High open-circuit voltage of the solution-processed organic solar cells based on benzothiadiazole–triphenylamine small molecules incorporating π-linkage

Two novel small molecular photovoltaic (PV) materials, BDPTBT and BDATBT were designed and synthesized, consisting of 5,6-bis-(octyloxy)benzo[c][1,2,5]thiadiazole (DOBT) as electron-withdrawing core (A), and triphenylamine (TPA) as electron-donating side group (D). Moreover, the benzene and ethynylbenzene as π-linkage were introduced to form donor–π-acceptor–π-donor (D–π-A–π-D) typed molecular structures, respectively. To fully investigate the linkage effect of a series of small molecules, two reference compounds BDCTBT and BDETBT were also studied systematically, consisting of 2-phenylacrylonitrile and styrene as π-linkage, respectively. As a result, the π-linkage units, benzene, styrene, ethynylbenzene and 2-phenylacrylonitrile played an important role in modifying molecular structure and improving PV performance. Bulk heterojunction (BHJ) solar cells based on BDPTBT/PC₆₁BM and BDATBT/PC₆₁BM yielded the power conversion efficiencies (PCEs) of 2.99% and 2.03%, respectively. Notably, BDATBT based device showed a high open-circuit voltage (Voc) of 1.03 V. Compared to the results we have reported previously, the reference devices based on BDCTBT/PC₆₁BM and BDETBT/PC₆₁BM with the optimized weight ratio showed dramatically enhanced PCEs of 4.84% and 3.40%, respectively, and BDCTBT based device showed a high Voc of 1.08 V. To our knowledge, the Voc of 1.08 V is the highest voltage reported to date for devices prepared from solution-processed small-molecule-donor materials, and the PCE of 4.84% is the highest efficiency reported so far for D–A–D-typed benzothiadiazole (BT)–TPA based solution-processed small molecules PV devices.     

Linear and propeller-like fluoro-isoindigo based donor–acceptor small molecules for organic solar cells

Two donor–acceptor type fluoro-isoindigo based small molecule semiconductors are synthesized and their optical, electrochemical, thermal, and charge transport properties are investigated. The two molecular chromophores differ by their architecture, linear (M1) vs propeller-like (M2). Both molecules present a broad absorption in the visible range and a low optical HOMO–LUMO gap (∼1.6 eV). AFM images of solution-processed thin films show that the trigonal molecule M2 forms highly oriented fibrils after a few seconds of solvent vapor annealing. The materials are evaluated as electron donor components in bulk heterojunction organic solar cells using PC₆₁BM as the electron acceptor. The devices based on the propeller-like molecule M2 exhibit a high open-circuit voltage (around 1.0 V) and a power conversion efficiency of 2.23%.     

Novel A-D-A type small molecules with β-alkynylated BODIPY flanks for bulk heterojunction solar cells

A serial of novel A-D-A type small molecules with BODIPY linked through alkynyl with various electron donor units such as fluorene, carbazole, benzodithiophene and phenothiazine, namely F-BDP, C-BDP, B-BDP and P-BDP, respectively, were designed and synthesized. Introducing the alkynyl bridge leads to extending the molecular absorption spectrum to the range of 320–700 nm with high molar extinction coefficients (10⁵ cm⁻¹ M⁻¹) and strong fluorescence quenching. The molecules showed relatively low HOMO ranging from −5.02 to −5.24 eV as estimated from cyclic voltammetry measurements. Interestingly, B-BDP with BDT as donor exhibits more obviously red-shifted absorption in the solid state compared to F-BDP, C-BDP and P-BDP. Furthermore, the solution-processed bulk-heterojunction organic solar cell based on B-BDP/PC₇₁BM present superior charge transport property and more favorable nanoscale morphology, resulting in a significant higher J_sc of 11.84 mA cm² and FF than the other counterparts, thus achieved a higher PCE of 4.65%, which is one of the best values among the ever reported BODIPY based organic solar cells.     

Benzo[1,2-b:4,5-b′]dithiophene and benzotriazole based small molecule for solution-processed organic solar cells

A novel deep HOMO A₁-π-A₂-D-A₂-π-A₁ type molecule (D(CATBTzT)BDT), which terminal electron-withdrawing octyl cyanoacetate group is connected to a benzo[1,2-b:4,5-b′]dithiophene (BDT) core through another electron-accepting benzotriazole block, has been synthesized, characterized, and employed as electron donor material for small molecule organic solar cells (SM-OSCs). By simple solution spin-coating fabrication process, D(CATBTzT)BDT/PC₆₁BM based OSCs exhibit a power conversion efficiency (PCE) of 3.61% with a high open-circuit voltage of 0.93 V. The D(CATBTzT)BDT based solar cells device also can show high FF of 72% with PCEs of 2.31% which is one of the best FF results for solution-processed SM-OSCs.     

D–A–Ar-type small molecules with enlarged π-system of phenanthrene at terminal for high-performance solution processed organic solar cells

Two novel D–A–Ar-type small molecules of TPA–DPP–P and TPA(DPP–P)₂ were synthesized and characterized, in which triphenylamine (TPA), diketopyrrolopyrrole (DPP) and phenanthrene (P) were used as the donor (D) core, acceptor (A) arm, and enlarged π-system of polycyclic arene (Ar) terminal. Their absorptive, electro-chemical, thermal, and photovoltaic properties were preliminary investigated. Significantly improved photophysical and photovoltaic performances were observed for both small molecules containing the planar P terminal in comparison with those for their parent D–A-type molecule of TPA–DPP. The highest power conversion efficiency (PCE) of 3.42% and a maximum short-circuit current density (J_sc) of 9.2 mA/cm² were obtained in the solution-processed TPA(DPP–P)₂-based solar cells using [6,6]-phenyl-C-71-butyric acid methyl ester (PC₇₁BM) as acceptor. The PCE and J_sc values are 8.76 and 4.97 times higher than those of the TPA–DPP-based cells, respectively. It indicates that appending the enlarged π-system of the planar P terminal and incorporating the DPP–P arm into D–A-type small molecule are efficient approaches to improve photophysical and photovoltaic performances for its resulting molecules.     

All-optical switching in 3,3′-diethyl-2,2′-thiatricarbocyanine Iodide dye molecules

All-optical switching has been theoretically analyzed in the 3,3＇-diethyl-2,2＇-thiatricarboeyanine iodide （DTTCI） carbocyanine dye that exhibits large excited-state absorption to achieve high contrast and fast switching. Switching has been analyzed both ns and ps pump pulse widths. It is shown that there is an optimum value of concentration for given peak pump intensity at which maximum modulation can be achieved. We can get 93.84% modulation of transmission of a CW probe laser beam at 532 nm at peak pumping intensity of 500 kW/cm^2 at 763 nm, with At =1 ns and concentration of 80 μM in alcohol, resulting in switch-off and on time of 2 ns and 8 ns, respectively. The results have been also used to design all-optical NOT and the universal NOR and NAND logic gates with multiple pump laser pulses.     

Indoline as electron donor unit in “Push–Pull” organic small molecules for solution processed organic solar cells: Effect of the molecular π-bridge on device efficiency

In this work we have synthesized and characterized four indoline-based small organic molecules for their use as electron donor moiety in bulk-heterojunction solution processed organic solar cells combined with PC₇₀BM as electron acceptor. Our results show a wide range of light to energy efficiencies from 0.8% to 3.5% under standard measurement conditions. An initial analysis suggests that the main limitation is the device photocurrent due to the device film thickness. Yet, charge transfer dynamics were studied to correlate charge loss mechanisms to π-bridge structural variations and, moreover, mobility measurements were also carried out to fully explain these device limitations.     

Donor–acceptor–acceptor–donor small molecules for solution processed bulk heterojunction solar cells

We report on the optical and electrochemical characterization (experimental and theoretical) of two donor substituted benzothiadiazole with different cyano based acceptor π-linkers, tetracyanobutadiene (TCBD) SM1 and dicyanoquinomethane (DCNQ) SM2, and explore them as the donor component for solution processed bulk heterojunction organic solar cells, along with PC₇₁BM as the electron acceptor. The solution bulk heterojunction (BHJ) solar cells based on dichloromethane (DCM) processed active layer with SM1 and SM2 as donor and PC₇₁BM as acceptor achieve power conversion efficiency (PCE) of 2.76% and 3.61%, respectively. The solar cells based on these two small molecules exhibit good Voc, which is attributed to their deep HOMO energy level. The higher PCE of the device based on SM2 compared to SM1 is attributed to the its small bandgap, broader absorption profile and enhanced hole mobility. Additionally, the PCE of the SM2:PC₇₁BM based solar cells processed with 1-chloronaphthalene CN (3 v%)/DCM is further improved reaching upto 4.86%. This increase in PCE has been attributed to the improved nanoscale morphology and more balanced charge transport in the device, due to the solvent additive.     

A–D–A type organic donors employing coplanar heterocyclic cores for efficient small molecule organic solar cells

Two linear organic A–D–A molecules (DTPT and DTPTT) comprised of electron-donating (D) coplanar heteroacenes as core end-capping with electron-accepting (A) dicyanovinylene were investigated as electron donor materials in organic photovoltaic (OPV) applications. The photophysical and electrochemical properties of these two dyes were examined. The A–D–A configuration renders these two molecules to have intense and red-shifted absorption characteristics for better light-harvesting (higher photocurrent density), while retaining relatively low HOMO energy levels for keeping sufficiently high open circuit voltage (V_oc) in OPV. The optical constants and molecular orientation of thin films were acquired with variable-angle spectroscopic ellipsometry (VASE). Due to the anisotropic behavior observed in thin film, these two organic donors were firstly adopted to combine with electron acceptor C₆₀ in a vacuum-processed planar heterojunction (PHJ) solar cells. The optimized DTPT-based PHJ device yielded a PCE of 3.01%, whereas the PHJ device based on DTPTT, delivered an inferior PCE of 1.70%. The exciton diffusion length extracted from spectrum-response modeling of PHJ devices is ∼5 nm and ∼4 nm for DTPT and DTPTT, respectively. Replacement of C₆₀ with C₇₀ for a better spectral response in 400–500 nm, planar-mixed heterojunction (PMHJ) SMOSCs without a thin donor layer in between the active layer and MoO₃ was found to produce optimum device results. The optimized DTPTT-based device showed a PCE of 3.02%, while the shorter counterpart DTPT delivered a PCE up to 5.64%.     

Triarylamine-based dual-function coadsorbents with extended π-conjugation aryl linkers for organic dye-sensitized solar cells

Triarylamine-based dual-function coadsorbents containing a carboxylic acid acceptor linked by extended π-conjugation aryl linkers (e.g., phenylene: HC-A3, naphthalene: HC-A4 and anthracene: HC-A5) were newly designed and synthesized. They were used as coadsorbents in organic dye-sensitized solar cells (DSSCs) based on a porphyrin dye (hexyloxy-biphenyl-ZnP-CN-COOH (HOP)). For comparison, the π-conjugated phenyl linker (HC-A3) previously developed by our group was also used as a coadsorbent. The structural effects on the photophysical and electrochemical properties and DSSC performance were systematically investigated. As a result, the DSSCs based on HC-A4 and HC-5 displayed power conversion efficiencies (PCEs) of 8.2% and 5.1%, respectively, while the HC-A3-based DSSC achieved a PCE of 7.7%. In the case of HC-A4, both the short-circuit photocurrent densities (J_sc) and open-circuit voltages (V_oc) of DSSCs were simultaneously improved to a large extent due to the more effective prevention of π−π stacking of organic dye molecules and the better light-harvesting effect at short wavelengths. The HC-A5-based DSSC exhibited a much lower short-circuit current (J_sc) and open-circuit voltages (V_oc) compared to the HC-A4-based DSSC, due to the fact that the dihedral angle of the π-conjugated linkers was too high for electron injection into the TiO₂ conduction band (CB) level. This had a reduced effect on preventing the π−π stacking of dye molecules, resulting in lower J_sc and V_oc values.     

A strategy to enhance both VOC and JSC of A–D–A type small molecules based on diketopyrrolopyrrole for high efficient organic solar cells

Four different diketopyrrolopyrrole (DPP)-based small molecules (SMs) with A–D–A type structure were synthesized, where electron-donating unit (D) was systematically varied with different electron-donating power (thiophene vs. phenylene; thienothiophene vs. naphthalene) and different molecular planarity (bithiophene vs. thienothiophene; and biphenylene vs. naphthalene). The small molecules with weak donating unit (phenylene or naphthalene) have deeper HOMO energy levels than those with strong donating unit (thiophene or thienothiophene), and thus exhibit higher V_OC. When the fused aromatic ring (thienothiophene or naphthalene) with planar molecular structure is introduced in SMs, the SMs exhibit high hole mobility and thus afford high J_SC. As a result, the introduction of naphthalene (weak donating power and planar structure) enhances both V_OC and J_SC, resulting in a promising power conversion efficiency of 4.4%. This result provides a valuable guideline for rational design of conjugated small molecules for high performance organic solar cells.     

Inorganic perovskite/organic tandem solar cells with efficiency over 20%

The rapid development of perovskite solar cells is beyond our imagination.The power conversion efficiency(PCE)of organic-inorganic hybrid perovskite solar cells has reached 25.5%(https://www.nrel.gov/pv/cell-efficiency.html).However,the unsatisfactory stability of hybrid perovskites is an obstacle for their commercialization,which results from the volatile and hygroscopic organic cations[1].     

Acetylene-bridged D–A–D type small molecule comprising pyrene and diketopyrrolopyrrole for high efficiency organic solar cells

To explore effects of acetylene-incorporation, acetylene-bridged D–A–D type small molecules ((HD/OD)-DPP-A-PY) using pyrene as a donor and diketopyrrolopyrrole as an acceptor were successfully synthesized and characterized. (HD/OD)-DPP-A-PY exhibited planar back-bone, conjugation extension, enhanced light absorption, and low HOMO energy level. Combined with the advanced properties, solution-processed OSCs based on a blend of HD-DPP-A-PY as a donor and [6,6]-phenyl-C₇₁-butyric-acid-methyl-ester (PC₇₀BM) as an acceptor exhibited PCEs as high as 3.15%.     

A crystalline D-π-A organic small molecule with naphtho[1,2-b:5,6-b′]dithiophene-core for solution processed organic solar cells

In this work, we have designed and synthesized a new naphtho[1,2-b:5,6-b′]dithiophene-containing enlarged π-conjugated donor–acceptor (D–A) small molecule, NDT(TTz)₂, for use in solution-processed organic photovoltaics. NDT(TTz)₂, which contains a thiophene-bridged naphtho[1,2-b:5,6-b′]dithiophene as the central fused core and triphenylamine-flanked thiophene thiazolothiazole as a spacer, was synthesized via sequential Suzuki and Stille coupling reactions. The thermal, physiochemical, and electrochemical properties of NDT(TTz)₂ have been evaluated by differential scanning calorimetry, thermogravimetry, UV–Vis spectroscopy, photoluminescence spectroscopy, X-ray diffraction, and cyclic voltammetry. As desired for photovoltaic applications, NDT(TTz)₂ possesses good solubility, thermal stability, and a well-ordered, π–π stacked, crystallinity. The optical band gap and HOMO level of NDT(TTz)₂ were determined to be 2.0 eV and −5.23 eV, respectively. In addition to organic thin film transistor studies, application of NDT(TTz)₂ to preliminary photovoltaic devices has also been investigated by fabricating solution-processed bulk heterojunction solar cells together with PC₇₁BM in a typical layered device structure, ITO/PEDOT:PSS/NDT(TTz)₂:PC₇₁BM/LiF/Al. Without extensive optimization of the device, NDT(TTz)₂ in these devices shows a maximum power conversion efficiency of 1.44% under AM 1.5 illumination at a 100 mW/cm² intensity.     

Novel dithieno[3,2-b:2′,3′-d]pyrrole-based organic dyes with high molar extinction coefficient for dye-sensitized solar cells

Three new metal-free organic dyes FD1–3 with a planar dithieno[3,2-b:2′,3′-d]pyrrole unit as linker were synthesized and used for dye-sensitized solar cells with high molar extinction coefficients. In this work, dithieno[3,2-b:2′,3′-d]pyrrole was employed as π-conjugated bridge to construct A–π–d–π–A organic dyes, where 9,9-dihexyl-9H-fluorene was used as a donor, and cyanoacrylic acid as an electron acceptor. For a typical device, a solar energy conversion efficiency (η) of 6.36% based on FD2 was achieved under simulated AM 1.5 solar irradiation (100 mW cm^?2) with a short-circuit photocurrent density (J_sc) of 13.76 mA cm^?2, an open-circuit voltage (V_oc) of 669 mV, a fill factor (ff) of 0.691. The results suggest that the organic dye with a functionalized dithienopyrrole unit is a promising candidate for DSSCs due to its high molar extinction coefficients.     

Poly(2,2’-(2,5-difluoro-1,4-phenylene)dithiophene-alt-naphthalene diimide) synthesized by direct (hetero)arylation reaction for all-polymer solar cells

The weak donor-strong acceptor polymer acceptors for all-polymer solar cells (all-PSCs) have gained much less attention compared with the typical donor-strong acceptor counterparts. Direct (hetero)arylation polymerization reaction is a rising synthetic method, although most of the naphthalene diimide polymer photovoltaic acceptors have been prepared by classic Stille polymerization. A weak donor-strong acceptor polymer acceptor PNB2F has been successfully designed and synthesized by the two-step direct (hetero)arylation reaction and further applied in all-PSCs. The all-PSC device based on PNB2F and electron-donating polymer PBDB-T gained a PCE of 4.49%. The results demonstrate that direct (hetero)arylation reaction is a promising tool for building efficient polymer acceptors with convenient and low-cost synthesis ideas.     

D–π–A organic dyes with various bulky amine-typed donor moieties for dye-sensitized solar cells employing the cobalt electrolyte

SGT dyes containing various amine-typed donors as triphenylamine, bis-fluorenylamine and bis-phenothiazinylamine as the electron donor and a cyanoacrylic acid moiety as electron acceptor in D–π–A system, were developed to use in dye-sensitized solar cells (DSSCs). The SGT-102 dye containing bis-fluorenylamine had a better prevented charge recombination than other SGT dyes; leading to improvement in V_oc. As a result, the conversion efficiency of 7.22% was achieved with a J_sc of 12.1 mA cm⁻², V_oc of 865 mV and a FF of 69.1 for the DSSC employing a dye containing the bulky bis-fluorenylamine donor unit, while the DSSC based on a dye containing the bulky bis-phenothiazinylamine donor unit showed a lower J_sc and V_oc, leading to a lower efficiency of 5.16%, due to slow charge recombination associated with differently geometric structure orientations.     

Characterization of two new (A–π)2–D–A type dyes with different central D unit and their application for dye sensitized solar cells

We report the photophysical, electrochemical and theoretical properties of two dyes with same acceptor, π-linker and anchoring acceptor unit and different TPA (D1) and pyran (D2) donor central unit. The change in the central unit resulted in corresponding different photophysical and electrochemical properties. The dye sensitized solar cell fabricated using dye D1 showed the higher incident photon to current efficiency of 54%, a short circuit current (J_sc) of 11.86 mA/cm², an open circuit voltage of 0.64 V, and fill factor (FF) of 0.68, corresponding an overall power conversion efficiency of 5.16% which is higher than that for D2 based DSSCs (4.42%). The difference in the PCE of DSSCs based on D1 and D2 is partly, due to the smaller amount of dye loading, higher dark current and charge recombination rate of D1 based DSSC. The electrochemical spectra of DSSCs demonstrated longer electron life time and charge recombination resistance and small charge transport resistance for D1 sensitized DSSC, results the higher PCE.     

N,N′-diphenylperylene diimide functioning as a sensitizing light absorber based on excitation transfer for organic thin-film solar cells

We demonstrated that N,N′-diphenylperylene tetracarbonic diimide (PTCDI-Ph) could work as an n-type sensitizing layer for the C₆₀ n-type layer owing to interlayer excitation transfer (ET) when the PTCDI-Ph layer was placed between the C₆₀ layer and the aluminum anode coupled with the bathocuproine layer. Well-aligned lowest unoccupied molecular orbitals between C₆₀ and PTCDI-Ph (?4.55 eV for PTCDI-Ph and ?4.5 eV for C₆₀) and a larger bandgap for PTCDI-Ph than C₆₀ (2.04 eV for PTCDI-Ph and 2.0 eV for C₆₀) enabled this interlayer ET-based sensitization. Further, the optical interference effect could be also involved in the sensitization. It was also demonstrated that the combination of both n-type materials C₆₀ and PTCDI-Ph could successfully reduce the amount of the expensive C₆₀ used, and a thin C₆₀ layer was indispensable for efficient charge separation. PTCDI-Ph could work as a light-harvesting n-type material incorporating C₆₀-based cells to compensate for C₆₀’s weak optical absorption.     

Low-LUMO 56π-electron fullerene acceptors bearing electron-withdrawing cyano groups for small-molecule organic solar cells

56π-Electron fullerene derivatives with electron-withdrawing cyano groups were synthesized by the reaction of 58π-electron fullerenes with NaCN, followed by in situ treatment with TsCN or MeOTf. The fullerene derivatives have low-lying LUMO levels, which are comparable with or lower than that of pristine C₆₀. They were used as solution-processable electron acceptors in small-molecule organic solar cells that showed a maximum power conversion efficiency of 2.0% (J_SC = 7.05 mA/cm², V_OC = 0.62 V and FF = 0.45) using chloroindium phthalocyanine as an electron donor.