the simulation box shape, whereas in a strong field two regimes are observed. During the first one a rapid melting of the liquid crystalline order is accompanied by the contraction of the polymer along the field direction (the effect similar to the one observed experimentally in azopenzene containing elastomers). During the slower second regime, the smectic layers are rebuilt to accomodate the preferential direction of chromophores perperdicular to the field.
We investigated the spectral properties of light-emitting diodes based on a deep blue-emitting pyrazoloquinoline dye doped into a poly(N-vinylcarbazole)-based matrix. Even though the electroluminescence (EL) of the host is redshifted and broadened with respect to the emission of the dye, the EL spectrum becomes fully dominated by the dye emission at concentrations of ca. 2 wt %. This is attributed to a competition of exciplex formation on the matrix and exciton formation on the dye.
Tuning of the excited-state properties and photovoltaic performance in PPV-based polymer blends
(2008)
We report that the performances of blue polymer electrophosphorescent devices are crucially depending on the choice of the electron transporting material incorporated into the emissive layer. Devices with 1,3-bis[(4-tert- butylphenyl)-1,3,4-oxidiazolyl]phenylene (OXD-7) doped at similar to 40 wt% into a poly(vinylcarbazole) matrix exhibited significantly higher efficiencies than those with 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), yielding maximum luminous and power efficiency values of 18.2 Cd/A and 8.8 lm/W, respectively. Time resolved photoluminescence measurements revealed a long lifetime phosphorescence component in layers with PBD, which we assign to significant triplet harvesting by this electron-transporting component. (c) 2006 American Institute of Physics
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
Compared to their inorganic counterparts, organic semiconductors suffer from relatively low charge carrier mobilities. Therefore, expressions derived for inorganic solar cells to correlate characteristic performance parameters to material properties are prone to fail when applied to organic devices. This is especially true for the classical Shockley-equation commonly used to describe current-voltage (JV)-curves, as it assumes a high electrical conductivity of the charge transporting material. Here, an analytical expression for the JV-curves of organic solar cells is derived based on a previously published analytical model. This expression, bearing a similar functional dependence as the Shockley-equation, delivers a new figure of merit α to express the balance between free charge recombination and extraction in low mobility photoactive materials. This figure of merit is shown to determine critical device parameters such as the apparent series resistance and the fill factor.