Enhanced Photovoltaic Performance of Amorphous Donor–Acceptor Copolymers Based on Fluorine‐Substituted Benzodioxocyclohexene‐Annelated Thiophene

Donor–acceptor (D‐A) type π‐conjugated copolymers with crystalline behavior have been extensively investigated as donor semiconductors in organic photovoltaics (OPVs). On the other hand, the development of high‐performance amorphous donor materials is still behind. The amorphous donor copolymer DTS‐C₀(F₂) consisting of dithieno[3,2‐b:2′,3′‐d]silole ( DTS ) donor unit and the recently developed fluorine‐substituted naphtho[2,3‐c]thiophene‐4,9‐dione ( C₀(F₂) ) acceptor unit shows moderate photovoltaic performance upon blending with PC₇₁BM. In this work, to enhance the hole‐transporting characteristics, a 3‐hexylthiophene ( HT ) spacer unit is integrated into the conjugated backbone, resulting in a new amorphous copolymer DTS‐HT‐C₀(F₂) . The strong electron‐accepting nature of C₀(F₂) allows the introduction of the HT spacer without affecting the frontier orbital energies and thus the D‐A character. Without using solvent additives and thermal annealing, OPVs based on DTS‐HT‐C₀(F₂) and [6,6]‐phenyl‐C71‐butyric acid methyl ester PC₇₁BM show an improved power conversion efficiency of 9.12%. Investigation of the device physics unambiguously reveals that the hole mobility of the copolymer in the blend is increased by an order of magnitude by the introduction of HT , while keeping an amorphous film nature, leading to higher short‐circuit current density and fill factor. These results demonstrate the realization of high‐performance OPVs based on amorphous active layers.     

Fabricating High Performance,Donor–Acceptor Copolymer Solar Cells by Spray‐Coating in Air

We report the fabrication of high performance organic solar cells by spray‐coating the photoactive layer in air. The photovoltaic blends consist of a blend of carbazole and benzothiadiazole based donor–acceptor copolymers and the fullerene derivative PC₇₀BM. Here, we formulate a number of photovoltaic inks using a range of solvent systems that we show can all be deposited by spray casting. We use a range of techniques to characterize the structure of such films, and show that spray‐cast films have comparable surface roughness to spin‐cast films and that vertical stratification that occurs during film drying reduces the concentration of PCBM towards the underlying PEDOT:PSS interface. We also show that the active layer thickness and the drying kinetics can be tuned through control of the substrate temperature. High power conversion efficiencies of 4.3%, 4.5% and 4.6% were obtained for solar cells made from a blend of PC₇₀BM with the carbazole‐based co‐polymers PCDTBT, P2 and P1. By applying a low temperature anneal after the deposition of the cathode, the efficiency of spray‐cast solar‐cells based on a P2:PC₇₀BM blend is increased to 5.0%. Spray coating holds significant promise as a technique capable of fabricating large‐area, high performance organic solar cells in air.     

Interplay Between Side Chain Pattern,Polymer Aggregation,and Charge Carrier Dynamics in PBDTTPD:PCBM Bulk‐Heterojunction Solar Cells

Poly(benzo[1,2‐b:4,5‐b′]dithiophene–alt–thieno[3,4‐c]pyrrole‐4,6‐dione) (PBDTTPD) polymer donors with linear side‐chains yield bulk‐heterojunction (BHJ) solar cell power conversion efficiencies (PCEs) of about 4% with phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as the acceptor, while a PBDTTPD polymer with a combination of branched and linear substituents yields a doubling of the PCE to 8%. Using transient optical spectroscopy it is shown that while the exciton dissociation and ultrafast charge generation steps are not strongly affected by the side chain modifications, the polymer with branched side chains exhibits a decreased rate of nongeminate recombination and a lower fraction of sub‐nanosecond geminate recombination. In turn the yield of long‐lived charge carriers increases, resulting in a 33% increase in short circuit current (J _sc). In parallel, the two polymers show distinct grazing incidence X‐ray scattering spectra indicative of the presence of stacks with different orientation patterns in optimized thin‐film BHJ devices. Independent of the packing pattern the spectroscopic data also reveals the existence of polymer aggregates in the pristine polymer films as well as in both blends which trap excitons and hinder their dissociation.     

Atmospheric‐Pressure Chemical Vapor Deposition of Iron Pyrite Thin Films

Iron pyrite (cubic FeS₂) is a promising candidate absorber material for earth‐abundant thin‐film solar cells. In this report, single‐phase, large‐grain, and uniform polycrystalline pyrite thin films are fabricated on glass and molybdenum‐coated glass substrates by atmospheric‐pressure chemical vapor deposition (AP‐CVD) using the reaction of iron(III) acetylacetonate and tert‐butyl disulfide in argon at 300 °C, followed by sulfur annealing at 500–550 °C to convert marcasite impurities to pyrite. The pyrite‐marcasite phase composition depends strongly on the concentration of sodium in the growth substrate and the sulfur partial pressure during annealing. Phase and elemental composition of the films are characterized by X‐ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, Rutherford backscattering spectrometry, and X‐ray photoelectron spectroscopy. The in‐plane electrical properties are surprisingly insensitive to phase and elemental impurities, with all films showing p‐type, thermally activated transport with a small activation energy (≈30 meV), a room‐ temperature resistivity of ≈1 Ω cm, and low mobility. These ubiquitous electrical properties may result from robust surface effects. These CVD pyrite thin films are well suited to fundamental electrical studies and the fabrication of pyrite photovoltaic device stacks.     

Intra‐Molecular Donor–Acceptor Interaction Effects on Charge Dissociation,Charge Transport,and Charge Collection in Bulk‐Heterojunction Organic Solar Cells

This article reports experimental studies on internal charge dissociation, transport, and collection by using magnetic field effects of photocurrent (MFE_PC) and light‐assisted dielectric response (LADR) in highly‐efficient organic solar cells based on photovoltaic polymer PTB2 and PTB4 with intra‐molecular “donor–acceptor” interaction. The MFE_PC at low‐field (< 150 mT) indicates that intra‐molecular “donor‐acceptor” interaction generates charge dissociation in un‐doped PTB2 and PTB4 films, which is similar to that in lightly doped P3HT (Poly(3‐hexylthiophene)) with 5 wt% PCBM (1‐(3‐methyloxycarbonyl)‐propyl‐1‐phenyl (6,6) C₆₁). After PTB2 and PTB4 are mixed with PCBM to form bulk‐heterojunctions, the MFE_PC at high‐field (> 150 mT) reveals that the charge‐transfer complexes formed at PTB2:PCBM and PTB4:PCBM interfaces have much lower binding energies due to stronger electron‐withdrawing abilities, as compared to the P3HT:PCBM device, towards the generation of photocurrent. Furthermore, the light‐assisted dielectric response: LADR indicates that the PTB2:PCBM and PTB4:PCBM solar cells exhibit larger capacitances relative to P3HT:PCBM device under photoexcitation. This reflects that the PTB2:PCBM and PTB4:PCBM bulk heterojunctions have more effective charge transport and collection than the P3HT:PCBM counterpart. As a result, our experimental results indicate that intra‐molecular “donor‐acceptor” interaction plays an important role to enhance charge dissociation, transport, and collection in bulk‐heterojunction organic solar cells.     

Effects of Shortened Alkyl Chains on Solution‐Processable Small Molecules with Oxo‐Alkylated Nitrile End‐Capped Acceptors for High‐Performance Organic Solar Cells

Solution‐processable small molecules are significant for producing high‐performance bulk heterojunction organic solar cells (OSCs). Shortening alkyl chains, while ensuring proper miscibility with fullerene, enables modulation of molecular stacking, which is an effective method for improving device performance. Here, the design and synthesis of two solution‐processable small molecules based on a conjugated backbone with a novel end‐capped acceptor (oxo–alkylated nitrile) using octyl and hexyl chains attached to π–bridge, and octyl and pentyl chains attached to the acceptor is reported. Shortening the length of the widely used octyl chains improves self‐assembly and device performance. Differential scanning calorimetry and grazing incidence X‐ray diffraction results demonstrated that the molecule substituted by shorter chains shows tighter molecular stacking and higher crystallinity in the mixture with 6,6‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) and that the power conversion efficiency (PCE) of the OSC is as high as 5.6% with an open circuit voltage (V_oc) of 0.87 V, a current density (J_sc) of 9.94 mA cm^‐2, and an impressive filled factor (FF) of 65% in optimized devices. These findings provide valuable insights into the production of highly efficient solution‐processable small molecules for OSCs.     

π‐Extended Narrow‐Bandgap Diketopyrrolopyrrole‐Based Oligomers for Solution‐Processed Inverted Organic Solar Cells

A series of narrow‐bandgap π‐conjugated oligomers based on diketopyrrolopyrrole chromophoric units coupled with benzodithiophene, indacenodithiophene, thiophene, and isoindigo cores are designed and synthesized for application as donor materials in solution‐processed small‐molecule organic solar cells. The impacts of these different central cores on the optoelectronic and morphological properties, carrier mobility, and photovoltaic performance are investigated. These π‐extended oligomers possess broad and intense optical absorption covering the range from 550 to 750 nm, narrow optical bandgaps of 1.52–1.69 eV, and relatively low‐lying highest occupied molecular orbital (HOMO) energy levels ranging from ?5.24 to ?5.46 eV in their thin films. A high power conversion efficiency of 5.9% under simulated AM 1.5G illumination is achieved for inverted organic solar cells based on a small‐molecule bulk‐heterojunction system consisting of a benzodithiophene‐diketopyrrolopyrrole‐containing oligomer as a donor and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as an acceptor. Transmission electron microscopy and energy‐dispersive X‐ray spectroscopy reveal that interpenetrating and interconnected donor/acceptor domains with pronounced mesoscopic phase segregation are formed within the photoactive binary blends, which is ideal for efficient exciton dissociation and charge transport in the bulk‐heterojunction devices.     

Slow Organic‐to‐Inorganic Sub‐Lattice Thermalization in Methylammonium Lead Halide Perovskites Observed by Ultrafast Photoluminescence

Carrier dynamics in methylammonium lead halide (CH₃NH₃PbI_3–xCl_x) perovskite thin films, of differing crystal morphology, are examined as functions of temperature and excitation wavelength. At room temperature, long‐lived (>nanosecond) transient absorption signals indicate negligible carrier trapping. However, in measurements of ultrafast photoluminescence excited at 400 nm, a heretofore unexplained, large amplitude (50%–60%), 45 ps decay process is observed. This feature persists for temperatures down to the orthorhombic phase transition. Varying pump photon energy reveals that the fast, band‐edge photoluminescence (PL) decay only appears for excitation ≥2.38 eV (520 nm), with larger amplitudes for higher pump energies. Lower photon‐energy excitation yields slow dynamics consistent with negligible carrier trapping. Further, sub‐bandgap two‐photon pumping yields identical PL dynamics as direct absorption, signifying sensitivity to the total deposited energy and insensitivity to interfacial effects. Together with first principles electronic structure and ab initio molecular dynamics calculations, the results suggest the fast PL decay stems from excitation of high energy phonon modes associated with the organic sub‐lattice that temporarily enhance wavefunction overlap within the inorganic component owing to atomic displacement, thereby transiently changing the PL radiative rate during thermalization. Hence, the fast PL decay relates a characteristic organic‐to‐inorganic sub‐lattice equilibration timescale at optoelectronic‐relevant excitation energies.     

Band‐like Charge Photogeneration at a Crystalline Organic Donor/Acceptor Interface

Organic photovoltaic cells possess desirable practical characteristics, such as the potential for low‐cost fabrication on flexible substrates, but they lag behind their inorganic counterparts in performance due in part to fundamental energy loss mechanisms, such as overcoming the charge transfer (CT) state binding energy when photogenerated charge is transferred across the donor/acceptor interface. However, recent work has suggested that crystalline interfaces can reduce this binding energy due to enhanced CT state delocalization. Solar cells based on rubrene and C₆₀ are investigated as an archetypal system because it allows the degree of crystallinity to be moldulated from a highly disordered to highly ordered system. Using a postdeposition annealing method to transform as‐deposited amorphous rubrene thin films into ones that are highly crystalline, it is shown that the CT state of a highly crystalline rubrene/C₆₀ heterojunction undergoes extreme delocalization parallel to the interface leading to a band‐like state that exhibits a linear Stark effect. This state parallels the direct charge formation of inorganic solar cells and reduces energetic losses by 220 meV compared with 12 other archetypal heterojunctions reported in the literature.     

Understanding Film Formation Morphology and Orientation in High Member 2D Ruddlesden–Popper Perovskites for High‐Efficiency Solar Cells

2D Ruddlesden–Popper (RP) perovskites have recently emerged as promising candidates for hybrid perovskite photovoltaic cells, realizing power‐conversion efficiencies (PCEs) of over 10% with technologically relevant stability. To achieve solar cell performance comparable to the state‐of‐the‐art 3D perovskite cells, it is highly desirable to increase the conductivity and lower the optical bandgap for enhanced near‐IR region absorption by increasing the perovskite slab thickness. Here, the use of the 2D higher member (n = 5) RP perovskite (n‐butyl‐NH₃)₂(MeNH₃)₄Pb₅I₁₆ in depositing highly oriented thin films from dimethylformamide/dimethylsulfoxide mixtures using the hot‐casting method is reported. In addition, they exhibit superior environmental stability over thin films of their 3D counterpart. These films are assembled into high‐efficiency solar cells with an open‐circuit voltage of ≈1 V and PCE of up to 10%. This is achieved by fine‐tuning the solvent ratio, crystal growth orientation, and grain size in the thin films. The enhanced performance of the optimized devices is ascribed to the growth of micrometer‐sized grains as opposed to more typically obtained nanometer grain size and highly crystalline, densely packed microstructures with the majority of the inorganic slabs preferentially aligned out of plane to the substrate, as confirmed by X‐ray diffraction and grazing‐incidence wide‐angle X‐ray scattering mapping.     

Multi‐Length‐Scale Morphologies in PCPDTBT/PCBM Bulk‐Heterojunction Solar Cells

Additives are known to improve the performance of organic photovoltaic devices based on mixtures of a low bandgap polymer, poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]‐dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)] (PCPDTBT) and [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM). The evolution of the morphology during the evaporation of the mixed solvent, which comprises additive and chlorobenzene (CB), is investigated by in‐situ grazing incidence X‐ray scattering, providing insight into the key role the additive plays in developing a multi‐length‐scale morphology. Provided the additive has a higher vapor pressure and a selective solubility for PCBM, as the host solvent (CB) evaporates, the mixture of the primary solvent and additive becomes less favorable for the PCPDTBT, while completely solubilizing the PCBM. During this process, the PCPDTBT first crystallizes into fibrils and then the PCBM, along with the remaining PCPDTBT, is deposited, forming a phase‐separated morphology comprising domains of pure, crystalline PCPDTBT fibrils and another domain that is a PCBM‐rich mixture with amorphous PCPDTBT. X‐ray/neutron scattering and diffraction methods, in combination with UV–vis absorption spectroscopy and transmission electron microscopy, are used to determine the crystallinity and phase separation of the resultant PCPDTBT/PCBM thin films processed with or without additives. Additional thermal annealing is carried out and found to change the packing of the PCPDTBT. The two factors, degree of crystallinity and degree of phase separation, control the multi‐length‐scale morphology of the thin films and significantly influence device performance.     

Microstructure of Nanoscaled La0.6Sr0.4CoO3‐δ Cathodes for Intermediate‐Temperature Solid Oxide Fuel Cells

Nanocrystalline La_1‐xSr_xCoO_3‐δ (LSC) thin films with a nominal Sr‐content of x = 0.4 were deposited on Ce_0.9Gd_0.1O_1.95 electrolyte substrates using a low temperature sol‐gel process. The structural and chemical properties of the LSC thin films were studied after thermal treatment, which included a calcination step and a variable, extended annealing time at 700 °C or 800 °C. Transmission electron microscopy combined with selected‐area electron diffraction, energy‐dispersive X‐ray spectrometry, and scanning transmission electron microscopy tomography was applied for the investigation of grain size, porosity, microstructure, and analysis of the local chemical composition and element distribution on the nanoscale. The area specific resistance (ASR) values of the thin film LSC cathodes, which include the lowest ASR value reported so far (ASR_chem = 0.023 Ωcm² at 600 °C) can be interpreted on the basis of the structural and chemical characterization.     

Open‐Circuit Voltage in Organic Solar Cells: The Impacts of Donor Semicrystallinity and Coexistence of Multiple Interfacial Charge‐Transfer Bands

In organic solar cells (OSCs), the energy of the charge‐transfer (CT) complexes at the donor–acceptor interface, E _CT, determines the maximum open‐circuit voltage (V _OC). The coexistence of phases with different degrees of order in the donor or the acceptor, as in blends of semi‐crystalline donors and fullerenes in bulk heterojunction layers, influences the distribution of CT states and the V _OC enormously. Yet, the question of how structural heterogeneities alter CT states and the V _OC is seldom addressed systematically. In this work, we combine experimental measurements of vacuum‐deposited rubrene/C₆₀ bilayer OSCs, with varying microstructure and texture, with density functional theory calculations to determine how relative molecular orientations and extents of structural order influence E _CT and V _OC. We find that varying the microstructure of rubrene gives rise to CT bands with varying energies. The CT band that originates from crystalline rubrene lies up to ≈0.4 eV lower in energy compared to the one that arises from amorphous rubrene. These low‐lying CT states contribute strongly to V _OC losses and result mainly from hole delocalization in aggregated rubrene. This work points to the importance of realizing interfacial structural control that prevents the formation of low E _CT configurations and maximizes V _OC.     

Inorganic CsPb1−xSnxIBr2 for Efficient Wide‐Bandgap Perovskite Solar Cells

Recently, the stability of organic–inorganic perovskite thin films under thermal, photo, and moisture stresses has become a major concern for further commercialization due to the high volatility of the organic cations in the prototype perovskite composition (CH₃NH₃PbI₃). All inorganic cesium (Cs) based perovskite is an alternative to avoid the release or decomposition of organic cations. Moreover, substituting Pb with Sn in the organic–inorganic lead halide perovskites has been demonstrated to narrow the bandgap to 1.2–1.4 eV for high‐performance perovskite solar cells. In this work, a series of CsPb_1?xSn_xIBr₂ perovskite alloys via one‐step antisolvent method is demonstrated. These perovskite films present tunable bandgaps from 2.04 to 1.64 eV. Consequently, the CsPb_0.75Sn_0.25IBr₂ with homogeneous and densely crystallized morphology shows a remarkable power conversion efficiency of 11.53% and a high V_oc of 1.21 V with a much improved phase stability and illumination stability. This work provides a possibility for designing and synthesizing novel inorganic halide perovskites as the next generation of photovoltaic materials.     

2‐(4‐Ethoxy phenyl)‐4‐phenyl quinoline organic phosphor for solution processed blue organic light‐emitting diodes

This paper reports the synthesis and characterization of 2‐(4‐ethoxyphenyl)‐4‐phenyl quinoline (OEt‐DPQ) organic phosphor using an acid‐catalyzed Friedlander reaction and the preparation of blended thin films by molecularly doping OEt‐DPQ in poly(methyl methacrylate) (PMMA) at different wt%. The molecular structure of the synthesized phosphor was confirmed by Fourier transform infra‐red (FTIR) spectroscopy and nuclear magnetic resonance spectra (NMR). Surface morphology and percent composition of the elements were assessed by scanning electron microscopy (SEM) and energy dispersive analysis of X‐rays (EDAX). The thermal stability and melting point of OEt‐DPQ and thin films were probed by thermo‐gravimetric analysis (TGA)/differential thermal analysis (DTA) and were found to be 80°C and 113.6°C, respectively. UV–visible optical absorption spectra of OEt‐DPQ in the solid state and blended films produced absorption bands in the range 260–340 nm, while photoluminescence (PL) spectra of OEt‐DPQ in the solid state and blended thin films demonstrated blue emission that was registered at 432 nm when excited at 363–369 nm. However, solvated OEt‐DPQ in chloroform, tetrahydrofuran or dichloromethane showed a blue shift of 31–43 nm. Optical absorption and emission parameters such as molar extinction coefficient (ε), energy gap (E_g), transmittance (T), reflectance (R), refractive index (n), oscillator energy (E₀) and oscillator strength (f), quantum yield (φ_f), oscillator energy (E₀), dispersion energy (E_d), Commission Internationale de l'Éclairage (CIE) co‐ordinates and energy yield fluorescence (E_F) were calculated to assess the phosphor's suitability as a blue emissive material for opto‐electronic applications such as organic light‐emitting diodes (OLEDs), flexible displays and solid‐state lighting technology.     

14.2% Efficiency Dye‐Sensitized Solar Cells by Co‐sensitizing Novel Thieno[3,2‐b]indole‐Based Organic Dyes with a Promising Porphyrin Sensitizer

A new series of 4‐hexyl‐4H‐thieno[3,2‐b]indole (HxTI) based organic chromophores is developed by structural engineering of the electron donor (D) group in the D–HxTI–benzothiadiazole‐phenyl‐acceptor platform with different fluorenyl moieties, such as unsubstituted fluorenyl (SGT‐146) and hexyloxy (SGT‐147), decyloxy (SGT‐148) and hexyloxy‐phenyl substituted (SGT‐149) fluorenyl moieties. In comparison to a reference dye SGT‐137 with a biphenyl‐based donor, the effects of the donating ability and bulkiness of the fluorenyl based donor in this D–π–A‐structured platform on molecular properties and photovoltaic performance are investigated to establish the structure–property relationship. The photovoltaic performance of dye‐sensitized solar cells (DSSCs) is improved according to the bulkiness of the donor groups. As a result, the DSSCs based on SGT‐149 show high power conversion efficiencies (PCEs) of 11.7% and 10.0% with a [Co(bpy)₃]^2+/3+ (bpy = 2,2′‐bipyridine) and an I^?/I₃^? redox electrolyte, respectively. Notably, the co‐sensitization of SGT‐149 with a SGT‐021 porphyrin dye by utilizing a simple “cocktail” method, exhibit state‐of‐the‐art PCEs of 14.2% and 11.6% with a [Co(bpy)₃]^2+/3+ and an I^?/I₃^? redox electrolyte, respectively.     

Effect of thermal annealing on the structural and optical properties of tris‐(8‐hydroxyquinoline)aluminum(III) (Alq3) films

Tris‐(8‐hydroxyquionoline)aluminum (Alq₃) was synthesized and coated on to a glass substrate using the dip coating method. The structural and optical properties of the Alq₃ film after thermal annealing from 50°C to 300°C in 50° steps was studied. The films have been prepared with 2 to 16 layers (42–324 nm). The thickness and thermal annealing of Alq₃ films were optimized for maximum luminescence yield. The Fourier transform infrared spectrum confirms the formation of quinoline with absorption in the region 700 ? 500/cm. Partial sublimation and decomposition of quinoline ion was observed with the Alq₃ films annealed at 300°C. The X‐ray diffraction pattern of the Alq₃ film annealed at 50°C to 150°C reveals the amorphous nature of the films. The Alq₃ film annealed above 150°C were crystalline nature. Film annealed at 150°C exhibits a photoluminescence intensity maximum at 512 nm when excited at 390 nm. The Alq₃ thin film deposited with 10 layers (220 nm) at 150°C exhibited maximum luminescence yield. Copyright © 2014 John Wiley & Sons, Ltd.     

Terthieno[3,2‐b]Thiophene (6T) Based Low Bandgap Fused‐Ring Electron Acceptor for Highly Efficient Solar Cells with a High Short‐Circuit Current Density and Low Open‐Circuit Voltage Loss

A terthieno[3,2‐b]thiophene ( 6T ) based fused‐ring low bandgap electron acceptor, 6TIC , is designed and synthesized for highly efficient nonfullerene solar cells. The chemical, optical, and physical properties, device characteristics, and film morphology of 6TIC are intensively studied. 6TIC shows a narrow bandgap with band edge reaching 905 nm due to the electron‐rich π‐conjugated 6T core and reduced resonance stabilization energy. The rigid, π‐conjugated 6T also offers lower reorganization energy to facilitate very low V_OC loss in the 6TIC system. The analysis of film morphology shows that PTB7‐Th and 6TIC can form crystalline domains and a bicontinuous network. These domains are enlarged when thermal annealing is applied. Consequently, the device based on PTB7‐Th : 6TIC exhibits a high power conversion efficiency (PCE) of 11.07% with a high J_SC > 20 mA cm^?2 and a high V_OC of 0.83 V with a relatively low V_OC loss (≈0.55 V). Moreover, a semitransparent solar cell based on PTB7‐Th : 6TIC exhibits a relatively high PCE (7.62%). The device can have combined high PCE and high J_SC is quite rare for organic solar cells.     

Medium Bandgap Polymer Donor Based on Bi(trialkylsilylthienyl‐benzo[1,2‐b:4,5‐b′]‐difuran) for High Performance Nonfullerene Polymer Solar Cells

A new 2D‐conjugated medium bandgap donor–acceptor copolymer, J81 , based on benzodifuran with trialkylsilyl thiophene side chains as donor unit and fluorobenzothiazole as acceptor, is synthesized and successfully used in nonfullerene polymer solar cells (PSCs) with low bandgap n‐type organic semiconductor (n‐OS) 3,9‐bis(2‐methylene‐ (3‐(1,1‐dicyanomethylene)‐indanone)‐5,5,11,11‐tetrakis(4‐ hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]‐ dithiophene (ITIC) and m ‐ITIC as acceptor. J81 possesses a lower‐lying highest occupied molecular orbital (HOMO) energy level of ?5.43 eV and medium bandgap of 1.93 eV with complementary absorption in the visible–near infrared region with the n‐OS acceptor. The PSCs based on J81 :ITIC and J81 :m ‐ITIC yield high power conversion efficiency of 10.60% and 11.05%, respectively, with high V _oc of 0.95–0.96 V benefit from the lower‐lying HOMO energy level of J81 donor. The work indicates that J81 is another promising polymer donor for the nonfullerene PSCs.     

Balancing High Open Circuit Voltage over 1.0 V and High Short Circuit Current in Benzodithiophene‐Based Polymer Solar Cells with Low Energy Loss: A Synergistic Effect of Fluorination and Alkylthiolation

Based on the most recently significant progress within the last one year in organic photovoltaic research from either alkylthiolation or fluorination on benzo[1,2‐b:4,5‐b′]dithiophene moiety for high efficiency polymer solar cells (PSCs), two novel simultaneously fluorinated and alkylthiolated benzo[1,2‐b:4,5‐b′] dithiophene (BDT)‐based donor–acceptor (D–A) polymers, poly(4,8‐bis(5′‐((2″‐ethylhexyl)thio)‐4′‐fluorothiophen‐2′‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl)‐alt‐2′‐ethylhexyl‐3‐fluorothieno[3,4‐b]thiophene‐2‐carboxylate (PBDTT‐SF‐TT) and poly(4,8‐bis(5′‐((2″‐ethylhexyl)thio)‐4′‐fluorothiophen‐2′‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl)‐alt‐1,3‐bis(thiophen‐2‐yl)‐5,7‐bis(2‐ethylhexyl)benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione (PBDTT‐SF‐BDD), namely, via an advantageous and synthetically economic route for the key monomer are reported herein. Synergistic effects of fluorination and alkylthiolation on BDT moieties are discussed in detail, which is based on the superior balance between high V_oc and large J_sc when PBDTT‐SF‐TT/PC₇₁BM and PBDTT‐SF‐BDD/PC₇₁BM solar cells present their high V_oc as 1.00 and 0.97 V (associated with their deep highest occupied molecular orbital level of ?5.54 and ?5.61 eV), a moderately high J_sc of 14.79 and 14.70 mA cm^?2, and thus result a high power conversion efficiency of 9.07% and 9.72%, respectively. Meanwhile, for PBDTT‐SF‐TT, a very low energy loss of 0.59 eV is pronounced, leading to the promisingly high voltage, and furthermore performance study and morphological results declare an additive‐free PSC from PBDTT‐SF‐TT, which is beneficial to practical applications.