End-capping Groups Research Articles

Structure engineering of small molecules for organic solar cells

Two 1,3-bis(thiophen-2-yl)−5,7-bis(2-ehtylhexyl)benzo-[1,2-c:4,5-c]-dithiophene-4,8-dione (BDD) based small molecules, SM1 and SM2 are designed and synthesized by incorporating benzodithiophene (BDT) central core, BDD dual accepting units and 3-ethyl rhodamine as endcap group with various number of BDT units. We systematically investigated the synthesis, optical and electrochemical properties, and photovoltaic characteristics of these donor materials. The number of BDT units have a significant influence on Jsc due to interconnected structure and results in a broader absorption on thin film. The inverted devices employed for both small molecules exhibited power conversion efficiencies of 0.41% for SM1 and 0.82% for SM2.

Investigations of New Phenothiazine-Based Compounds for Dye-Sensitized Solar Cells with Theoretical Insight.

New D-π-D-π-A low-molecular-weight compounds, based on a phenothiazine scaffold linked via an acetylene unit with various donor moiety and cyanoacrylic acid anchoring groups, respectively, were successfully synthesized. The prepared phenothiazine dyes were entirely characterized using nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The compounds were designed to study the relationship between end-capping donor groups’ structure on their optoelectronic and thermal properties as well as the dye-sensitized solar cells’ performance. The effect of π-conjugation enlargement by incorporation of different heterocyclic substituents possessing various electron–donor affinities was systematically experimentally and theoretically examined. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were implemented to determine the electronic properties of the novel molecules.

Designing indenothiophene-based acceptor materials with efficient photovoltaic parameters for fullerene-free organic solar cells.

Non-fullerene small molecular acceptors (NFSMAs) exhibit promising photovoltaic performance which promoted the rapid progress of organic solar cells (OSCs). In this study, an attempt is done to explore indenothiophene-based high-performance small molecular electron acceptors for organic solar cells. We have designed five acceptor molecules (M1-M5) with strong donor moiety indenothiophene linked to five different end-capped group acceptor moieties: diflouro-2-methylene-3-oxo-2,3-dihydroindene-1-ylidene)malononitrile (A1), 1-(dicyanomethylene)-2-methylene-3-oxo-2,3-dihydro-1H-indene-5,6-dicarbonitrile (A2), methyl-6-cyano-3-(dicyanomethylene)-2-methylene-1-oxo-2,3-dihydro-1H-indene-5-carboylate (A3), 2-(6-cyano-5-fluoro-2-methylene-3-oxo-2,3 dihydro-1H-indene-1-ylidene)malononitrile (A4), and (Z)-methyl 3-(benzo [c][1,2,5]thiadiazol-4-yl)-2-cyanoacrylate (A5) respectively. The structure-property relationship was studied and effects of structural modification on the optoelectronic properties of these acceptors (M1-M5) were determined systematically by comparing it with reference molecule R, which is recently reported as excellent non-fullerene-based small acceptor molecule. Among all designed molecules, M5 is proven as a suitable candidate for organic solar cell applications due to better photovoltaic properties including narrow HOMO-LUMO energy gap (2.11 eV), smallest electron mobility (λe= 0.0038eV), highest λmax values (702.82 nm in gas) and (663.09 nm in chloroform solvent) and highest open-circuit voltage (Voc = 1.49V) with respect to HOMOPTB7-Th-LUMOacceptor. Our results indicate that introducing more end-capped electron-accepting units is a simple and effective alternative strategy for the design of promising NFSMAs. This theoretical framework also proves that the conceptualized NFSMAs are superior and thus are recommended for the future construction of high-performance organic solar cell devices. Graphical abstract.

Synthesis and Photophysical Properties of Bromination the Small-Molecule Acceptor for Organic Solar Cells

At present, the modification of the benzene ring based terminal group IC is widely studied and a series of progress has been made. Our work designed and synthesized a new brominated fused ring small molecule receptor FBDTEH-2Br by introducing bromine atoms into terminal group. On the one hand, the electron-withdrawing effect of bromine enhances the push-pull electron effect between the core electron-donating segment and the end-capping group, making the absorption spectrum of FBDTEH-2Br more suitable. It shows broad absorption in the range of 600–800 nm in solution, the maximum absorption peak of FBDTEH-2Br in solution is 742nm, While for the thin film, the absorption extended broader with an obvious red-shift in the range of 800–900 nm, it is beneficial to higher JSC. The maximum absorption peak is 800nm in the film, which can be explained by it’s nearly planar structure and the good intermolecular π-π stacking in the solid state caused by the dibromide IC. On the other hand, the introduction of Br atoms will also enhance the intermolecular interactions and improve the electron mobility. The optical band gap of FBDTEH-2Br is 1.43 eV. These results demonstrated that due to the bromine atom has a larger size, the end groups of adjacent molecules still exhibit strong interactions with short π-π distance Because of the O···S and Br···S interactions, which is beneficial for the charge to transport along multidirections. Therefore, the introduction of bromine atoms into theterminal group to design and synthesize new brominated small molecule acceptors is expected to obtain better performance in organic solar cell materials.

Influences of the terminal groups on the performances of asymmetric small molecule acceptors-based polymer solar cells

By altering the end-capping groups from 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile to 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile, three asymmetric non-fullerene electron-acceptors (T-TT, T-TT-4F, and T-TT-4Cl) containing thiophene–phenylene–thieno[3,2-b]thiophene fused-ring as the electron-donating core were synthesized. Although the three asymmetric molecules all have bent geometries, the di-fluorinated and di-chlorinated acceptors show bathochromically-shifted spectra, enhanced molar extinct coefficients, deepened molecular energy levels, and reduced dipole moments. When blending with a wide-bandgap polymer PM6 in inverted solar cells, the T-TT-based device exhibits the highest open-circuit voltage (VOC) of 0.966 V, while the T-TT-4Cl-based device has the biggest short-circuit current density (JSC) of 19.00 mA cm−2, and the T-TT-4F-based device possesses the best fill factor (FF) of 66.1%, a moderate VOC (0.859 V), and a medium JSC (18.48 mA cm−2). As a result of the above properties and parameters, the T-TT-4F- and T-TT-4Cl-based solar cells successfully achieved high power conversion efficiencies of 10.49% and 10.16%, in comparison with that of 9.70% for the T-TT-based device, illustrating the importance of the influences of the terminal groups on the performances of asymmetric small molecular acceptors-based polymer solar cells.

Designing alkoxy-induced based high performance near infrared sensitive small molecule acceptors for organic solar cells

Scientist are dedicated to design and synthesize efficient photovoltaic materials to overcome the energy crises. In this regard, herein, we have designed four new small acceptor molecules namely ( A1, A2, A3 and A4 ) for better performance in organic solar cells. These molecules consist Alkoxy-Induced Naphtho-dithiophene core unit flanked with 2,2-ethylidene-5,6-dicyano-3-oxo-2,3-dihydroinden-1-ylidene-malononitrile ( A1 ), methyl-2-cyano-2,2-ethylidene-5,6-difluoro-3-oxo-2,3-dihydroinden-1-ylidene-acetate ( A2 ), 5,2-ethylidene-5,6-difluoro-3-oxo-2,3-dihydroinden-1-ylidene-3-methyl-2-thioxothiazolidin-4-one ( A3 ) and 2,5-ethylidene-6-oxo-5,6-dihydrocyclopenta-thiophen-4-ylidene-malononitrile ( A4 ) end-capped acceptor groups. Their optical, electrical and geometries have been compared with reported molecule R. Frontier molecular orbital diagram reveal excellent charge transfer rate, The electron density is shifted from donor to acceptor unit. Among all, A1 exhibits the highest absorption in the visible region (λ max ) at 798 nm in chloroform solvent. The maximum open circuit voltage (2.08 V) is observed for A3 when blended with PTB7-Th donor polymer. All studied molecules have high charge mobilities due to lower reorganization energy values with respect to model molecule R . A1 has the highest electron mobility among all molecules due to lower value of reorganization energy which is 0.0034. Furthermore, all designed molecules show good Solubilities in organic solvent. A2 exhibit high value of dipole moment which reveal good solubilities in fabrication process. We have designed four ( A1, A2, A3 and A4 ) fused ring electron acceptor for their use in OSCs. These molecules contain Alkoxy-Induced Naphtho-dithiophene core unit attached with different acceptor groups to enhance PCE of OSCs. All newly designed molecule have better performance as compared to R . Additionally, A1 exhibits strong absorption in visible region in both gas phase (λ max = 724.1 nm) and solvent (λ max = 798.4 nm) and exhibit lowest energy band gap (1.92 eV). • A1 shows the highest absorption maximum (λ max ) 798.4 nm in chloroform solvent. • The Designed molecules are blended with well-known donor polymer PTB7-Th. • All designed molecules have lower binding energy as compared to reference molecule R. • All newly designed molecules have excellent opto-electronic properties with respect to R.

Novel Nitrogen-Containing Heterocyclic Non-Fullerene Acceptors for Organic PhotovoltaicCells: Different End-Capping Groups Leading to a Big Difference of Power Conversion Efficiencies.

Novel cores for high performance nonfullerene acceptors (NFAs) remain to be developed. In this work, two new n-type nitrogen-containing organic heterocyclic NFAs, namely, BDTN-BF and BDTN-Th, were designed and synthesized based on a new seven fused-ring core (BDTN) with two different end-capping groups. As a result, BDTN-BF possessed similar absorption spectra in solution and solid state to BDTN-Th, but a slightly higher maximum molar extinction coefficient. Manufacturing the polymer solar cells with PM6 as the donor, the photovoltaic performance of BDTN-BF and BDTN-Th was investigated. The PM6:BDTN-BF-based device achieved the highest power conversion efficiency (PCE) of 11.54% with a high Jsc of 20.20 mA cm-2, a fill factor (FF) of 61.46%, and a large Voc of 0.93 V, and the energy loss (Eloss) was calculated to be 0.48 eV. Comparatively, the PM6:BDTN-Th-based device achieved the maximum PCE value of only 3.53% because of inadequate Jsc and FF. The higher Jsc and FF for the PM6:BDTN-BF-based device was mainly due to the effective electron transfer from PM6 to BDTN-BF, more balanced μh/μe, higher electron mobility of the neat film, better charge collection and dissociation efficiency, and more favorable morphology. These results demonstrate that the acceptors with nearly identical absorption spectra could result in a significant difference in photovoltaic performance, which stress the importance of end-capping units. Furthermore, few NFA-based devices achieve large Voc and high Jsc simultaneously as one based on PM6:BDTN-BF, indicating that nitrogen hybridization of NFAs may be an efficient strategy to realize high and balanced Voc and Jsc.

Bromination: An Alternative Strategy for Non-Fullerene Small Molecule Acceptors.

The concept of bromination for organic solar cells has received little attention. However, the electron withdrawing ability and noncovalent interactions of bromine are similar to those of fluorine and chlorine atoms. A tetra‐brominated non‐fullerene acceptor, designated as BTIC‐4Br, has been recently developed by introducing bromine atoms onto the end‐capping group of 2‐(3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene) malononitrile and displayed a high power conversion efficiency (PCE) of 12%. To further improve its photovoltaic performance, the acceptor is optimized either by introducing a longer alkyl chain to the core or by modulating the numbers of bromine substituents. After changing each end‐group to a single bromine, the BTIC‐2Br‐m‐based devices exhibit an outstanding PCE of 16.11% with an elevated open‐circuit voltage of V oc = 0.88 V, one of the highest PCEs reported among brominated non‐fullerene acceptors. This significant improvement can be attributed to the higher light harvesting efficiency, optimized morphology, and higher exciton quenching efficiencies of the di‐brominated acceptor. These results demonstrate that the substitution of bromine onto the terminal group of non‐fullerene acceptors results in high‐efficiency organic semiconductors, and promotes the use of the halogen‐substituted strategy for polymer solar cell applications.

Trifluoromethyl Group-Modified Non-Fullerene Acceptor toward Improved Power Conversion Efficiency over 13% in Polymer Solar Cells.

Herein, we report a new molecule structure modification strategy for non-fullerene small-molecule electron acceptors (NFAs) for solar cells through trifluoromethylation of end-capping groups. The synthesized trifluoromethylated acceptor ITCF3 exhibits narrower band gap, stronger light absorption, lower molecular energy levels, and better electron transport property compared to the reference NFA without the trifluoromethyl group (ITIC). Bulk heterojunction solar cells based on ITCF3 combined with the PM6 polymer donor exhibit a significantly improved power conversion efficiency of 13.3% compared with the ITIC-based device (8.4%). This work reveals great potential of trifluoromethylation in the design of efficient photovoltaic acceptor materials.

End-capped group manipulation of non-fullerene acceptors for efficient organic photovoltaic solar cells: a DFT study.

A series of acceptors, S1-S5, has been designed based on the acceptor-π-donor-π-acceptor (A-π-D-π-A) architecture by incorporating a phenothiazine unit as the central donor unit. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods have been employed to study the effect of various end-capped groups on the geometric, electronic, optical and charge transport properties of the designed acceptor molecules. The results reveal that on increasing the electron-withdrawing nature of the end-capped groups, the performance of the acceptor molecules increases. It is also observed that on increasing the flexibility of the end-capped groups, the planarity of the molecules gets destroyed and, as a result, the performance of the acceptor molecules decreases. The investigated molecules exhibit high electron affinity (EA) and low reorganization energy for electrons (λ-), indicating the electron acceptor nature of the designed molecules. The absorption properties of the molecules manifest that compounds S2-S4 possess high values of the maximum wavelength (λmax) of absorption. We have also studied the properties of a D/A active layer by considering PffBT4T-2OD as the electron donor and arranging PffBT4T-2OD/S1-S5 molecules in a face to face manner. Properties of the D/A blend indicate that molecules S2-S4 have capacity to promote charge carrier separation at the D/A active layer. Our results provide guidelines for further designing of acceptors to enhance the performance of organic solar cells (OSCs).

End-capped group manipulation of indacenodithienothiophene-based non-fullerene small molecule acceptors for efficient organic solar cells.

As the key component of organic solar cells (OSCs), the acceptor plays key roles in determining the power conversion efficiency (PCE). Based on the famous non-fullerene acceptor ITIC, a series of acceptors (A1-A5) were designed by introducing fused-ring units (phenanthrene, pyrene, benzopyrazine, dibenzo[a,c]phenazine, and phenanthro[4,5-abc]phenazine) as the end groups. Theoretical calculations showed that A1-A5 display improved solubility and redshifted absorption spectra compared with ITIC. More importantly, the newly designed acceptors exhibit much higher electron mobility, where the electron mobility of A5_h (similar to A5 but with the same hexyl side chain as ITIC) is about four orders of magnitude larger than that of ITIC. The computed binding energies of the donor PBDB-TF with the acceptor ITIC and A5_h are -2.52 eV and -3.75 eV, indicating much stronger interface interactions in PBDB-TF/A5_h. In terms of charge-transfer (CT) mechanism, we found that both PBDB-TF/ITIC and PBDB-TF/A5_h can generate CT states through direct excitation and hot excitons, meanwhile there exist more opportunities of producing CT states via the intermolecular electric field (IEF) mechanism in PBDB-TF/A5_h. Our results not only offer a set of promising ITIC-based acceptors, but also provide new insights into the donor/acceptor interface properties, which are closely related to the PCE of OSCs.

Molecular Acceptors Based on a Triarylborane Core Unit for Organic Solar Cells.

Triarylboranes that exhibit p-π* conjugation serve as versatile building blocks to design n-type organic/polymer semiconductors. A series of new molecular acceptors based on triarylborane is reported here. These molecules are designed with a boron atom that bears a bulky 2,4,6-tri-tert-butylphenyl (Mes*) substituent at the core and strong electron-withdrawing 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (IC) units as the end-capping groups that are linked to the core by bithiophene bridges. Butyl or butoxy groups are introduced to the bithiophene units to tune the optoelectronic properties. These molecules show nearly planar backbones with highly localized steric hindrance at the core, low LUMO/HOMO energy levels, and broad absorption bands spanning the visible region, which are all very desirable characteristics for use as electron acceptors in organic solar cell (OSC) applications. The attachment of butyl groups to the bithiophene bridges brings about a slightly twisted backbone, which in turn promotes good solubility and homogeneous donor/acceptor blend morphology, whereas the introduction of butoxy groups leads to improved planarity, favorable stacking in the film state, and a greatly reduced band gap. OSC devices based on these molecules exhibit encouraging photovoltaic performances with power conversion efficiencies reaching up to 4.07 %. These results further substantiate the strong potential of triarylboranes as the core unit of small molecule acceptors for OSC applications.

N-Type Thin-Film Transistors Based on Diketopyrrolopyrrole Derivatives: Role of Siloxane Side Chains and Electron-Withdrawing Substituents.

The physical properties, packing, morphology, and semiconducting performance of a planar π-conjugated system can be effectively modified by introducing side chains and substituent groups, both of which can be complementary to the π framework in changing the intermolecular association, frontier molecular orbital energy, optical band gap, and others. We herein show that installation of end-capped electron-withdrawing groups (EWGs), such as dicyanovinyl (-DCV), 3-ethylrhodanine (-RD), and 2-(3-oxo-indan-1-ylidene)-malononitrile (-INCN), together with siloxane side chains to the backbones of dithienyldiketopyrrolopyrrole (DPPT), such as DPPT-Si-DCV, DPPT-Si-RD, and DPPT-Si-INCN, can greatly improve its solubility, air stability, and film morphology to serve as an n-channel in thin-film transistor fabrication. The EWGs attached to the DPPT core narrowed the optical band gap (Egopt) and changed the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies (EHOMO and ELUMO), making them suitable for n-channel field-effect transistor (FET) applications. The benefits of introducing siloxane side chains to the DPPT core include enhanced solubility, low crystallization barrier, enantiotropic phase behavior, and much improved FET performance. The DPPT-Si-INCN film displayed low-lying HOMO (-5.82 eV) and LUMO (-4.60 eV) energy levels and an optical band gap as low as 1.22 eV, all of which suggest that this derivative can be quite resistant toward aerial oxidation. Thin films of these derivatives were prepared by the solution-shear method. A comparison of the solution-sheared films indicated that the molecular packing motif of DPPT-Si-INCN film was somehow different from that of DPPT-Si-DCV and DPPT-Si-RD, in which the π-π stacking tended to align orthogonally to the shearing direction. This specific π-π stacking alignment could have an impact on the electron mobility (μe) values in transistors based on the solution-sheared films.

Effects of Monofluorinated Positions at the End-Capping Groups on the Performances of Twisted Non-Fullerene Acceptor-Based Polymer Solar Cells.

Recently, main-chain twisted small molecules are attractive as electron-acceptors in polymer solar cells (PSCs) for their upshifted molecular energy levels, enhanced extinction coefficients, and better charge extraction properties along with longer carrier lifetimes and lower recombination rates relative to their planar analogues, which are conducive to the power conversion efficiency (PCE) promotion of PSCs. To further probe the "structure-performance" correlation of main-chain twisted acceptors, in particular the monofluorine-substituted sites on the performances of the resultant acceptors, two new main-chain twisted small molecules were synthesized, in which a fluorine atom was introduced at different sites on the end-capping group 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN). Although fine structural modification was adopted, quite different performances were obtained for the two acceptors. Compared to the 3-fluorinated analogue (i-IEICO-F3), a mixture of 4-fluorinated and 5-fluorinated isomers (i-IEICO-2F) exhibited a higher dipole moment, enlarged molar extinction coefficient with a bathochromic-shifted absorption region, suppressed charge recombinations with balanced charge mobilities, and slightly enhanced crystallinity. In combination with a fluorobenzotriazole-based medium-band gap polymer (J52), a high efficiency of 12.86% was resultantly achieved in an i-IEICO-2F-based device, which is superior to the result (7.65%) of the i-IEICO-F3 device, revealing the importance of monofluorinated positions on the performances of main-chain twisted non-fullerene acceptors.

Nonfullerene Small-Molecule Acceptors with Extended Optical Absorption Based on the “Spliced” Strategy for Organic Solar Cells

How to broaden the optical absorption of photovoltaic materials is one of the key issues in the design of high-performance organic solar cells. Nowadays, the sunlight of 400–550 nm wavelength range is not effectively utilized for most small-molecule nonfullerene acceptors. In this work, we proposed the “spliced” strategy of combining the acceptor–donor–acceptor type narrow band-gap small molecules and wide-band-gap perylene diimide (PDI) moieties via a flexible alkyl chain linkage, which could give the superposition effect of the absorption spectra, and three small-molecule acceptors (S1, S2, and S3) were designed based on various end-capping groups with different electron withdrawing abilities. Encouragingly, the as-constructed molecules can well make use of 400–550 nm sunlight with two independent absorption regions. Meanwhile, the aggregation of S1 with a highly planar end-capping group was dominated by both the PDI unit and main skeleton, while S2 and S3 exhibited PDI-controlled aggregation. When fabricated into organic solar cells, S1-based devices achieved a superior efficiency of 3.41% in comparison with those of the other two. The poor photovoltaic performance could be attributed to severe PDI aggregation, which can hinder the charge transfer through the main skeletons. This work could provide a new perspective to modulate optical absorption through the spliced strategy.

Significantly improving the performance of polymer solar cells by the isomeric ending-group based small molecular acceptors: Insight into the isomerization

Compared to benzene-fused end-capping groups (EGs), thiophene-fused EGs have some unique characteristics due to the non-centrosymmetric structure of the thiophene ring, which make them easy to form different types of isomers. Here, we develop three isomeric brominated thiophene-fused EGs, which are linked to the IDTT core to acquire three novel isomeric small-molecule acceptors (SMAs) named ITC-2Br, ITC-2Br1, and ITC-2Br2. From ITC-2Br to ITC-2Br1, the change of the bromine substituent group on the thiophene ring has only a minor impact on the physicochemical properties and photovoltaic performance. However, from ITC-2Br to ITC-2Br2, the change in the fused sites on the thiophene leads to dramatically modified absorption, energy levels, and photovoltaic performance. Theoretical simulations provide an in-depth understanding of the absorption and electrochemical differences among the three acceptors. Thanks to the favorable properties, the ITC-2Br2-based polymer solar cells (PSCs) yield a significantly higher power conversion efficiency (PCE) (13.1%) than the devices based on ITC-2Br (10.9%) and ITC-2Br1 (11.9%). From the ITC-2Br-, ITC-2Br1-to the ITC-2Br2-based devices, the JSC and FF exhibit a monotonic increase similar to the trend of PCE, which demonstrates the success of the isomerization strategy, highlighting its future prospects for the development of high-performance SMAs.

Polycondensation of Hexamethylenetetramine in Anhydrous Acid Media as a New Approach to Carbyne-Like Materials and Its Application as Dispersant of Carbon Materials

Aminocumulene (AC), a technical name that results from the hexamethylenetetramine polycondensation in anhydrous sulfuric acid, was successfully performed toward the synthesis of oligomeric cumulenic compounds made up of carbyne-like (=C=C)x fragments as a main moiety together with amino endcapping groups. The tentative mechanism for the synthesis of the soluble and insoluble AC likely included the participation of carbene species as an intermediate. Spectral properties obtained from UV-Vis, infrared, and Raman spectroscopies, and surface chemistry analysis through X-ray photoelectron spectroscopy of the soluble AC confirmed the presence of a mixture of linear and branched aminocumulene-based oligomers. AC displayed high performance as a dispersant and stabilizer agent of both multi-walled carbon nanotubes and graphene in aqueous solutions after powerful insonation treatment under controlled temperature compared to the most commonly used dispersant agents. Thereby, AC is vitally important for the preparation of carbonaceous materials based on nanoinks in a wide variety of fields.

Development of fullerene free acceptors molecules for organic solar cells: A step way forward toward efficient organic solar cells

Continuous strides are being made to explore non-fullerene acceptors for organic solar cells. Here, optoelectronic properties of four new acceptor-donor-acceptor (A-D-A) type non-fullerene acceptor molecules are evaluated for their potential use in organic solar cells. The designed molecules contain indacenodithiophene (IDT) donor core connected with various acceptor groups through benzothiadiazole (BT) bridge unit. The designed molecules differ from each other in end-capped acceptor groups. The end-capped acceptors are 2-methylene-3-oxo-2,3-dihydroinden-1-ylidene) malononitrile (M1), 2,5,6-difluoro-2-methylene-3-oxo-2,3-dihydroinden-1-ylidene) malononitrile (M2), 2-methylene-2-H-indene-1,3-dione (M3), and 2,5-methylene-6-oxo-5,6-dihydrocyclopenta-c-thiphen-4-ylidene-malononitrile (M4). The optoelectronic properties are evaluated in comparison with the recently reported R which is structurally similar to the designed molecules. The reference compound R contains indacenodithiophene (IDT) donor core unit with 3-ethyl-d-ethylidene-2-thioxothiazolidin-4-one end capped acceptor group. The A-D-A acceptor molecules evaluated here exhibit proper frontier molecular orbital diagram to facilitate the charge mobility. M2, containing 2-(5,6-difluoro-2-methylene-3-oxo-2,3-dihydroinden-1-ylidene) malononitrile end-capped acceptor group, exhibits maximum absorption at 805 nm which is attributed to extended conjugation with the BT unit. Results of transition density matrix (TDM) show clear effect of end caped acceptor group on electro-hole exciton. Small coupling of electron and hole in M4 illustrates easy dissociation of exciton as compared with other molecules. Among all, M4 shows the highest hole transfer rate as revealed from low hole reorganization energy (λh). The open circuit voltage (Voc) of reference R is 1.96 V with donor polymer PTB7-Th while the designed molecule M3 exhibits the Voc of 2.02 V. Hence, the designed fullerene free acceptor molecules are suitable for transparent organic solar cells.

Influences of Structural Modification of S, N-Hexacenes on the Morphology and OFET Characteristics.

Although chemical modifications on conjugated molecules are widely applied for the purpose of improving processability and device performances, the effect of the modification was far less investigated. Here, five S, N-hexacenes are studied to reveal the influences of (1) the lateral alkyl chain, (2) the terminal group (thiophene vs benzene), and (3) the end-capping phenyl group of the hexacenes on the morphology and organic field-effect transistor (OFET) performances. Crystal arrays of the hexacenes were prepared via polydimethylsiloxane (PDMS)-assisted crystallization (PAC) prior to morphological and OFET characterizations. The lattice structures and crystal quality of the hexacenes were evaluated by microscopy and diffraction techniques including single-crystal diffractometer, electron diffraction, and grazing incidence wide-angle X-ray scattering. The systematic analyses led to the following conclusions: (1) the bulkier alkyl side chain assists to form more densely packed crystals with less structural defects; (2) the terminal thiophene rings bring about higher-lying EHOMO, more ordered phase, and crystal orientation, whereas the terminal benzene rings deteriorate the structural order of the active layer and result in the liquid crystal phase; and (3) the phenyl end caps ameliorate the morphological order, intermolecular overlapping, thermal stability and elevate EHOMO. Thus, EH-DTPTt-Ph delivers the highest μh, contributing to high-lying EHOMO, well-oriented crystal array with a longer correlation length, and suitable lattice orientation. This systematic research provides the aspects about the effects of the functionalized S, N-hexacenes on the morphology and OFET characteristics, which is anticipated to be useful for the molecular design of heteroacenes.

Effect of π-bridges on the performance of indeno[1,2-b]fluorene-based non-fullerene small molecular acceptors

Two non-fullerene acceptors based on the indeno[1,2-b]fluorene central moiety, with selenophene or 2-vinylselenophene as π-bridges and 2-(5,6-difuoro-3-oxo-2,3- dihydro-1H-inden-1-ylidene)malononitrile as end-capping groups, i.e. FICBF-Se and FICBF-SeVi, were synthesized, and the structure-property relationships of the acceptors were systematically studied. The introduction of the vinylene group led to clearly redshifted and broader absorption and a smaller bandgap. FICBF-Se and FICBF-SeVi exhibited optical bandgaps of 1.68 and 1.54 eV, respectively. Solar cells using polymer PBDB-T as a donor and FICBF-Se as an acceptor demonstrated a power conversion efficiency (PCE) of 6.25% with a short-circuit current density (Jsc) of 11.61 mA cm−2. However, the device based on PBDB-T/FICBF-SeVi only delivered a PCE of 3.63% with a Jsc of 9.08 mA cm−2, which should be mainly because the vinylene group decreased the crystallinity and its active layer morphology showed no distinct phase separation.