arXiv subjects

Vladimir Dyakonov

Publications and source records attributed to Vladimir Dyakonov.

At least 55 records · Page 3Linked to original sources

arXiv2012

Investigation of electronic trap states in organic photovoltaic materials by current-based deep level transient spectroscopy

Current-based deep level transient spectroscopy was used to study trap states in poly(3- hexylthiophene-2,5-diyl) (P3HT), [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) and P3HT:PCBM blend. The obtained spectra showed traps of 87 meV activation energy in pure P3HT and 21 meV for PCBM. The blend shows a complex emission rate spectrum consisting of several different emission rate bands in the range of (0.1-30) s^-1, yielding activation energies between about 30 meV and 160 meV.

cond-mat.mtrl-sci↗

arXiv2012

Direct and charge transfer mediated photogeneration in polymer-fullerene bulk heterojunction solar cells

We investigated photogeneration yield and recombination dynamics in blends of poly(3-hexyl thiophene) (P3HT) and poly[2-methoxy-5-(30,70-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) with [6,6]- phenyl-C61 butyric acid methyl ester (PC61BM) by means of temperature dependent time delayed collection field (TDCF) measurements. In MDMO-PPV:PC61BM we find a strongly field dependent polaron pair dissociation which can be attributed to geminate recombination in the device. Our findings are in good agreement with field dependent photoluminescence measurements published before, supporting a scenario of polaron pair dissociation via an intermediate charge transfer (CT) state. In contrast, polaron pair dissociation in P3HT:PC61BM shows only a very weak field dependence, indicating an almost field independent polaron pair dissociation or a direct photogeneration. Furthermore, we found Langevin recombination for MDMO-PPV:PC61BM and strongly reduced Langevin recombination for P3HT:PC61BM.

cond-mat.mtrl-sci↗

arXiv2012

Direct Detection of Photoinduced Charge Transfer Complexes in Polymer:Fullerene Blends

We report transient electron paramagnetic resonance (trEPR) measurements with sub-microsecond time resolution performed on a P3HT:PCBM blend at low temperature. The trEPR spectrum immediately following photoexcitation reveals signatures of spin-correlated polaron pairs. The pair partners (positive polarons in P3HT and negative polarons in PCBM) can be identified by their characteristic g-values. The fact that the polaron pair states exhibit strong non-Boltzmann population unambiguously shows that the constituents of each pair are geminate, i.e. originate from one exciton. We demonstrate that coupled polaron pairs are present even several microseconds after charge transfer and suggest that they embody the intermediate charge transfer complexes which form at the donor/acceptor interface and mediate the conversion from excitons into free charge carriers.

cond-mat.mtrl-sci↗

arXiv2011

Reversible and Irreversible Interactions of Poly(3-hexylthiophene) with Oxygen Studied by Spin-Sensitive Methods

Understanding of degradation mechanisms in polymer:fullerene bulk-heterojunctions on the microscopic level aimed at improving their intrinsic stability is crucial for the breakthrough of organic photovoltaics. These materials are vulnerable to exposure to light and/or oxygen, hence they involve electronic excitations. To unambiguously probe the excited states of various multiplicities and their reactions with oxygen, we applied combined magneto-optical methods based on multifrequency (9 and 275 GHz) electron paramagnetic resonance (EPR), photoluminescence (PL), and PL-detected magnetic resonance (PLDMR) to the conjugated polymer poly(3-hexylthiophene) (P3HT) and polymer:fullerene bulk heterojunctions (P3HT:PCBM; PCBM = [6,6]-phenyl-C61-butyric acid methyl ester). We identified two distinct photochemical reaction routes, one being fully reversible and related to the formation of polymer:oxygen charge transfer complexes, the other one, irreversible, being related to the formation of singlet oxygen under participation of bound triplet excitons on the polymer chain. With respect to the blends, we discuss the protective effect of the methanofullerenes on the conjugated polymer bypassing the triplet exciton generation.

cond-mat.mtrl-sci↗

arXiv2011

Binding energy of singlet excitons and charge transfer complexes in MDMO-PPV:PCBM solar cells

The influence of an external electric field on the photoluminescence intensity of singlet excitons and charge transfer complexes is investigated for a poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) diode and a bulk heterojunction of the PPV in combination with [6,6]-phenyl-C61 butyric acid methylester (PCBM), respectively. The experimental data is related to the dissociation probability derived from the Onsager-Braun model. In this way, a lower limit for the singlet exciton binding energy of MDMO-PPV is determined as (327 +- 30) meV, whereas a significantly lower value of (203 +- 18) meV is extracted for the charge transfer complex in a MDMO-PPV:PCBM blend.

cond-mat.mtrl-sci↗

arXiv2011

Observation of bi-polarons in blends of conjugated copolymers and fullerene derivatives

From a fundamental and application point of view it is of importance to understand how charge carrier generation and transport in a conjugated polymer (CP):fullerene blend are affected by the blend morphology. In this work light-induced electron spin resonance (LESR) spectra and transient ESR response signals are recorded on non-annealed and annealed blend layers consisting of alkyl substituted thieno[3,2-b]thiophene copolymers (pATBT) and the soluble fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) at temperatures ranging from 10 to 180 K. Annealing of the blend sample leads to a reduction of the steady state concentration of light-induced PCBM anions within the blend at low temperatures (T = 10 K) and continuous illumination. This is explained on the basis of the reducing interfacial area of the blend composite on annealing, and the high activation energy for electron diffusion in PCBM blends leading to trapped electrons near the interface with the CP. As a consequence, these trapped electrons block consecutive electron transfer from an exciton on a CP to the PCBM domain, resulting in a relatively low concentration charge carriers in the annealed blend. Analysis of the transient ESR data allows us to conclude that in annealed samples diamagnetic bi-polaronic states on the CPs are generated at low temperature. The formation of these states is related to the generation and interaction of multiple positive polarons in the large crystalline polymer domains present in the annealed sample.

cond-mat.soft↗

arXiv2011

Spin Signatures of Photogenerated Radical Anions in Polymer-[70]Fullerene Bulk Heterojunctions: High Frequency Pulsed EPR Spectroscopy

Charged polarons in thin films of polymer-fullerene composites are investigated by light-induced electron paramagnetic resonance (EPR) at 9.5 GHz (X-band) and 130 GHz (D-band). The materials studied were poly(3-hexylthiophene) (PHT), [6,6]-phenyl-C61-butyric acid methyl ester (C60-PCBM), and two different soluble C70-derivates: C70-PCBM and diphenylmethano[70]fullerene oligoether (C70-DPM-OE). The first experimental identification of the negative polaron localized on the C70-cage in polymer-fullerene bulk heterojunctions has been obtained. When recorded at conventional X-band EPR, this signal is overlapping with the signal of the positive polaron, which does not allow for its direct experimental identification. Owing to the superior spectral resolution of the high frequency D-band EPR, we were able to separate light-induced signals from P+ and P- in PHT-C70 bulk heterojunctions. Comparing signals from C70-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C70 molecule.

cond-mat.soft↗

arXiv2011

Detailed study of N,N'-(diisopropylphenyl)- terrylene-3,4:11,12-bis(dicarboximide) as electron acceptor for solar cells application

We report on terrylene-3,4:11,12-bis(dicarboximide) (TDI) as electron acceptor for bulk-heterojunction solar cells using poly(3-hexyl thiophene) (P3HT) as complementary donor component. Enhanced absorption was observed in the blend compared to pure P3HT. As shown by the very efficient photoluminescence (PL) quenching, the generated excitons are collected at the interface between the donor and acceptor, where they separate into charges which we detect by photoinduced absorption and electron-spin resonance (ESR). Time-of-flight (TOF) photoconductivity measurements reveal a good electron mobility of 10-3 cm2 V-1 s-1 in the blend. Nevertheless, the photocurrent in solar cells was found to be surprisingly low. Supported by the external quantum efficiency (EQE) spectrum as well as morphological studies by way of X-ray diffraction and atomic force microscopy, we explain our observation by the formation of a TDI hole blocking layer at the anode interface which prevents the efficiently generated charges to be extracted.

cond-mat.mtrl-sci↗

arXiv2011

Relation of open circuit voltage to charge carrier density in organic bulk heterojunction solar cells

The open circuit voltage Voc and the corresponding charge carrier density were measured in dependence of temperature and illumination intensity by current-voltage and charge extraction measurements for P3HT:PCBM and P3HT:bisPCBM solar cells. At lower temperatures a saturation of Voc was observed which can be explained by energetic barriers at the contacts (metal-insulator-metal model). Such injection barriers can also influence Voc at room temperature and limit the performance of the working solar cell, as was assured by macroscopic device simulations on temperature-dependent IV characteristics. However, under most conditions - room temperature and low barriers - Voc is given by the effective bandgap.

cond-mat.mtrl-sci↗

arXiv2011

Built-in potential and validity of Mott--Schottky analysis in organic bulk heterojunction solar cells

We investigated poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C61 butyric acid methyl ester bulk heterojunction (BHJ) solar cells by means of pulsed photocurrent, temperature dependent current-voltage and capacitance-voltage measurements. We show that a direct transfer of Mott-Schottky (MS) analysis from inorganic devices to organic BHJ solar cells is not generally appropriate to determine the built-in potential, since the resulting potential depends on the active layer thickness. Pulsed photocurrent measurements enabled us to directly study the case of quasi flat bands (QFB) in the bulk of the solar cell. It is well below the built-in potential and differs by diffusion-induced band-bending at the contacts. In contrast to MS analysis the corresponding potential is independent on the active layer thickness and therefore a better measure for flat band conditions in the bulk of a BHJ solar cell as compared to MS analysis.

cond-mat.mtrl-sci↗

arXiv2011

Electronic Trap States in Methanofullerenes

The trap states in three fullerene derivatives, namely PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), bisPC61BM (bis[6,6]-phenyl C61 butyric acid methyl ester) and PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), are investigated by thermally stimulated current measurements (TSC). Thereby, the lower limit of the trap densities for all studied methanofullerenes exhibits values in the order of 10^22 m^-3 with the highest trap density in bisPC61BM and the lowest in PC61BM. Fractional TSC measurements on PC61BM reveal a broad trap distribution instead of discrete trap levels with activation energies ranging from 15 meV to 270 meV and the maximum at about 75 meV. The activation energies of the most prominent traps in the other two fullerene derivatives are significantly higher, being at 96 meV and 223 meV for PC71BM and 184 meV for bisPC61BM, respectively. The influence of these findings on the performance of organic solar cells is discussed.

cond-mat.soft↗

arXiv2011

Triplet Exciton Generation in Bulk-Heterojunction Solar Cells based on Endohedral Fullerenes

Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu3N@C80 (Lu3N@C80-PCBEH) show an open circuit voltage (VOC) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC61BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (JSC) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the JSC in blends containing the high voltage absorber Lu3N@C80-PCBEH in view of both photogeneration but also transport and extraction of charge carriers. We apply optical, charge carrier extraction, morphology, and spin-sensitive techniques. In blends containing Lu3N@C80-PCBEH, we found 2 times weaker photoluminescence quenching, remainders of interchain excitons, and, most remarkably, triplet excitons formed on the polymer chain, which were absent in the reference P3HT:PC61BM blends. We show that electron back transfer to the triplet state along with the lower exciton dissociation yield due to intramolecular charge transfer in Lu3N@C80-PCBEH are responsible for the reduced photocurrent.

cond-mat.mtrl-sci↗

arXiv2011

Influence of Phase Segregation on Recombination Dynamics in Organic Bulk-Heterojunction Solar Cells

We studied the recombination dynamics of charge carriers in organic bulk heterojunction solar cells made of the blend system poly(2,5-bis(3-dodecyl thiophen-2-yl) thieno[2,3-b]thiophene) (pBTCT-C12):[6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) with a donor--acceptor ratio of 1:1 and 1:4. The techniques of charge carrier extraction by linearly increasing voltage (photo-CELIV) and, as local probe, time-resolved microwave conductivity (TRMC) were used. We observed a difference in the initially extracted charge carrier concentration in the photo-CELIV experiment by one order of magnitude, which we assigned to an enhanced geminate recombination due to a fine interpenetrating network with isolated phase regions in the 1:1 pBTCT-C12:PC61BM bulk heterojunction solar cells. In contrast, extensive phase segregation in 1:4 blend devices leads to an efficient polaron generation resulting in an increased short circuit current density of the solar cell. For both studied ratios a bimolecular recombination of polarons was found using the complementary experiments. The charge carrier decay order of above two for temperatures below 300 K can be explained by a release of trapped charges. This mechanism leads to a delayed bimolecular recombination processes. The experimental findings can be generalized to all polymer:fullerene blend systems allowing for phase segregation.

cond-mat.mtrl-sci↗

arXiv2011

Photoinduced C70 radical anions in polymer:fullerene blends

Photoinduced polarons in solid films of polymer-fullerene blends were studied by photoluminescence (PL), photoinduced absorption (PIA) and electron spin resonance (ESR). The donor materials used were P3HT and MEH-PPV. As acceptors we employed PC60BM as reference and various soluble C70-derivates: PC70BM, two different diphenylmethano-[70]fullerene oligoether (C70-DPM-OE) and two dimers, C70-C70 and C60-C70. Blend films containing C70 revealed characteristic spectroscopic signatures not seen with C60. Light-induced ESR showed signals at g\geq2.005, assigned to an electron localized on the C70 cage. The formation of C70 radical anions also leads to a subgap PIA band at 0.92 eV, hidden in the spectra of C70-based P3HT and MEH-PPV blends, which allows for more exact studies of charge separated states in conjugated polymer:C70 blends.

cond-mat.mtrl-sci↗

arXiv2010

Charge Carrier Extraction by Linearly Increasing Voltage:Analytic framework and ambipolar transients

Up to now the basic theoretical description of charge extraction by linearly increasing voltage (CELIV) is solved for a low conductivity approximation only. Here we present the full analytical solution, thus generalize the theoretical framework for this method. We compare the analytical solution and the approximated theory, showing that especially for typical organic solar cell materials the latter approach has a very limited validity. Photo-CELIV measurements on poly(3-hexyl thiophene-2,5-diyl):[6,6]-phenyl-C61 butyric acid methyl ester based solar cells were then evaluated by fitting the current transients to the analytical solution. We found that the fit results are in a very good agreement with the experimental observations, if ambipolar transport is taken into account, the origin of which we will discuss. Furthermore we present parametric equations for the mobility and the charge carrier density, which can be applied over the entire experimental range of parameters.

cond-mat.mtrl-sci↗

arXiv2010

Polymer-Fullerene Bulk Heterojunction Solar Cells

Organic solar cells have the potential to be low-cost and efficient solar energy converters, with a promising energy balance. They are made from carbon-based semiconductors, which exhibit favourable light absorption and charge generation properties, and can be manufactured by low temperature processes such as printing from solvent-based inks, which are compatible with flexible plastic substrates or even paper. In this review, we will present an overview of the physical function of organic solar cells, their state-of-the-art performance and limitations, as well as novel concepts to achieve a better material stability and higher power conversion efficiencies. We will also briefly review processing and cost in view of the market potential.

cond-mat.mtrl-sci↗

arXiv2010

Oxygen doping of P3HT:PCBM blends: Influence on trap states, charge carrier mobility and solar cell performance

We investigated the influence of oxygen on the performance of P3HT:PCBM (poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester) solar cells by current--voltage, thermally stimulated current (TSC) and charge extraction by linearly increasing voltage (CELIV) measurement techniques. The exposure to oxygen leads to an enhanced charge carrier concentration and a decreased charge carrier mobility. Further, an enhanced formation of deeper traps was observed, although the overall density of traps was found to be unaffected upon oxygen exposure. With the aid of macroscopic simulations, based on solving the differential equation system of Poisson, continuity and drift-diffusion equations in one dimension, we demonstrate the influence of a reduced charge carrier mobility and an increased charge carrier density on the main solar cell parameters, consistent with experimental findings.

cond-mat.mtrl-sci↗

arXiv2010

Effect of doping of zinc oxide on the hole mobility of poly(3-hexylthiophene) in hybrid transistors

Hybrid field effect transistors based on the organic polymer poly(3-hexylthiophene) (P3HT) and inorganic zinc oxide were investigated. In this report we present one of the first studies on hybrid transistors employing one polymeric transport layer. The sol-gel processed ZnO was modified via Al doping between 0.8 and 10 at.%, which allows a systematic variation of the zinc oxide properties, i.e. electron mobility and morphology. With increasing doping level we observe on the one hand a decrease of the electron mobilities by two orders of magnitude,on the other hand doping enforces a morphological change of the zinc oxide layer which enables the infiltration of P3HT into the inorganic matrix. X-ray reflectivity (XRR) measurements confirm this significant change in the interface morphology for the various doping levels. We demonstrate that doping of ZnO is a tool to adjust the charge transport in ZnO/P3HT hybrids, using one single injecting metal (Au bottom contact) on a SiO2 dielectric. We observe an influence of the zinc oxide layer on the hole mobility in P3HT which we can modify via Al doping of ZnO. Hence, maximum hole mobility of 5e-4 cm^2/Vs in the hybrid system with 2 at.% Al doping. 5 at.% Al doping leads to a balanced mobility in the organic/inorganic hybrid system but also to a small on/off ratio due to high off-currents.

cond-mat.mtrl-sci↗