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A novel fluorinated copolymer (F-PCPDTBT) is introduced and shown to exhibit significantly higher power conversion efficiency in bulk heterojunction solar cells with PC70BM compared to the well-known low-band-gap polymer PCPDTBT. Fluorination lowers the polymer HOMO level, resulting in high open-circuit voltages well exceeding 0.7 V. Optical spectroscopy and morphological studies with energy-resolved transmission electron microscopy reveal that the fluorinated polymer aggregates more strongly in pristine and blended layers, with a smaller amount of additives needed to achieve optimum device performance. Time-delayed collection field and charge extraction by linearly increasing voltage are used to gain insight into the effect of fluorination on the field dependence of free charge-carrier generation and recombination. F-PCPDTBT is shown to exhibit a significantly weaker field dependence of free charge-carrier generation combined with an overall larger amount of free charges, meaning that geminate recombination is greatly reduced. Additionally, a 3-fold reduction in non-geminate recombination is measured compared to optimized PCPDTBT blends. As a consequence of reduced non-geminate recombination, the performance of optimized blends of fluorinated PCPDTBT with PC70BM is largely determined by the field dependence of free-carrier generation, and this field dependence is considerably weaker compared to that of blends comprising the non-fluorinated polymer. For these optimized blends, a short-circuit current of 14 mA/cm(2), an open-circuit voltage of 0.74 V, and a fill factor of 58% are achieved, giving a highest energy conversion efficiency of 6.16%. The superior device performance and the low band-gap render this new polymer highly promising for the construction of efficient polymer-based tandem solar cells.
The incorporation of even small amounts of strontium (Sr) into lead-base hybrid quadruple cation perovskite solar cells results in a systematic increase of the open circuit voltage (V-oc) in pin-type perovskite solar cells. We demonstrate via absolute and transient photoluminescence (PL) experiments how the incorporation of Sr significantly reduces the non-radiative recombination losses in the neat perovskite layer. We show that Sr segregates at the perovskite surface, where it induces important changes of morphology and energetics. Notably, the Sr-enriched surface exhibits a wider band gap and a more n-type character, accompanied with significantly stronger surface band bending. As a result, we observe a significant increase of the quasi-Fermi level splitting in the neat perovskite by reduced surface recombination and more importantly, a strong reduction of losses attributed to non-radiative recombination at the interface to the C-60 electron-transporting layer. The resulting solar cells exhibited a V-oc of 1.18 V, which could be further improved to nearly 1.23 V through addition of a thin polymer interlayer, reducing the non-radiative voltage loss to only 110 meV. Our work shows that simply adding a small amount of Sr to the precursor solutions induces a beneficial surface modification in the perovskite, without requiring any post treatment, resulting in high efficiency solar cells with power conversion efficiency (PCE) up to 20.3%. Our results demonstrate very high V-oc values and efficiencies in Sr-containing quadruple cation perovskite pin-type solar cells and highlight the imperative importance of addressing and minimizing the recombination losses at the interface between perovskite and charge transporting layer.
We report on the structural and electronic interface formation between ITO (indium-tin-oxide) and prototypical organic small molecular semiconductors, i.e., CuPc (copper phthalocyanine) and alpha-NPD (N,N'-di(naphtalen-1-yl)- N,N'-diphenyl-benzidine). In particular, the effects of in situ oxygen plasma pretreatment of the ITO surface on interface properties are examined in detail: Organic layer-thickness dependent Kelvin probe measurements revealed a good alignment of the ITO work function and the highest occupied electronic level of the organic material in all samples. In contrast, the electrical properties of hole-only and bipolar organic diodes depend strongly on the treatment of ITO prior to organic deposition. This dependence is more pronounced for diodes made of polycrystalline CuPc than for those of amorphous alpha-NPD layers. X-ray diffraction and atomic force microscopic (AFM) investigations of CuPc nucleation and growth evidenced a more pronounced texture of the polycrystalline film structure on the ITO substrate that was oxygen plasma treated prior to organic layer deposition. These findings suggest that the anisotropic electrical properties of CuPc crystallites, and their orientation with respect to the substrate, strongly affect the charge carrier injection and transport properties at the anode interface.
We correlate the morphology and energy level alignment of bilayer structures comprising the donor poly(3-hexylthiophene) (P3HT) and the acceptor polyfluorene copolymer poly(9,90dialklylfluorene-alt-4,7-bis(2,5-thiendiyl)-2,1,3-benzothiadiazole) (PFTBTT) with the performance of these bilayers in organic photovoltaic cells (OPVCs). The conducting polymer poly(ethylenedioxythiophene): poly (styrenesulfonate) (PEDT:PSS) was used as the bottom electrode and Ca as the top electrode. Ultraviolet photoelectron spectroscopy (UPS) revealed that notable interface dipoles occur at all interfaces across the OPVC structure, highlighting that vacuum level alignment cannot reliably be used to estimate the electronic properties for device design. Particularly the effective electrode work function values (after contact formation with the conjugated polymers) differ significantly from those of the pristine electrode materials. Chemical reactions between PEDT: PSS and P3HT on the one hand and Ca and PFTBTT on the other hand are identified as cause for the measured interface dipoles. The vacuum level shift between P3HT and PFTBTT is related to mutual energy level pinning at gap states. Annealing induced morphological changes at the P3HT/PFTBTT interface increased the efficiency of OPVCs, while the electronic structure was not affected by thermal treatment.
The electrical conductivity of organic semiconductors can be enhanced by orders of magnitude via doping with strong molecular electron acceptors or donors. Ground-state integer charge transfer and charge-transfer complex formation between organic semiconductors and molecular dopants have been suggested as the microscopic mechanisms causing these profound changes in electrical materials properties. Here, we study charge-transfer interactions between the common molecular p-dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane and a systematic series of thiophene-based copolymers by a combination of spectroscopic techniques and electrical measurements. Subtle variations in chemical structure are seen to significantly impact the nature of the charge-transfer species and the efficiency of the doping process, underlining the need for a more detailed understanding of the microscopic doping mechanism in organic semiconductors to reliably guide targeted chemical design.
Electroluminescence (EL) spectra of hybrid charge transfer states at metal oxide/organic type-II heterojunctions exhibit bias-induced spectral shifts. The reasons for this phenomenon have been discussed controversially and arguments for either electric field-induced effects or the filling of trap states at the oxide surface have been put forward. Here, we combine the results of EL and photovoltaic measurements to eliminate the unavoidable effect of the series resistance of inorganic and organic components on the total voltage drop across the hybrid device. For SnOx combined with the conjugated polymer [ladder type poly-(para-phenylene)], we find a one-to-one correspondence between the blue-shift of the EL peak and the increase of the quasi-Fermi level splitting at the hybrid heterojunction, which we unambiguously assign to state filling. Our data are resembled best by a model considering the combination of an exponential density of states with a doped semiconductor. Published under license by AIP Publishing.
We investigate the bias dependence of the hybrid charge transfer state emission at planar heterojunctions between the metal oxide acceptor ZnO and three donor molecules. The electroluminescence peak energy linearly increases with the applied bias, saturating at high fields. Variation of the organic layer thickness and deliberate change of the ZnO conductivity through controlled photodoping allow us to confirm that this bias-induced spectral shift relates to the internal electric field in the organic layer rather than the filling of states at the hybrid interface. We show that existing continuum models overestimate the hole delocalization and propose a simple electrostatic model in which the linear and quadratic Stark effects are explained by the electrostatic interaction of a strongly polarizable molecular cation with its mirror image.
We use the Kelvin probe method to study the energy-level alignment of four conjugated polymers deposited on various electrodes. Band bending is observed in all polymers when the substrate work function exceeds critical values. Through modeling, we show that the band bending is explained by charge transfer from the electrodes into a small density of states that extends several hundred meV into the band gap. The energetic spread of these states is correlated with charge-carrier mobilities, suggesting that the same states also govern charge transport in the bulk of these polymers.
Moderate doping leads to high performance of semiconductor/insulator polymer blend transistors
(2013)
Polymer transistors are being intensively developed for next-generation flexible electronics. Blends comprising a small amount of semiconducting polymer mixed into an insulating polymer matrix have simultaneously shown superior performance and environmental stability in organic field-effect transistors compared with the neat semiconductor. Here we show that such blends actually perform very poorly in the undoped state, and that mobility and on/off ratio are improved dramatically upon moderate doping. Structural investigations show that these blend layers feature nanometre-scale semiconductor domains and a vertical composition gradient. This particular morphology enables a quasi three-dimensional spatial distribution of semiconductor pathways within the insulating matrix, in which charge accumulation and depletion via a gate bias is substantially different from neat semiconductor, and where high on-current and low off-current are simultaneously realized in the stable doped state. Adding only 5 wt% of a semiconducting polymer to a polystyrene matrix, we realized an environmentally stable inverter with gain up to 60.
A dual-characteristic polymer field-effect transistor has markedly different characteristics in low and high voltage operations. In the low-voltage range (<5 V) it shows sharp subthreshold slopes (0.3–0.4 V dec−1), using which a low-voltage inverter with gain 8 is realized, while high-voltage (>5 V) induces symmetric current with regard to drain and gate voltages, leading to discrete differential (trans) conductances.
Blending the conjugated polymer poly(3-hexylthiophene) (P3HT) with the insulating electret polystyrene (PS), we show that the threshold voltage V-t of organic field-effect transistors (OFETs) can be easily and reversely tuned by applying a gate bias stress at 130 degrees C. It is proposed that this phenomenon is caused by thermally activated charge injection from P3HT into PS matrix, and that this charge is immobilized within the PS matrix after cooling down to room temperature. Therefore, room-temperature hysteresis-free FETs with desired V-t can be easily achieved. The approach is applied to reversely tune the OFET mode of operation from accumulation to depletion, and to build inverters. (C) 2015 AIP Publishing LLC.
The optical signatures of molecular-doping induced polarons in poly(3-hexylthiophene-2,5-diyl)
(2020)
Optical absorption spectroscopy is a key method to investigate doped conjugated polymers and to characterize the doping-induced charge carriers, i.e., polarons. For prototypical poly(3-hexylthiophene-2,5-diyl) (P3HT), the absorption intensity of molecular dopant induced polarons is widely used to estimate the carrier density and the doping efficiency, i.e., the number of polarons formed per dopant molecule. However, the dependence of the polaron-related absorption features on the structure of doped P3HT, being either aggregates or separated individual chains, is not comprehensively understood in contrast to the optical absorption features of neutral P3HT. In this work, we unambiguously differentiate the optical signatures of polarons on individual P3HT chains and aggregates in solution, notably the latter exhibiting the same shape as aggregates in solid thin films. This is enabled by employing tris(pentafluorophenyl)borane (BCF) as dopant, as this dopant forms only ion pairs with P3HT and no charge transfer complexes, and BCF and its anion have no absorption in the spectral region of P3HT polarons. Polarons on individual chains exhibit absorption peaks at 1.5 eV and 0.6 eV, whereas in aggregates the high-energy peak is split into a doublet 1.3 eV and 1.65 eV, and the low-energy peak is shifted below 0.5 eV. The dependence of the fraction of solvated individual chains versus aggregates on absolute solution concentration, dopant concentration, and temperature is elucidated, and we find that aggregates predominate in solution under commonly used processing conditions. Aggregates in BCF-doped P3HT solution can be effectively removed upon simple filtering. From varying the filter pore size (down to 200 nm) and thin film morphology characterization with scanning force microscopy we reveal the aggregates' size dependence on solution absolute concentration and dopant concentration. Furthermore, X-ray photoelectron spectroscopy shows that the dopant loading in aggregates is higher than for individual P3HT chains. The results of this study help understanding the impact of solution pre-aggregation on thin film properties of molecularly doped P3HT, and highlight the importance of considering such aggregation for other doped conjugated polymers in general.
We investigate hybrid charge transfer states (HCTS) at the planar interface between a-NPD and ZnO by spectrally resolved electroluminescence (EL) and external quantum efficiency (EQE) measurements. Radiative decay of HCTSs is proven by distinct emission peaks in the EL spectra of such bilayer devices in the NIR at energies well below the bulk a-NPD or ZnO emission. The EQE spectra display low energy contributions clearly red-shifted with respect to the a-NPD photocurrent and partially overlapping with the EL emission. Tuning of the energy gap between the ZnO conduction band and a-NPD HOMO level (E-int) was achieved by modifying the ZnO surface with self-assembled monolayers based on phosphonic acids. We find a linear dependence of the peak position of the NIR EL on E-int, which unambiguously attributes the origin of this emission to radiative recombination between an electron on the ZnO and a hole on a-NPD. In accordance with this interpretation, we find a strictly linear relation between the open-circuit voltage and the energy of the charge state for such hybrid organicinorganic interfaces.
Current models for molecular electrical doping of organic semiconductors are found to be at odds with other well-established concepts in that field, like polaron formation. Addressing these inconsistencies for prototypical systems, we present experimental and theoretical evidence for intermolecular hybridization of organic semiconductor and dopant frontier molecular orbitals. Common doping-related observations are attributed to this phenomenon, and controlling the degree of hybridization emerges as a strategy for overcoming the present limitations in the yield of doping-induced charge carriers.
The authors present efficient all-polymer solar cells comprising two different low-bandgap naphthalenediimide (NDI)-based copolymers as acceptors and regioregular P3HT as the donor. It is shown that these naphthalene copolymers have a strong tendency to preaggregate in specific organic solvents, and that preaggregation can be completely suppressed when using suitable solvents with large and highly polarizable aromatic cores. Organic solar cells prepared from such nonaggregated polymer solutions show dramatically increased power conversion efficiencies of up to 1.4%, which is mainly due to a large increase of the short circuit current. In addition, optimized solar cells show remarkable high fill factors of up to 70%. The analysis of the blend absorbance spectra reveals a surprising anticorrelation between the degree of polymer aggregation in the solid P3HT:NDI copolymer blends and their photovoltaic performance. Scanning near-field optical microscopy (SNOM) and atomic force microscopy (AFM) measurements reveal important information on the blend morphology. It is shown that films with high degree of aggregation and low photocurrents exhibit large-scale phase-separation into rather pure donor and acceptor domains. It is proposed that, by suppressing the aggregation of NDI copolymers at the early stage of film formation, the intermixing of the donor and acceptor component is improved, thereby allowing efficient harvesting of photogenerated excitons at the donoracceptor heterojunction.
The recent development of donor–acceptor copolymers has led to an enormous improvement in the performance of organic solar cells and organic field-effect transistors. Here we describe the synthesis, detailed characterisation, and application of a series of structurally modified copolymers to investigate fundamental structure–property relationships in this class of conjugated polymers. The interplay between chemical structure and optoelectronic properties is investigated. These are further correlated to the charge transport and solar cell performance, which allows us to link their chemical structure to the observed physical properties.