Donor-acceptor Blends Research Articles

The Role of Electron–Hole Separation in Thermally Activated Delayed Fluorescence in Donor–Acceptor Blends

Thermally activated delayed fluorescence (TADF) is becoming an increasingly important OLED technology that extracts light from nonemissive triplet states via reverse intersystem crossing (RISC) to the bright singlet state. Here we present the rather surprising finding that in TADF materials that contain a mixture of donor and acceptor molecules the electron–hole separation fluctuates as a function of time. By performing time-resolved photoluminescence experiments, both with and without a magnetic field, we observe that at short times the TADF dynamics are insensitive to magnetic field, but a large magnetic field effect (MFE) occurs at longer times. We explain these observations by constructing a quantum mechanical rate model in which the electron and hole cycle between a near-neighbor exciplex state that shows no MFE and a separated polaron-pair state that is not emissive but does show magnetic field dependent dynamics. Interestingly, the model suggests that only a portion of TADF in these blends comes fr...

Nanoscale transport of charge-transfer states in organic donor-acceptor blends.

Charge-transfer (CT) states, bound combinations of an electron and a hole on separate molecules, play a crucial role in organic optoelectronic devices. We report direct nanoscale imaging of the transport of long-lived CT states in molecular organic donor-acceptor blends, which demonstrates that the bound electron-hole pairs that form the CT states move geminately over distances of 5-10 nm, driven by energetic disorder and diffusion to lower energy sites. Magnetic field dependence reveals a fluctuating exchange splitting, indicative of a variation in electron-hole spacing during diffusion. The results suggest that the electron-hole pair of the CT state undergoes a stretching transport mechanism analogous to an 'inchworm' motion, in contrast to conventional transport of Frenkel excitons. Given the short exciton lifetimes characteristic of bulk heterojunction organic solar cells, this work confirms the potential importance of CT state transport, suggesting that CT states are likely to diffuse farther than Frenkel excitons in many donor-acceptor blends.

Influence of side groups on the performance of infrared absorbing aza‐BODIPY organic solar cells

AbstractAbstractauthoren Organic solar cells are a promising technology for a large area conversion of sunlight into electricity. In particular for solar cells based on oligomers (small molecules), efficient donor materials absorbing wavelengths larger than 780 nm are still rare. Here, we investigate three aza‐BODIPY dyes absorbing in the infrared. The addition of side groups leads to a red shift of the optical gap from 802 to 818 nm. In optimized devices using these donors in a bulk heterojunction with , we observe a higher charge carrier mobility and a higher power conversion efficiency for the molecules without a methyl or methoxy side group lowering the molecular reorganization energy. Surprisingly, the donor–acceptor blend with the lowest energy loss during the electron transfer to the yields the highest short circuit current. With increasing size of the attached side chain, the devices exhibit a larger trap density, measured by impedance spectroscopy. Based on the investigation of different blend ratios, we conclude that these traps are mainly present in the donor phase.

Pronounced Cosolvent Effects in Polymer:Polymer Bulk Heterojunction Solar Cells with Sulfur-Rich Electron-Donating and Imide-Containing Electron-Accepting Polymers.

The performance of solar cells with a polymer:polymer bulk heterojunction (BHJ) structure, consisting of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th) donor and poly[[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)] (P(NDI2OD-T2)) acceptor polymers, was investigated as a function of cosolvent (p-xylene:chlorobenzene (pXL:CB)) composition ratio. A remarkable efficiency improvement (∼38%) was achieved by spin-coating the photoactive blend layer from pXL:CB = 80:20 (volume) rather than pXL alone, but the efficiency then decreased when the CB content increased further to pXL:CB = 60:40. The improved efficiency was correlated with a particular PTB7-Th:P(NDI2OD-T2) donor-acceptor blend nanostructure, evidenced by a fiber-like surface morphology, a red-shifted optical absorption, and enhanced PL quenching. Further device optimization for pXL:CB = 80:20 films yielded a power conversion efficiency of ∼5.4%. However, these devices showed very poor stability (∼15 min for a 50% reduction in initial efficiency), owing specifically to degradation of the PTB7-Th donor-component. Replacing PTB7-Th with a more stable donor polymer will be essential for any application potential to be realized.

Density of states determination in organic donor-acceptor blend layers enabled by molecular doping

Charge carrier transport is a key parameter determining the efficiency of organic solar cells, and is closely related to the density of free and trapped states. For trap characterization, impedance spectroscopy is a suitable, non-invasive method, applicable to complete organic semiconductor devices. In order to contribute to the capacitive signal, the traps must be filled with charge carriers. Typically, trap filling is achieved by illuminating the device or by injecting charge carriers through application of a forward bias voltage. However, in both cases, the exact number of charge carriers in the device is not known and depends strongly on the measurement conditions. Here, hole trap states of the model blend layer ZnPc:C60 are filled by weak p-doping, enabling trap characterization in a blend layer at a controlled hole density. We evaluate impedance spectra at different temperatures in order to determine the density of occupied states (DOOS) directly from the capacitance-frequency spectra by assuming a simple energy diagram. The reconstructed DOOS distribution is analyzed at different doping concentrations and device thicknesses and compared to thermally stimulated current measurements performed on the same devices. In both methods, a pronounced Gaussian peak at about 0.4 eV below the transport level is found as well as deep, exponential tail states, providing a deeper insight into the density of states distribution of this donor-acceptor blend layer. Additionally, the effect of doping-induced trap filling on the solar cell characteristics is studied in these devices.

Driving Force Dependence of Electron Transfer Kinetics and Yield in Low-Band-Gap Polymer Donor–Acceptor Organic Photovoltaic Blends

The rate of photoinduced electron transfer (PET) (κPET), quantum yield of PET (QYPET), and charge extraction yield (EQE) are determined for a series of donor–acceptor (DA) organic photovoltaic systems, comprising low-band-gap polymer donors and the phenyl-C61-butyric acid methyl ester (PCBM) acceptor. The energetic alignment of these polymer donors relative to PCBM provides driving forces for PET (ΔGPET) in the range of 0.18–0.57 eV. Femtosecond transient absorption (TA) spectroscopy was used to assess the PET kinetics and QYPET, while time-resolved charge extraction (TRCE) measurements were employed to assess EQE. Near unity QYPET was observed in DA blend films with a ΔGPET of 0.57 and 0.30 eV, whereas no resolvable PET was observed with a ΔGPET of 0.18 eV. For the DA blends that exhibit PET, both κPET and QYPET appear independent of ΔGPET, with an average κPET of 420 fs for the 70% PCBM blends. An increase in nanosecond charge separation yield (TA) and EQE (TRCE) between DA systems was observed, which appears not to be due to the PET process but rather the subsequent recombination processes. DA systems should be designed to minimize ΔGPET, minimizing associated losses in device open-circuit potential; however, picosecond bimolecular recombination severely limits achievable charge extraction yields in these DA systems.

Heteromolecular metal–organic interfaces: Electronic and structural fingerprints of chemical bonding

Beside the fact that they attract highest interest in the field of organic electronics, heteromolecular structures adsorbed on metal surfaces, in particular donor–acceptor blends, became a popular field in fundamental science, possibly since some surprising and unexpected behaviors were found for such systems. One is the apparent breaking of a rather fundamental rule in chemistry, namely that stronger chemical bonds go along with shorter bond lengths, as it is, e.g., well-known for the sequence from single to triple bonds. In this review we summarize the results of heteromolecular monolayer structures adsorbed on Ag(111), which – regarding this rule – behave in a counterintuitive way. The charge acceptor moves away from the substrate while its electronic structure indicates a stronger chemical interaction, indicated by a shift of the formerly lowest unoccupied molecular orbital toward higher binding energies. The donor behaves in the opposite way, it gives away charge, hence, electronically the bonding to the surface becomes weaker, but at the same time it also approaches the surface. It looks as if the concordant link between electronic and geometric structure was broken. But both effects can be explained by a substrate-mediated charge transfer from the donor to the acceptor. The charge reorganization going along with this transfer is responsible for both, the lifting-up of the acceptor molecule and the filling of its LUMO, and also for the reversed effects at the donor molecules. In the end, both molecules mutually enhance their respective donor and acceptor characters. We argue that this effect is of general validity for π-conjugated molecules adsorbing on noble metal surfaces.

The impact of driving force on electron transfer rates in photovoltaic donor-acceptor blends.

The effect of acceptor energy level on electron transfer rate in blends of the polymer solar-cell material poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7) is studied using time-resolved fluorescence. Fast electron transfer in less than 2 ps is observed for a driving force between 0.2 and 0.6 eV and the electron transfer is slower outside this range. This dependence is described by Marcus theory with a reorganization energy of ≈0.4 eV.

A charge carrier transport model for donor-acceptor blend layers

Highly efficient organic solar cells typically comprise donor-acceptor blend layers facilitating effective splitting of excitons. However, the charge carrier mobility in the blends can be substantially smaller than in neat materials, hampering the device performance. Currently, available mobility models do not describe the transport in blend layers entirely. Here, we investigate hole transport in a model blend system consisting of the small molecule donor zinc phthalocyanine (ZnPc) and the acceptor fullerene C60 in different mixing ratios. The blend layer is sandwiched between p-doped organic injection layers, which prevent minority charge carrier injection and enable exploiting diffusion currents for the characterization of exponential tail states from a thickness variation of the blend layer using numerical drift-diffusion simulations. Trap-assisted recombination must be considered to correctly model the conductivity behavior of the devices, which are influenced by local electron currents in the active layer, even though the active layer is sandwiched in between p-doped contacts. We find that the density of deep tail states is largest in the devices with 1:1 mixing ratio (Et = 0.14 eV, Nt = 1.2 × 1018 cm−3) directing towards lattice disorder as the transport limiting process. A combined field and charge carrier density dependent mobility model are developed for this blend layer.

Charge trapping in mixed organic donor-acceptor semiconductor thin films.

A pump-probe method, whereby trapped charges are optically induced to contribute to the total photocurrent, is applied to quantitatively determine the trap density in small-molecule organic semiconductor thin films and donor-acceptor blends used in organic solar cells. The trapped charge density is correlated to the cell performance, and the dependence of charge trapping on the presence of nanocrystalline domains is discussed.

High open circuit voltage organic solar cells based upon fullerene free bulk heterojunction active layers

We have recently reported on a small organic molecule containing a bithiophene core with end-capping phthalimide units (PthTh2Pth) that exhibited a H-aggregation tendency in the solid state and high electron mobility in organic field effect transistors. In this contribution, we have studied both the physical and electrical properties of poly(3-hexylthiophene) (P3HT) and PthTh2Pth thin films by measuring the optical absorption, Frontier molecular orbital energy levels, photoluminescence quenching, thermal properties, and photovoltaic response. Our results have provided a useful insight into the use of PthTh2Pth as an electron acceptor material for organic photovoltaic applications. In comparison with high-performance, fullerene-based, solution-processed bulk heterojunction solar cells reported in the literature, a relatively high open circuit voltage (∼0.94 V) was obtained for various donor–acceptor blend ratios. These results highlight the potential for PthTh2Pth to act as an alternative to fullerenes as acceptors in organic solar cell devices.

High efficiency organic photovoltaic cells based on inverted SubPc/C60/ITO cascade junctions

Conventional heterojunction organic photovoltaic cells typically involve the deposition of the electron donor layer (or donor–acceptor blend) on top of a transparent anode, with the cathode deposited last. Inverting the structure and deposition sequence usually worsens the performance characteristics, except device lifetime. We compare conventional (SubPc/C60) and inverted (C60/SubPc) junctions, the latter exhibiting a power conversion efficiency of 3.5%. We also find a significant trade-off between the open circuit voltage and short circuit photocurrent, potentially attributable to the formation of a C60/ITO Schottky junction, and a change from exciton-quenching to exciton-blocking behavior of the SubPc:MoOX interface in inverted devices.

Electrochemical Synthesis of Composites Based on Polythiophenes and Carbon Materials for Use in Photovoltaic Systems

Solar radiation is the renewable energy source with practically unlimited access. Scientific research has development devices capable of transforming this vast resource into electrical energy (solar cells). The organic solar cells (OSC) have emerged as a promising photovoltaic (PV) technology because of he possibility of low cost production and flexible devices. In a normal structured OSC device, the active layer of donor–acceptor blend is sandwiched between the indium tin oxide or ITO (anode) coated on the glass substrate and a low work function metal (cathode). The active layer of OPV is constituted by a mixture of a polymer electron-donating (conjugated polymer) and electron-acceptor compounds (usually fullerene derivatives). This material is blended in a bulk heterojunction architecture in order to enhance the performance device. Currently there are several ways to deposit the active layer (spary coting, thermal evaporation, spin coating), using mainly polymeric chains, aqueous systems and high weight molecules.The use of electrochemical techniques for the development of conductive polymers, has primarily focused on understanding the mechanisms of polymerization, growth and redox behavior of these. The use of these methods has resulted in the development of polymer films with potential use in transistors, diodes and others.The aim of this research is the development of photovoltaic devices using electrochemical techniques (cyclic voltammetry and constant potential) to generate the active layer of a conventional device. Performing in situ polymerization, incorporating of electroaceptor material in organic solvents.The deposits of the active layer is made using a three electrode cell convecional, ITO working electrode, a platinum plate counter electrode, and Ag/AgNO3 reference electrode in acetonitrile, using bithiophene as electron donor molecules, oxidized multi-walled carbon nanotubes, oxidized graphene, ICBA and PCBM as acceptor molecules. Getting different morphologies and behaviors. Morphological analysis of the films were performed using an atomic force microscope (AFM). Determining the morphology and thickness of these layers.The photovoltaic device was completed using Wood's metal as cathode, thus different devices were obtained.Finally, the JV curves were obtained of the photovoltaic devices.

Short-lived charge-transfer excitons in organic photovoltaic cells studied by high-field magneto-photocurrent.

The main route of charge photogeneration in efficient organic photovoltaic cells based on bulk hetero-junction donor-acceptor blends involves short-lived charge-transfer excitons at the donor-acceptor interfaces. The cell efficiency is critically affected by the charge-transfer exciton recombination and dissociation processes. By measuring the magneto-photocurrent under ambient conditions at room temperature, we show here that magnetic field-induced spin-mixing among the charge-transfer exciton spin sublevels occurs in fields up to at least 8.5 Tesla. The resulting magneto-photocurrent increases at high fields showing non-saturating behaviour up to the highest applied field. We attribute the observed high-field spin-mixing mechanism to the difference in the donor-acceptor g-factors. The non-saturating magneto-photocurrent response at high field indicates that there exist charge-transfer excitons with lifetime in the sub-nanosecond time domain. The non-Lorentzian high-field magneto-photocurrent response indicates a dispersive decay mechanism that originates due to a broad distribution of charge-transfer exciton lifetimes.

Relationship between interchain interaction, exciton delocalization, and charge separation in low-bandgap copolymer blends.

We present a systematic study of the roles of crystallinity, interchain interaction, and exciton delocalization on ultrafast charge separation pathways in donor-acceptor copoloymer blends. We characterize the energy levels, excited state structures, and dynamics of the interchain species by combined ultrafast spectroscopy and computational quantum chemistry approaches. The alkyl side chain of a highly efficient donor-acceptor copolymer for solar cell applications, PBDTTT (poly(4,8-bis-alkyloxybenzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-(alkylthieno[3,4-b]thiophene-2-carboxylate)-2,6-diyl), is varied to tune the molecular packing and interchain interaction of the polymers in order to elucidate the charge separation pathways originating from intrachain and interchain species. Polymers with linear side chains result in more crystalline polymer domain that lead to preferential formation of interchain excitons delocalizing over more than one polymer backbone in the solid state. Our results demonstrate that the higher polymer crystallinity leads to slower charge separation due to coarser phase segregation and formation of the interchain excited states that are energetically unfavorable for charge separation. Such energetics of the interchain excitons in low-bandgap copolymers calls for optimized solar cell morphologies that are fundamentally different from those based on homopolymers such as P3HT (poly-3-hexylthiophene). A long-range crystalline polymer domain is detrimental rather than beneficial to solar cell performance for a low-bandgap copolymer which is in direct contrast to the observed behavior in P3HT based devices.

Improvement of intramolecular charge transfer within a donor–acceptor blend by doping novel synthesized benzothiadiazole small molecules in solid state

Three electron-deficient small molecules based on 2,1,3-benzothiadiazole (BTD) units namely, 4,7-bis(3-methoxyphenyl)-2,1,3-benzothiadiazole (BT1), (3-{7-[3-(dimethylamino)phenyl]-2,1,3-benzothiadiazole-4-yl}phenyl)dimethylamine (BT2) and 3,3′-(2,1,3-benzothiadiazole-4,7-dyl)dianiline (BT3) were synthesized and their photophysical properties were investigated systematically to understand their potential usage in ternary organic solar cells (OSCs) as additive material to enhance the cell efficiency. All these molecules show broad absorption bands in 350–750nm on glass substrate and their optical band gaps were calculated to be around 2.50–2.80eV. BTD fluorescence dynamics were measured in polymer:BT1:fullerene blends with varying emission wavelengths of active layer. Fluorescence emission and time resolved measurements indicated photoinduced energy shift from BT1 dye to fullerene and also from polymer to BT1 dye upon excitation of the active layer.

Inverted bulk-heterojunction solar cell with cross-linked hole-blocking layer

We have developed a hole-blocking layer for bulk-heterojunction solar cells based on cross-linked polyethylenimine (PEI). We tested five different ether-based cross-linkers and found that all of them give comparable solar cell efficiencies. The initial idea that a cross-linked layer is more solvent resistant compared to a pristine PEI layer could not be confirmed. With and without cross-linking, the PEI layer sticks very well to the surface of the indium–tin–oxide electrode and cannot be removed by solvents used to process PEI or common organic semiconductors. The cross-linked PEI hole-blocking layer functions for multiple donor–acceptor blends. We found that using cross-linkers improves the reproducibility of the device fabrication process.

Polymer nanofibers: preserving nanomorphology in ternary blend organic photovoltaics.

The morphology of donor-acceptor blends holds the key to good performance through the balancing of good exciton dissociation efficiency and interconnectivity for good charge collection. In this work, the good morphology is preserved in ternary blend systems through the use of poly(3-hexylthiophene) (P3HT) nanofibers. The iridium(III)-based metal complex is incorporated in P3HT-PCBM blends as a triplet exciton sensitizer in the bulk heterojunction (BHJ) organic photovoltaics (OPV). The devices using triplet-sensitized ternary blends of P3HT experience a significant degradation in performance, a tendency further aggravated by thermal treatment. This is due to disruption in the morphology thus affecting charge generation and collection. In order to overcome these morphological issues and to circumvent the restriction due to the crystallization of the polymers, here we demonstrate the use of pre-assembled nanofibers in these ternary blends. The concept of stabilizing the nanomorphology of the blend material through the use of nanofibers can also be applied to other ternary systems.

Synthesis and optoelectronic properties of new D–A copolymers based on fluorinated benzothiadiazole and benzoselenadiazole

Two donor–acceptor (D–A) copolymers (PBDTBT and PBDTBSe) based on bithienyl-benzodithiophene (BDT) as the donor (D) unit, fluorinated benzothiadiazole (BT) or benzoselenadiazole (BSe) as the acceptor (A) unit, were designed and synthesized. The optoelectronic properties of the two polymers, including the absorption spectra, electronic energy levels, hole mobility and photovoltaic properties, were fully studied and compared. The effects of the replacement of S by Se in the BT unit and F substitution on their optoelectronic properties were investigated in detail. The replacement of S by Se in the benzothiadiazole unit red-shifted the absorption spectra and increased the hole mobility of the D–A copolymers. Polymer solar cells (PSCs) based on the polymers as the donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM) as the acceptor were fabricated, and the photovoltaic performance of the PSCs was optimized by optimizing the device fabrication conditions, including the solvent, donor–acceptor blend ratio, thermal annealing and solvent additive. The highest power conversion efficiency (PCE) of the optimized PSCs based on the polymers reached 5.06% and 2.20% for PBDTBT and PBDTBSe, respectively. The lower photovoltaic performance of the PSCs based on PBDTBSe is due to the poorer morphology of its active layer.

Improved efficiency of bulk heterojunction hybrid solar cells by utilizing CdSe quantum dot-graphene nanocomposites.

We present a significant efficiency enhancement of hybrid bulk heterojunction solar cells by utilizing CdSe quantum dots attached to reduced graphene oxide (rGO) as the electron accepting phase, blended with the PCPDTBT polymer. The quantum dot attachment to rGO was achieved following a self-assembly approach, recently developed, using thiolated reduced graphene oxide (TrGO) to form a TrGO-CdSe nanocomposite. Therefore, we are able to obtain TrGO-CdSe quantum dot/PCPDTBT bulk-heterojunction hybrid solar cells with power conversion efficiencies of up to 4.2%, compared with up to 3% for CdSe quantum dot/PCPDTBT devices. The improvement is mainly due to an increase of the open-circuit voltage from 0.55 V to 0.72 V. We found evidence for a significant change in the heterojunction donor-acceptor blend nanomorphology, observable by a more vertical alignment of the TrGO-quantum dot nanocomposites in the z-direction and a different nanophase separation in the x-y direction compared to the quantum dot only containing device. Moreover, an improved charge extraction and trap state reduction were observed for TrGO containing hybrid solar cells.