TL;DR: A trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si–C bond interaction is developed and indicates that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials.
Abstract: Simutaneously high open circuit voltage and high short circuit current density is a big challenge for achieving high efficiency polymer solar cells due to the excitonic nature of organic semdonductors. Herein, we developed a trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si–C bond interaction. The polymer solar cells obtained by pairing this polymer with a non-fullerene acceptor demonstrated a high power conversion efficiency of 11.41% with both high open circuit voltage of 0.94 V and high short circuit current density of 17.32 mA cm−2 benefitted from the complementary absorption of the donor and acceptor, and the high hole transfer efficiency from acceptor to donor although the highest occupied molecular orbital level difference between the donor and acceptor is only 0.11 eV. The results indicate that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials. In organic photovoltaics, non-fullerene acceptors relax matching rules and allow for the development of new donor polymers. Here, Bin et al. design a donor polymer and obtain high photoconversion efficiencies despite the low energy offset for hole transfer between the acceptor and the donor.
TL;DR: An efficient fused-ring electron acceptor based on indacenodithieno[3,2-b]thiophene core and thienyl side-chains for organic solar cells (OSCs) is developed and rivals some of the highest efficiencies for single junction OSCs based on fullerene acceptors.
Abstract: We develop an efficient fused-ring electron acceptor (ITIC-Th) based on indacenodithieno[3,2-b]thiophene core and thienyl side-chains for organic solar cells (OSCs). Relative to its counterpart with phenyl side-chains (ITIC), ITIC-Th shows lower energy levels (ITIC-Th: HOMO = −5.66 eV, LUMO = −3.93 eV; ITIC: HOMO = −5.48 eV, LUMO = −3.83 eV) due to the σ-inductive effect of thienyl side-chains, which can match with high-performance narrow-band-gap polymer donors and wide-band-gap polymer donors. ITIC-Th has higher electron mobility (6.1 × 10–4 cm2 V–1 s–1) than ITIC (2.6 × 10–4 cm2 V–1 s–1) due to enhanced intermolecular interaction induced by sulfur–sulfur interaction. We fabricate OSCs by blending ITIC-Th acceptor with two different low-band-gap and wide-band-gap polymer donors. In one case, a power conversion efficiency of 9.6% was observed, which rivals some of the highest efficiencies for single junction OSCs based on fullerene acceptors.
TL;DR: The results indicate that m-ITIC is a promising low bandgap n-OS for the application as an acceptor in PSCs, and the side-chain isomerization could be an easy and convenient way to further improve the photovoltaic performance of the donor and acceptor materials for high efficiency P SCs.
Abstract: Low bandgap n-type organic semiconductor (n-OS) ITIC has attracted great attention for the application as an acceptor with medium bandgap p-type conjugated polymer as donor in nonfullerene polymer solar cells (PSCs) because of its attractive photovoltaic performance. Here we report a modification on the molecular structure of ITIC by side-chain isomerization with meta-alkyl-phenyl substitution, m-ITIC, to further improve its photovoltaic performance. In a comparison with its isomeric counterpart ITIC with para-alkyl-phenyl substitution, m-ITIC shows a higher film absorption coefficient, a larger crystalline coherence, and higher electron mobility. These inherent advantages of m-ITIC resulted in a higher power conversion efficiency (PCE) of 11.77% for the nonfullerene PSCs with m-ITIC as acceptor and a medium bandgap polymer J61 as donor, which is significantly improved over that (10.57%) of the corresponding devices with ITIC as acceptor. To the best of our knowledge, the PCE of 11.77% is one of the highe...
TL;DR: Three medium bandgap 2D-conjugated bithienyl-benzodithiophene-alt-fluorobenzotriazoleCopolymers J52, J60, and J61 are synthesized for the application as donor in the PSCs with low bandgap n-OS ITIC as acceptor and results indicate that J61 is a promising medium band gap polymer donor in non-fullerene P SCs.
Abstract: Non-fullerene polymer solar cells (PSCs) with solution-processable n-type organic semiconductor (n-OS) as acceptor have seen rapid progress recently owing to the synthesis of new low bandgap n-OS, such as ITIC. To further increase power conversion efficiency (PCE) of the devices, it is of a great challenge to develop suitable polymer donor material that matches well with the low bandgap n-OS acceptors thus providing complementary absorption and nanoscaled blend morphology, as well as suppressed recombination and minimized energy loss. To address this challenge, we synthesized three medium bandgap 2D-conjugated bithienyl-benzodithiophene-alt-fluorobenzotriazole copolymers J52, J60, and J61 for the application as donor in the PSCs with low bandgap n-OS ITIC as acceptor. The three polymers were designed with branched alkyl (J52), branched alkylthio (J60), and linear alkylthio (J61) substituent on the thiophene conjugated side chain of the benzodithiophene (BDT) units for studying effect of the substituents o...
TL;DR: High-efficiency all-polymer solar cells with less thickness-dependent behavior are demonstrated by using a low bandgap n-type conjugated polymer N2200 as acceptor and an absorption-complementary difluorobenzotriazole-based medium-bandgap polymer J51 as donor.
Abstract: High-efficiency all-polymer solar cells with less thickness-dependent behavior are demonstrated by using a low bandgap n-type conjugated polymer N2200 as acceptor and an absorption-complementary difluorobenzotriazole-based medium-bandgap polymer J51 as donor.
TL;DR: A novel perylene bisimide (PBI) acceptor, SdiPBI-Se, in which selenium atoms were introduced into the perylene core, suggesting that non-fullerene acceptors have enormous potential to rival or even surpass the performance of their fullerene counterparts.
Abstract: Non-fullerene acceptors have recently attracted tremendous interest because of their potential as alternatives to fullerene derivatives in bulk heterojunction organic solar cells. However, the power conversion efficiencies (PCEs) have lagged far behind those of the polymer/fullerene system, mainly because of the low fill factor (FF) and photocurrent. Here we report a novel perylene bisimide (PBI) acceptor, SdiPBI-Se, in which selenium atoms were introduced into the perylene core. With a well-established wide-band-gap polymer (PDBT-T1) as the donor, a high efficiency of 8.4% with an unprecedented high FF of 70.2% is achieved for solution-processed non-fullerene organic solar cells. Efficient photon absorption, high and balanced charge carrier mobility, and ultrafast charge generation processes in PDBT-T1:SdiPBI-Se films account for the high photovoltaic performance. Our results suggest that non-fullerene acceptors have enormous potential to rival or even surpass the performance of their fullerene counterparts.
TL;DR: A novel non-fullerene acceptor, possessing a very low bandgap of 1.34 eV and a high-lying lowest unoccupied molecular orbital level of -3.95 eV, is designed and synthesized by introducing electron-donating alkoxy groups to the backbone of a conjugated small molecule.
Abstract: A novel non-fullerene acceptor, possessing a very low bandgap of 1.34 eV and a high-lying lowest unoccupied molecular orbital level of -3.95 eV, is designed and synthesized by introducing electron-donating alkoxy groups to the backbone of a conjugated small molecule. Impressive power conversion efficiencies of 8.4% and 10.7% are obtained for fabricated single and tandem polymer solar cells.
TL;DR: The crystal structure of DTCBPy reveals a substantial interaction between the ortho donor (carbazolyl) and acceptor (4-pyridylcarbonyl) unit, likely play a key role to achieve very small ΔEST with high photoluminescence quantum yield.
Abstract: Two benzoylpyridine-carbazole based fluorescence materials DCBPy and DTCBPy, bearing two carbazolyl and 4-(t-butyl)carbazolyl groups, respectively, at the meta and ortho carbons of the benzoyl ring, were synthesized. These molecules show very small ΔEST of 0.03 and 0.04 eV and transient PL characteristics indicating that they are thermally activated delayed fluorescence (TADF) materials. In addition, they show extremely different photoluminescent quantum yields in solution and in the solid state: in cyclohexane the value are 14 and 36%, but in the thin films, the value increase to 88.0 and 91.4%, respectively. The OLEDs using DCBPy and DTCBPy as dopants emit blue and green light with EQEs of 24.0 and 27.2%, respectively, and with low efficiency roll-off at practical brightness level. The crystal structure of DTCBPy reveals a substantial interaction between the ortho donor (carbazolyl) and acceptor (4-pyridylcarbonyl) unit. This interaction between donor and acceptor substituents likely play a key role to ...
TL;DR: In this article, the authors show that the energy gap for singlet and triplet excitons with charge-transfer character can be tuned from positive to negative values via the rotation of donor and acceptor about the metal-amide bond.
Abstract: The efficiency of an organic light-emitting diode (OLED) is fundamentally governed by the spin of recombining electron-hole pairs (singlet and triplet excitons), since triplets cannot usually emit light. The singlet-triplet energy gap, a key factor for efficient utilization of triplets, is normally positive. Here we show that in a family of materials with amide donor and carbene acceptor moieties linked by a metal, this energy gap for singlet and triplet excitons with charge-transfer character can be tuned from positive to negative values via the rotation of donor and acceptor about the metal-amide bond. When the gap is close to zero, facile intersystem crossing is possible, enabling efficient emission from singlet excitons. We demonstrate solution-processed LEDs with exceptionally high quantum efficiencies (near-100% internal and >27% external quantum efficiencies), and current and power efficiencies (87 cd/A and 75 lm/W) comparable to, or exceeding, those of state-of-the-art vacuum-processed OLEDs and quantum dot LEDs.
TL;DR: A novel polymer acceptor based on the double B←N bridged bipyridine building block is reported that shows a power conversion efficiency of as high as 6.26% at a photon energy loss of only 0.51 eV.
Abstract: A novel polymer acceptor based on the double B←N bridged bipyridine building block is reported. All-polymer solar cells based on the new polymer acceptor show a power conversion efficiency of as high as 6.26% at a photon energy loss of only 0.51 eV.
TL;DR: Direct evidence of enhanced non-radiative energy transfer between two J-aggregated cyanine dyes strongly coupled to the vacuum field of a cavity is presented and has fundamental implications for coherent energy transport and light-energy harvesting.
Abstract: We present direct evidence of enhanced non-radiative energy transfer between two J-aggregated cyanine dyes strongly coupled to the vacuum field of a cavity. Excitation spectroscopy and femtosecond pump-probe measurements show that the energy transfer is highly efficient when both the donor and acceptor form light-matter hybrid states with the vacuum field. The rate of energy transfer is increased by a factor of seven under those conditions as compared to the normal situation outside the cavity, with a corresponding effect on the energy transfer efficiency. The delocalized hybrid states connect the donor and acceptor molecules and clearly play the role of a bridge to enhance the rate of energy transfer. This finding has fundamental implications for coherent energy transport and light-energy harvesting.
TL;DR: It is shown that quantum coherence and donor-acceptor delocalization facilitate rapid charge transfer at a MoS2/MoSe2 interface, and atomistic, time-domain studies provide valuable insights into excitation dynamics in two-dimensional transition metal dichalcogenides.
Abstract: Two-dimensional transition metal dichalcogenides (MX2, M = Mo, W; X = S, Se) hold great potential in optoelectronics and photovoltaics. To achieve efficient light-to-electricity conversion, electron–hole pairs must dissociate into free charges. Coulomb interaction in MX2 often exceeds the charge transfer driving force, leading one to expect inefficient charge separation at a MX2 heterojunction. Experiments defy the expectation. Using time-domain density functional theory and nonadiabatic (NA) molecular dynamics, we show that quantum coherence and donor–acceptor delocalization facilitate rapid charge transfer at a MoS2/MoSe2 interface. The delocalization is larger for electron than hole, resulting in longer coherence and faster transfer. Stronger NA coupling and higher acceptor state density accelerate electron transfer further. Both electron and hole transfers are subpicosecond, which is in agreement with experiments. The transfers are promoted primarily by the out-of-plane Mo–X modes of the acceptors. Li...
TL;DR: A nonfullerene polymer solar cell with a high efficiency of 9.26% is realized by using benzodithiophene-alt-fluorobenzotriazole copolymer J51 as a medium-band gap polymer donor and the low-bandgap organic semiconductor ITIC with high extinction coefficients as the acceptor.
Abstract: A nonfullerene polymer solar cell with a high efficiency of 9.26% is realized by using benzodithiophene-alt-fluorobenzotriazole copolymer J51 as a medium-bandgap polymer donor and the low-bandgap organic semiconductor ITIC with high extinction coefficients as the acceptor.
TL;DR: A series of twisted Dπ-A type emitters based on the acridine donor unit and CN-substituted pyridine, pyrimidine, and benzene acceptor units are studied in this paper.
Abstract: A series of twisted D–π–A type emitters based on the acridine donor unit and CN-substituted pyridine, pyrimidine, and benzene acceptor units are studied. They not only allow one to systematically probe the influence of different acceptor strengths, but also permit one to intriguingly probe the influence of tunable conformations (twist angles) within the acceptor moieties through controlling the orientation of asymmetric heteroaromatic ring relative to the donor component. Intramolecular charge-transfer transitions are observed in all these compounds and emission wavelengths are widely tunable from deep blue to yellow not only by the general acceptor strength due to the characters of heteroarene and CN-substitution pattern but also by the subtle control of in-acceptor conformation (twist angles). Small triplet-to-singlet energy gaps (ΔEST) and significant thermally activated delayed fluorescence (TADF) characteristics are obtained in a series of D–π–A compounds with sufficient acceptor strengths and tunable in-acceptor conformation, yielding a series of efficient blue-green to yellow TADF emitters with promisingly high photoluminescence quantum yields of 90%–100%. Highly efficient blue-green to yellow TADF organic light-emitting diodes (OLEDs) having external quantum efficiencies of up to 23.1%–31.3% are achieved using these efficient TADF emitters, which are among the most efficient TADF OLEDs ever reported.
TL;DR: A non-fullerene electron acceptor bearing a fused 10-heterocyclic ring with a narrow band gap (∼1.5 eV) was designed and synthesized in this paper.
Abstract: A non-fullerene electron acceptor bearing a fused 10-heterocyclic ring (indacenodithiopheno-indacenodithiophene) with a narrow band gap (∼1.5 eV) was designed and synthesized. It possesses excellent planarity and enhanced effective conjugation length compared to previously reported fused-ring electron acceptors. When this acceptor was paired with PTB7-Th and applied in polymer solar cells, a power conversion efficiency of 6.5% was achieved with a high open circuit voltage of 0.94 V. More significantly, an energy loss as low as 0.59 eV and an external quantum efficiency as high as 63% were obtained simultaneously.
TL;DR: The alloy acceptor (indene-C60 bis-adduct (ICBA)/[6,6]-phenyl-C71 -butyric acid-methyl-ester (PC71 BM) is employed to replace the widely used fullerene acceptor in organic solar cells based on five different polymer donors, which exhibit a higher efficiency and much better device stability than the PC71 BM counterpart.
Abstract: The alloy acceptor (indene-C60 bis-adduct (ICBA)/[6,6]-phenyl-C71 -butyric acid-methyl-ester (PC71 BM)) is employed to replace the widely used fullerene acceptor (PC71 BM) in organic solar cells based on five different polymer donors, which exhibit a higher efficiency and much better device stability than the PC71 BM counterpart.
TL;DR: By employing both a novel polymer donor and a nonfullerene small-molecule acceptor in the solution-processed organic solar cells, a high-power conversion efficiency of close to 6% is demonstrated.
Abstract: A new 3D nonfullerene small-molecule acceptor is reported. The 3D interlocking geometry of the small-molecule acceptor enables uniform molecular conformation and strong intermolecular connectivity, facilitating favorable nanoscale phase separation and electron charge transfer. By employing both a novel polymer donor and a nonfullerene small-molecule acceptor in the solution-processed organic solar cells, a high-power conversion efficiency of close to 6% is demonstrated.
TL;DR: The methodologies for investigating the two charge generation channels are reviewed and the factors that affect charge generation via Channel I and II pathways, including energy levels of the materials involved, exciton diffusion, and other considerations are discussed.
Abstract: Photocurrent generation in organic bulk heterojunction (BHJ) solar cells is most commonly understood as a process which predominantly involves photoexcitation of the lower ionization potential species (donor) followed by electron transfer to the higher electron affinity material (acceptor) [i.e., photoinduced electron transfer (PET), which we term Channel I]. A mirror process also occurs in which photocurrent is generated through photoexcitation of the acceptor followed by hole transfer to the nonexcited donor or photoinduced hole transfer (PHT), which we term Channel II. The role of Channel II photocurrent generation has often been neglected due to overlap of the individual absorption spectra of the donor and acceptor materials that are commonly used. More recently Channel II charge generation has been explored for several reasons. First, many of the new high-efficiency polymeric donors are used as the minority component in bulk heterojunction blends, and therefore, the acceptor absorption is a significa...
TL;DR: The results clearly indicate the significance of mobility balance in governing the efficiency of exciplex-based OLED.
Abstract: A star-shaped 1,3,5-triazine/cyano hybrid molecule CN-T2T was designed and synthesized as a new electron acceptor for efficient exciplex-based OLED emitter by mixing with a suitable electron donor (Tris-PCz). The CN-T2T/Tris-PCz exciplex emission shows a high ΦPL of 0.53 and a small ΔET-S = −0.59 kcal/mol, affording intrinsically efficient fluorescence and highly efficient exciton up-conversion. The large energy level offsets between Tris-PCz and CN-T2T and the balanced hole and electron mobility of Tris-PCz and CN-T2T, respectively, ensuring sufficient carrier density accumulated in the interface for efficient generation of exciplex excitons. Employing a facile device structure composed as ITO/4% ReO3:Tris-PCz (60 nm)/Tris-PCz (15 nm)/Tris-PCz:CN-T2T(1:1) (25 nm)/CN-T2T (50 nm)/Liq (0.5 nm)/Al (100 nm), in which the electron–hole capture is efficient without additional carrier injection barrier from donor (or acceptor) molecule and carriers mobilities are balanced in the emitting layer, leads to a highly...
TL;DR: In this paper, a non-fullerene electron acceptor bearing a fused five-heterocyclic ring containing selenium atoms, denoted as IDSe-T-IC, was presented for fullerene-free polymer solar cells (PSCs).
Abstract: In this work, we present a non-fullerene electron acceptor bearing a fused five-heterocyclic ring containing selenium atoms, denoted as IDSe-T-IC, for fullerene-free polymer solar cells (PSCs). This molecule exhibits a low band gap (Eg = 1.52 eV), strong absorption in the 600–850 nm region and a high LUMO level (−3.79 eV). When a large band gap polymer J51 (Eg = 1.91 eV) was used as the donor, complementary absorption of the polymer donor and acceptor was obtained in the wavelength range of 350–850 nm. The solar cell based on J51:IDSe-T-IC gives a maximum PCE of 8.6%, with a high Voc of 0.91 V, a Jsc of 15.20 mA cm−2 and a fill factor (FF) of 62.0%. Moreover, this performance is much higher than that of J51:PC71BM based PSCs under similar device fabrication conditions (PCE = 6.0%). The trade-off features of the Jsc and Voc existing in PSCs with fullerene acceptors have been minimized in the fullerene-free PSCs based on IDSe-T-IC and J51. The results demonstrate that fine-tuning the absorption and electronic energy levels of non-fullerene acceptors, and properly selecting a polymer donor to achieve complementary absorption, is a promising way to further improve the performance of the PSCs.
TL;DR: In this article, density functional theory calculations of electronic structure and dielectric and defect properties of CsGeI3 (a lead-free halide perovskite material) are presented.
Abstract: Many metal halides that contain cations with the ns2 electronic configuration have recently been discovered as high-performance optoelectronic materials. In particular, solar cells based on lead halide perovskites have shown great promise as evidenced by the rapid increase of the power conversion efficiency. In this paper, we show density functional theory calculations of electronic structure and dielectric and defect properties of CsGeI3 (a lead-free halide perovskite material). The potential of CsGeI3 as a solar cell material is assessed based on its intrinsic properties. We find anomalously large Born effective charges and a large static dielectric constant dominated by lattice polarization, which should reduce carrier scattering, trapping, and recombination by screening charged defects and impurities. Defect calculations show that CsGeI3 is a p-type semiconductor and its hole density can be modified by varying the chemical potentials of the constituent elements. Despite the reduction of long-range Coulomb attraction by strong screening, the iodine vacancy in CsGeI3 is found to be a deep electron trap due to the short-range potential, i.e., strong Ge–Ge covalent bonding, which should limit electron transport efficiency in p-type CsGeI3. This is in contrast to the shallow iodine vacancies found in several Pb and Sn halide perovskites (e.g., CH3NH3PbI3, CH3NH3SnI3, and CsSnI3). The low-hole-density CsGeI3 may be a useful solar absorber material but the presence of the low-energy deep iodine vacancy may significantly reduce the open circuit voltage of the solar cell. On the other hand, CsGeI3 may be used as an efficient hole transport material in solar cells due to its small hole effective mass, the absence of low-energy deep hole traps, and the favorable band offset with solar absorber materials such as dye molecules and CH3NH3PbI3.
TL;DR: These are the first highly efficient artificial light-harvesting systems based on nanocrystals of difluoroboron chromophores to mimic the chlorosomes, one of the most efficient light- Harvesting systems found in green photosynthetic bacteria.
Abstract: We report the first highly efficient artificial light-harvesting systems based on nanocrystals of difluoroboron chromophores to mimic the chlorosomes, one of the most efficient light-harvesting systems found in green photosynthetic bacteria. Uniform nanocrystals with controlled donor/acceptor ratios were prepared by simple coassembly of the donors and acceptors in water. The light-harvesting system funneled the excitation energy collected by a thousand donor chromophores to a single acceptor. The well-defined spatial organization of individual chromophores in the nanocrystals enabled an energy transfer efficiency of 95 %, even at a donor/acceptor ratio as high as 1000:1, and a significant fluorescence of the acceptor was observed up to donor/acceptor ratios of 200 000:1.
TL;DR: In this paper, a series of perylenediimide (PDI) dimers are evaluated as acceptors for organic photovoltaic (OPV) cells using a wide variety of physical and computational techniques.
Abstract: A series of perylenediimide (PDI) dimers are evaluated as acceptors for organic photovoltaic (OPV) cells. The materials are characterized using a wide variety of physical and computational techniques. These dimers are first linked at the bay position of each PDI molecule via an aromatic spacer; subsequent photocyclization affords ring-fused dimers. Thus, photocyclization of the thiophene-linked dimer 2,5-bis-[N,N′-bis-perylenediimide-1-yl]-thiophene (T1) affords the twisted acceptor [2,3-b:2′,3′-d]-bis-[N,N′-bis-perylenediimide-1,12-yl]-thiophene (T2), while photocyclization of the thienothiophene-linked dimer, 2,5-bis-[N,N′-bis-perylenediimide-1-yl]-thienothiophene (TT1) affords the planar acceptor [2,3-b:2′,3′-d]-bis-[N,N′-bis-perylenediimide-1,12-yl]-thienothiophene (TT2). Furthermore, a dimer linked by a phenylene group, 1,4-bis-[N,N′-bis-perylenediimide-1-yl]-benzene (Ph1), can be selectively photocyclized to form either the twisted dimer, [1,2:3,4]-bis-[N,N′-bis-perylenediimide-1,12-yl]-benzene (Ph1a) or the planar dimer [1,2:4,5]-bis-[N,N′-bis-perylenediimide-1,12-yl]-benzene (Ph2b). Ring-fusion results in increased electronic coupling between the PDI units, and increased space-charge limited thin film electron mobility. While charge transport is efficient in bulk-heterojunction blends of each dimer with the polymeric donor PBDTT-FTTE, in the case of the twisted dimers ring fusion leads to a significant decrease in geminate recombination, hence increased OPV photocurrent density and power conversion efficiency. This effect is not observed in planar dimers where ring fusion leads to increased crystallinity and excimer formation, decreased photocurrent density, and decreased power conversion efficiency. These results argue that ring fusion is an effective approach to increasing OPV bulk-heterojunction charge carrier generation efficiency in PDI dimers as long as they remain relatively amorphous, thereby suppressing excimer formation and coulombically trapped charge transfer states.
TL;DR: In this article, a polythiophene derivative (PBDD4T) was used to increase the rotation barrier and stabilize its backbone conformation by introducing fluorine into the β- and β-position of the α-linked bithiophene segments.
Abstract: Here, taking a polythiophene derivative (PBDD4T) as a starting polymer, we tried to increase the rotation barrier and hence stabilize its backbone conformation by introducing fluorine into the β- and β′-position of the α-linked bithiophene segments and then synthesized a new polymer named as PBDD4T-2F. Our results demonstrate that the rotation barrier between the α-linked bithiophene significantly increases after the fluorination, so PBDD4T-2F has a more stable backbone conformation than PBDD4T. Compared to PBDD4T, PBDD4T-2F shows stronger aggregation effect in solution state and more compact π–π stacking in solid thin film and also possesses deeper HOMO level. These properties make PBDD4T-2F being an ideal donor material in PSCs. When blended with PC71BM, a fullerene acceptor, the PBDD4T-2F-based device showed a power conversion efficiency (PCE) of 9.04%, which is 38% higher than that of the PBDD4T-based device; when blended with ITIC, a non-fullerene acceptor, the PBDD4T-2F-based device showed a PCE of ...
TL;DR: In this paper, the authors proposed a twisted-ICT framework for a flattened molecular backbone and introduced a strong acceptor possessing nπ* transition character, hypsochromic color, a large radiative rate (kF), and small singlet-triplet splitting energy (ΔEST) for reverse intersystem crossing from nonemissive triplet state to radiative singlet state.
Abstract: A barely reached balance between weak intramolecular-charge-transfer (ICT) and small singlet–triplet splitting energy (ΔEST) for reverse intersystem crossing from non-emissive triplet state to radiative singlet state impedes the realization of deep-blue thermally activated delayed fluorescence (TADF) materials. By discarding the twisted-ICT framework for a flattened molecular backbone and introducing a strong acceptor possessing n–π* transition character, hypsochromic color, a large radiative rate (kF), and small ΔEST are achieved simultaneously. Six molecules with a 9,9-dimethyl-10-phenyl-9,10-dihydroacridine (i-DMAc) donor are synthesized and investigated. Coinciding with time-dependent density functional theory, the reduced dihedral angles between donor (D) and acceptor (A) weaken ICT from dispersed charge density and enable a large kF from increased frontier molecular orbitals overlap. Despite the separated highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) population, the intercalation of phenyl bridges between D–A increases kF but significantly lowers the local triplet excited state, indicating small HOMO and LUMO overlap is not a sufficient, but necessary condition for reduced ΔEST. Integrating short conjugation length and carbonyl or triazine acceptors into the complanation molecules, deep-blue TADF organic light-emitting diodes demonstrate maximum external quantum efficiencies of 11.5% and 10.9% with Commission Internationale de l'Eclairage coordinates of (0.16, 0.09) and (0.15, 0.11), respectively, which is quite close to the stringent National Television System Committee blue standard.
TL;DR: In this article, the authors studied the methodologies of searching for novel organic charge transfer binary compounds and large-size crystal growth, in the case that only the two starting organic substances are known but the phase diagram is not known, the thermodynamic data of the binary compound are not known.
Abstract: The methodologies of searching for novel organic charge transfer binary compounds and large-size crystal growth, in the case that only the two starting organic substances are known but the phase diagram is not known, the thermodynamic data of the binary compound are not known, and even the existence of new binary compounds is not known, were studied. Centimeter-long crystals of novel perylene-F1TCNQ, perylene-F2TCNQ, and perylene-F4TCNQ charge transfer binary compounds are obtained from the gas phase. Kinetically lowering the sublimation rate is the key factor for growing large-size charge transfer compound single crystals. Changing the number of fluorine atoms in FxTCNQ results in the variation of the electron affinity, which further changes the HOMO–LUMO of acceptor. Charge transfer degree is increased with increasing of fluorine atoms in the perylene-FxTCNQ system. Therefore, the structure, stoichiometry, and kind of donor and acceptor enable HOMO–LUMO engineering of the charge transfer compound and tu...
TL;DR: In this article, a weak acceptor P═O group was employed to construct a series of WASD-type emitters with a phenoxazine donor, namely 10-(4-(diphenylphosphoryl)phenyl)-10H-phenoxazine (SPXZPO), 10,10′,10
Abstract: Blue thermally activated delayed fluorescence (TADF) dyes are basically combinations of strong acceptors and weak donors. In this work, a weak acceptor P═O group was employed to construct a series of weak acceptor–strong donor (WASD)-type emitters with a phenoxazine donor, namely 10-(4-(diphenylphosphoryl)phenyl)-10H-phenoxazine (SPXZPO), 10,10′-(4,4′-(phenylphosphoryl)bis(4,1-phenylene))bis(10H-phenoxazine) (DPXZPO), and 10,10′,10″-(4,4′,4″-phosphoryltris(benzene-4,1-diyl))tris(10H-phenoxazine) (TPXZPO). Owing to the insulating effect of P═O on conjugation extension and intramolecular electronic communications, the photoluminescence spectra of these molecules are almost identical, manifesting the superiority of WASD structure in emission color preservation. Simultaneously, the multi-dipolar characteristics of TPXZPO enhance the intramolecular charge transfer (ICT), facilitating reverse intersystem crossing for higher TADF efficiency and shorter lifetime. As a consequence, TPXZPO realized the desired pure...
TL;DR: 36 halogen-bonded complexes YXARm have been investigated at the CCSD(T)/aug-cc-pVTZ level of theory and the covalent character of a halogen bond increases in the way 3c-4e (three-center-four-electron) bonding becomes possible.
Abstract: 36 halogen-bonded complexes YX⋯ARm (X: F, Cl, Br; Y: donor group; ARm acceptor group) have been investigated at the CCSD(T)/aug-cc-pVTZ level of theory. Binding energies, geometries, NBO charges, charge transfer, dipole moments, electrostatic potential, electron and energy density distributions, difference density distributions, vibrational frequencies, local stretching and bending force constants, and relative bond strength orders n have been calculated and used to order the halogen bonds according to their intrinsic strength. Halogen bonding is found to arise from electrostatic and strong covalent contributions. It can be strengthened by H-bonding or lone pair delocalization. The covalent character of a halogen bond increases in the way 3c-4e (three-center-four-electron) bonding becomes possible. One can characterize halogen bonds by their percentage of 3c-4e bonding. FCl–phosphine complexes can form relatively strong halogen bonds provided electronegative substituents increase the covalent contributions in form of 3c-4e halogen bonding. Binding energies between 1 and 45 kcal mol−1 are calculated, which reflects the large variety in halogen bonding.
TL;DR: In this paper, the importance of the electronic properties of acceptor comonomers in determining the reactivity of 4,8-di(thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene (DBD)-based PCP photocatalyst for photocatalytic hydrogen production (PHP) was reported.
Abstract: Porous conjugated polymer (PCP) is a new kind of photocatalyst for photocatalytic hydrogen production (PHP). Here, we report the importance of the electronic properties of acceptor comonomer in determining the reactivity of 4,8-di(thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene (DBD)-based PCP photocatalyst for PHP application. It was found that the incorporation of nitrogen-containing ligand acceptor monomers into PCP network is an effective strategy to enhance the PHP activity. These moderately electron-deficient comonomers enhanced the dipole polarization effect. These PCPs exhibit appropriate solid-state morphology for charge transport. Powder X-ray diffraction (XRD) studies demonstrate that these PCP materials are semicrystalline materials. A strong correlation between the crystalline property and PHP activity is observed. The replacement of nitrogen-containing ligand acceptors with ligand-free strong acceptors is proved to be detrimental to the PHP process, indicating the proper choice in the electroni...
TL;DR: This study of PTPD[2F]T polymers shows that linear, all-thiophene systems with adequately substituted main chains can also be conducive to efficient BHJ solar cells with polymer donors.
Abstract: Branched-alkyl-substituted poly(thieno[3,4-c]pyrrole-4,6-dione-alt-3,4-difluorothiophene) (PTPD[2F]T) can be used as a polymer acceptor in bulk heterojunction (BHJ) solar cells with a low-band-gap polymer donor (PCE10) commonly used with fullerenes. The “all-polymer” BHJ devices made with PTPD[2F]T achieve efficiencies of up to 4.4 %. While, to date, most efficient polymer acceptors are based on perylenediimide or naphthalenediimide motifs, our study of PTPD[2F]T polymers shows that linear, all-thiophene systems with adequately substituted main chains can also be conducive to efficient BHJ solar cells with polymer donors.