Influence of halogen elements in organic salts on n-type doping of CNT yarn for thermoelectric applications.

Doping control of carbon nanotube (CNT) is crucial for thermoelectric (TE) application to maximize the power conversion efficiency. Despite the recent achievement of good air stability by organic salts for n-type carrier doping, their doping mechanism has not been systematically investigated so far. Here, we demonstrate doping of CNT yarn using ammonium salts with different halogen elements (tetra-butylammonium salts, TBAX where X = Cl, Br, or I) through the dipping technique. By changing the halogen element, we specifically investigated the halogen effect in the n-type doping process of CNT. The introduction of each material into the CNT yarn and its doping reaction were then studied by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Halogen element was found to affect the excess amount of TBA+ cation in the CNT yarn. The largest amount of excess TBA+ is found in the TBAI-doped yarn, which stabilizes the most amount of negative charge in CNT, enhancing the TE performance and its stability over one month in air. This study discovers the importance of the halogen element in the doping process of CNT-based TE materials by organic salts, simultaneously offering an efficient and stable n-type doping strategy.

Extreme Orientational Uniformity in Large-Area Floating Films of Semiconducting Polymers for Their Application in Flexible Electronics.

Layer-by-layer fabrication of uniformly oriented thin films over large areas by cost-effective solution-based approaches can open new horizons for the realization of high-performance organic circuits in various applications. In this work, fabrication of a large-area ≈40 cm2 film with uniform orientation is reported for poly(3,3‴-dialkylquaterthiophene) (PQT) using a unidirectional floating film transfer method (UFTM). Orientation characteristics and charge transport anisotropy were analyzed using polarized UV-vis spectral mapping and fabrication of bottom-gated organic field-effect transistors (OFETs) from different regions. Films were found to be highly oriented with an optical dichroic ratio of ca. 15. Orientation characteristics reveal that films were highly oriented along the width of the film, covering >70% of the area, and angle-dependent field-effect mobilities are in good agreement with the orientation of the polymer backbones. These highly oriented films resulted in charge transport anisotropy of 8.9. An array of bottom-gated OFETs fabricated along the length of single large-area (≈15 × 2.5 cm2) thin film demonstrated the average field-effect mobility of 0.0262 cm2/(V s) with a very narrow standard deviation of 12.6%. We also demonstrated that film thickness can be easily tuned from 5.6 to 45 nm by increasing the PQT concentration, and field-effect mobility is highly reproducible even when the film thickness is 10 nm. Microstructural characterization of the thus-prepared large-area thin films revealed the edge-on stacked polymer backbones and surface roughness of <1 nm as probed by grazing incidence X-ray diffraction and atomic force microscopy, respectively. Flexible OFETs with bottom-gate top-contact geometry were also fabricated, having average field-effect mobility of 0.0181 cm2/(V s). There was no considerable change in mobility after bending the flexible devices at different radii.

Enhanced Charge Transport in a Conjugated Polymer Blended with an Insulating Polymer.

Herein, the hole transport in a quinoxaline-thiophene based conjugated polymer (PTQ1) mixed with an insulating polystyrene (PS) was studied by macroscopic and local current density-voltage characteristics measurements. As a result, we found that the hole conductivity in PTQ1 : PS blends increases as the weight ratio of PTQ1 is reduced down to 20 wt%. This is mainly ascribed to increases in mobility because the charge carrier density would be constant in the insulating PS matrix. With decreasing PTQ1 weight ratio in the blends, the absorption bandwidth of PTQ1 and additional emission due to excimer decreased, suggesting that interchain interactions are suppressed. By measuring the temperature-dependent conductivity, we also found that the activation energy for the hole conductivity is smaller in PTQ1 : PS blends than in PTQ1 neat films. These findings suggest that trap sites decrease because of the suppressed interaction between PTQ1 chains in blend films. We also measured conductive atomic force microscope images of the blend films to clarify the local conductive property. For PTQ1 neat films, a low conductive image was observed over the entire film. For PTQ1 : PS blends, on the other hand, many highly conductive spots were locally found. We thus conclude that the dilution of PTQ1 chains in the PS matrix leads to a lower formation of trap sites, resulting in more conductive transport in PTQ1 : PS blends than in PTQ1 neat films.

Investigations on the charge transfer mechanism at donor/acceptor interfaces in the quest for descriptors of organic solar cell performance.

Herein, we theoretically and experimentally investigated the mechanisms of charge separation processes of organic thin-film solar cells. PTB7, PTB1, and PTBF2 have been chosen as donors and PC71BM has been chosen as an acceptor considering that effective charge generation depends on the difference between the material combinations. Experimental results of transient absorption spectroscopy show that the hot process is a key step for determining external quantum efficiency (EQE) in these systems. From the quantum chemistry calculations, it has been found that EQE tends to increase as the transferred charge, charge transfer distance, and variation of dipole moments between the ground and excited states of the donor/acceptor complexes increase; this indicates that these physical quantities are a good descriptor to assess the donor-acceptor charge transfer quality contributing to the solar cell performance. We propose that designing donor/acceptor interfaces with large values of charge transfer distance and variation of dipole moments of the donor/acceptor complexes is a prerequisite for developing high-efficiency polymer/PCBM solar cells.

Origin of Open-Circuit Voltage Loss in Polymer Solar Cells and Perovskite Solar Cells.

Herein, the open-circuit voltage (VOC) loss in both polymer solar cells and perovskite solar cells is quantitatively analyzed by measuring the temperature dependence of VOC to discuss the difference in the primary loss mechanism of VOC between them. As a result, the photon energy loss for polymer solar cells is in the range of about 0.7-1.4 eV, which is ascribed to temperature-independent and -dependent loss mechanisms, while that for perovskite solar cells is as small as about 0.5 eV, which is ascribed to a temperature-dependent loss mechanism. This difference is attributed to the different charge generation and recombination mechanisms between the two devices. The potential strategies for the improvement of VOC in both solar cells are further discussed on the basis of the experimental data.

Charge Transport in Intermixed Regions of All-Polymer Solar Cells Studied by Conductive Atomic Force Microscopy.

Charge transport in intermixed regions of all-polymer solar cells based on a blend of poly(3-hexylthiophene) (P3HT; electron donor) with poly[2,7-(9,9-didodecylfluorene)-alt-5,5-(4',7'-bis(2-thienyl)-2',1',3'-benzothiadiazole)] (PF12TBT; electron acceptor) was studied by conductive atomic force microscopy (C-AFM). For a blend film fabricated from a chlorobenzene solution, intermixed regions were detected between the P3HT-rich and PF12TBT-rich domains. The overall hole current in the intermixed regions remained almost constant, both before and after thermal annealing at 80 °C, but it increased in the P3HT-rich domains. For a blend film fabricated from a chloroform solution, the entire observed area constituted an intermixed region, both before and after thermal annealing. The overall hole current in this film was significantly improved following thermal annealing at 120 °C. These finely mixed structures with efficient charge transport yielded a maximum power conversion efficiency of 3.5%. The local charge-transport properties in the intermixed region, as observed via C-AFM, was found to be closely related to the photovoltaic properties, rather than the bulk-averaged properties or topological features.

Photovoltaic Performance of Perovskite Solar Cells with Different Grain Sizes.

Perovskite solar cells exhibit improved photovoltaic parameters with increasing perovskite grain size. The larger photocurrent is due to the enhanced absorption efficiency for thicker perovskite layers. The larger open-circuit voltage (VOC ) is ascribed to the reduced trap-assisted recombination for the larger grains. As a result, the power conversion efficiency exceeds 19% at best. Further improvement in VOC would be possible if the trap density were reduced.

Ultrafast Singlet Fission in a Push-Pull Low-Bandgap Polymer Film.

Excited-state dynamics in poly[4,6-(dodecyl-thieno[3,4-b]thiophene-2-carboxylate)-alt-2,6-(4,8-dioctoxylbenzo[1,2-b:4,5-b]dithiophene)] (PTB1) was studied by transient absorption spectroscopy. Upon photoexcitation at 400 nm, an additional transient species is promptly generated along with singlet excitons and survives up to nanoseconds, while singlet excitons disappear completely. In order to assign the long-lived species, we measured transient absorption spectra over the wide spectral range from 900 to 2500 nm. As a result, we found that the long-lived species is ascribed not to polarons but to triplet excitons, which is formed through the ultrafast singlet fission (SF). We discuss the ultrafast SF mechanism in push-pull low-bandgap polymer PTB1 films on the basis of the excited-state dynamics under various excitation wavelengths and intensities.

Highly efficient exciton harvesting and charge transport in ternary blend solar cells based on wide- and low-bandgap polymers.

We have designed highly efficient ternary blend solar cells based on a wide-bandgap crystalline polymer, poly(3-hexylthiophene) (P3HT), and a low-bandgap polymer, poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2'3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PSBTBT), and a fullerene derivative (PCBM). By using highly crystalline P3HT, high fill factors were obtained even for ternary blend solar cells, suggesting efficient charge transport due to large P3HT crystalline domains. In such large crystalline domains, some P3HT excitons could not diffuse into the interface with PCBM but can be collected in PSBTBT domains by efficient energy transfer because of large spectral overlap between the P3HT fluorescence and the PSBTBT absorption. Consequently, all the P3HT excitons can contribute to the photocurrent generation at the P3HT/PCBM interface and/or PSBTBT domains mixed with PCBM in the ternary blends. As a result, P3HT/PSBTBT/PCBM ternary blend solar cells exhibit a power conversion efficiency of 5.6%, which is even higher than those of both individual binary devices of P3HT/PCBM and PSBTBT/PCBM.

Interface engineering for ternary blend polymer solar cells with a heterostructured near-IR dye.

Ternary-blend polymer solar cells can be effectively improved by incorporating a heterostructured near-IR dye, which has a hexyl group compatible with the polymer and a benzyl group compatible with the fullerene. Because of the compatibility with both materials, the heterostructured dye can be loaded up to 15 wt% and hence can boost the photocurrent generation by 30%.

Exciton Diffusion in Conjugated Polymers: From Fundamental Understanding to Improvement in Photovoltaic Conversion Efficiency.

Singlet exciton diffusion plays a central role in the photovoltaic conversion in organic photovoltaics (OPVs). Upon light absorption, singlet excitons are promptly generated in organic materials instead of charge carriers because the dielectric constant (εr) is small (∼3-4), which is in sharp contrast to inorganic and perovskite solar cells. In order to convert to charge carriers, excitons need to diffuse into an interface between electron donor and acceptor materials before deactivating to the ground state. Therefore, fundamental understanding of exciton diffusion dynamics is one of the most important issues to further improve OPVs. We highlight recent leading studies in this field and describe several approaches for efficient exciton harvesting at the interface in OPVs.

Molecular design of near-IR dyes with different surface energy for selective loading to the heterojunction in blend films.

We have synthesized three silicon phthalocyanine dyes with different hydrophobic substituents in order to control surface energy in the solid state, aiming at selective loading of the dyes into blend films of poly(3-hexylthiophene) (P3HT) and polystyrene (PS). These three dyes are differently located at P3HT domains, at P3HT/PS interface, and at PS domains, respectively, which are fully consistent with the locations predicted by the wetting coefficient derived from the surface energy of each material.

Efficient Exciton Harvesting through Long-Range Energy Transfer.

Efficient exciton collection at charge-generation sites is one of the key requirements for the improvement in power conversion efficiency (PCE) of organic solar cells, because only excitons arriving at a donor/acceptor interface can be dissociated into free charge carriers. We evaluated the effective diffusion length in poly(3-hexylthiophene) (P3HT) by using donor/acceptor bilayers with two different exciton-quenching acceptors. One is an insoluble fullerene polymer (p-PCBVB), which is an efficient electron-accepting material with negligible absorption in the visible region. The other is a low-bandgap polymer, poly[(4,4-bis(2-ethylhexyl)-dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl], (PSBTBT). This polymer has a large absorption band in the near-IR region, which overlaps well with the emission band of P3HT. The effective diffusion length of P3HT excitons is evaluated to be 15 nm for P3HT/p-PCBVB bilayers and improved to 30 nm for P3HT/PSBTBT bilayers. This improvement is ascribed to long-range energy transfer from P3HT to PSBTBT. This finding suggests that the effective diffusion length of P3HT excitons can be increased through long-range energy transfer by incorporating PSBTBT into P3HT/PCBM blends.

Electron Transport Nanostructures of Conjugated Polymer Films Visualized by Conductive Atomic Force Microscopy.

We have successfully measured electron transport nanostructures of conjugated polymer thin films by conductive atomic force microscopy, using an air-stable electron-injecting electrode coated with ethoxylated polyethylenimine. Electron- and hole-transport networks in donor/acceptor polymer blends can be selectively observed by using an appropriately coated electrode. This approach enables us to visualize phase-separated nanostructures of donor/acceptor polymer blends for thin-film electronic devices based on their semiconducting properties.

Ternary blend hybrid solar cells incorporating wide and narrow bandgap polymers.

Ternary hybrid solar cells based on zinc oxide with wide bandgap poly(3-hexylthiophene) (P3HT) and narrow bandgap poly[2,3-bis(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (PTQ1) exhibit improved photovoltaic performance compared to that of individual binary hybrid solar cells. The increase in the photocurrent is partly due to the complementary absorption bands, which can extend the light-harvesting range from visible to near-infrared regions, and partly due to efficient energy transfer from P3HT to PTQ1, by which P3HT excitons are more efficiently collected at the PTQ1/ZnO interface and hence convert to charge carriers effectively. Furthermore, the improvement in the fill factor may be due to efficient hole transfer from PTQ1 to P3HT with higher hole mobility, and thereby, hole polarons are more efficiently collected on the electrode.

Measurement of exciton diffusion in a well-defined donor/acceptor heterojunction based on a conjugated polymer and cross-linked fullerene derivative.

We designed a well-defined donor/acceptor heterojunction for measuring exciton diffusion lengths in conjugated polymers. To obtain an insoluble electron acceptor layer, a new cross-linkable fullerene derivative (bis-PCBVB) was synthesized by functionalizing [6,6]-diphenyl-C62-bis(butyric acid methyl ester) (bis-PCBM) with two styryl groups. The spin-coated bis-PCBVB film was cross-linked in situ by heating at 170 °C for 60 min. Surface characterizations by UV-visible absorption, atomic force microscopy, and photoelectron yield spectroscopy revealed that a smooth and solvent-resistant film (p-PCBVB) was obtained. In bilayer films with a donor conjugated polymer, poly[2,7-(9,9-didodecylfluorene)-alt-5,5-(4',7'-bis(2-thienyl)-2',1',3'-benzothiadiazole)] (PF12TBT), spin-coated on top of the p-PCBVB acceptor layer, the photoluminescence (PL) of the PF12TBT was effectively quenched. This is because the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the p-PCBVB film are nearly the same as those of the parent bis-PCBM spin-coated film. On the basis of the PL quenching results, the exciton diffusion length and exciton diffusion coefficient in the PF12TBT were evaluated to be 11 nm and 9.8 × 10(-4) cm(2) s(-1), respectively.

Charge-carrier generation in organic solar cells using crystalline donor polymers.

Charge generation and recombination dynamics in a blend film of a crystalline low-bandgap polymer, poly[(4,4-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-4,7-diyl] (PSBTBT), and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) were studied by transient absorption spectroscopy. Upon photoexcitation of the PSBTBT absorption band at 800 nm, singlet excitons were promptly generated, and then rapidly converted into polarons in a few picoseconds. We found that there are two different polarons in PSBTBT: one is ascribed to polarons generated in the disorder phase and the other is ascribed to polarons in the crystalline phase. On a time scale of nanoseconds, ∼50% of polarons in the disorder phase recombined geminately to the ground state. On the other hand, such geminate recombination was negligible for polarons in the crystalline phase. As a result, the overall charge dissociation efficiency is as high as ∼75% for PSBTBT/PCBM blend films. On the basis of these analyses, we discuss the role of polymer crystallinity in the charge-carrier generation in organic solar cells.

One-Dimensional Singlet Exciton Diffusion in Poly(3-hexylthiophene) Crystalline Domains.

Singlet exciton dynamics in crystalline domains of regioregular poly(3-hexylthiophene) (P3HT) films was studied by transient absorption spectroscopy. Upon the selective excitation of crystalline P3HT at the absorption edge, no red shift of the singlet exciton band was observed with an elapse of time, suggesting singlet exciton dynamics in relatively homogeneous P3HT crystalline domains without downhill relaxation in the energetic disorder. Even under such selective excitation conditions, the annihilation rate coefficient γ(t) was still dependent on time, γ(t) ∝ t(-1/2), which is attributed to anisotropic exciton diffusion in P3HT crystalline domains. From the annihilation rate coefficient, the singlet exciton diffusion coefficient D and exciton diffusion length LD in the crystalline domains were evaluated to be 7.9 × 10(-3) cm(2) s(-1) and 20 nm, respectively. The origin of the time-dependent exciton dynamics is discussed in terms of dimensionality.

Dynamical excimer formation in rigid carbazolophane via charge transfer state.

Formation dynamics of intramolecular excimer in dioxa[3.3](3,6)carbazolophane (CzOCz) was studied by time-resolved spectroscopic methods and computational calculations. In the ground state, the most stable conformer in CzOCz is the anti-conformation where two carbazole rings are in antiparallel alignment. No other isomers were observed even after the solution was heated up to 150 °C, although three characteristic isomers were found by the molecular mechanics calculation: the first is the anti-conformer, the second is the syn-conformer where two carbazole rings are stacked in the same direction, and the third is the int-conformer where two carbazole rings are aligned in an edge-to-face geometry. Because of the anti-conformation, the interchromophoric interaction in CzOCz is negligible in the ground state. Nonetheless, the intramolecular excimer in CzOCz was dynamically formed in an acetonitrile (MeCN) solution, indicating strong interchromophoric interaction and the isomerization from the anti- to syn-conformation in the excited state. The excimer formation in CzOCz is more efficient in polar solvents than in less polar solvents, suggesting the contribution of the charge transfer (CT) state to the excimer formation. The stabilization in the excited state is discussed in terms of molecular orbital interaction between two carbazole rings. The solvent-polarity-induced excimer formation is discussed in terms of the CT character in the int-conformation.

Pyrrole-fused azacoronene family: the influence of replacement with dialkoxybenzenes on the optical and electronic properties in neutral and oxidized states.

A novel pyrrole-fused azacoronene family was synthesized via oxidative cyclodehydrogenation of the corresponding hexaarylbenzenes as the key step, and the crystal structures of tetraazacoronene 3b and triazacoronene 4a were elucidated. The photophysical properties for neutral compounds 1-4 were investigated using steady-state UV-vis absorption/emission spectroscopy and time-resolved spectroscopy (emission spectra and lifetime measurements) at both room temperature and 77 K. The observation of both fluorescence and phosphorescence allowed us to estimate the small S1-T1 energy gap (ΔES-T) to be 0.35 eV (1a), 0.26 eV (2a), and 0.36 eV (4a). Similar to the case of previously reported hexapyrrolohexaazacoronene 1 (HPHAC), electrochemical oxidation revealed up to four reversible oxidation processes for all of the new compounds. The charge and spin delocalization properties of the series of azacoronene π-systems were examined using UV-vis-NIR absorption, ESR, and NMR spectroscopies for the chemically generated radical cations and dications. Combined with the theoretical calculations, the experimental results clearly demonstrated that the replacement of pyrrole rings with dialkoxybenzene plays a critical role in the electronic communication, where resonance structures significantly contribute to the thermodynamic stability of the cationic charges/spins and determine the spin multiplicities. For HPHAC 1 and pentaazacoronene 2, the overall aromaticity predicted for closed-shell dications 1(2+) and 2(2+) was primarily based on the theoretical calculations, and the open-shell singlet biradical or triplet character was anticipated for tetraazacoronene 3(2+) and triazacoronene 4(2+) with the aid of theoretical calculations. These polycyclic aromatic hydrocarbons (PAHs) represent the first series of nitrogen-containing PAHs that can be multiply oxidized.