Donor and Acceptor Unit Sequences Influence Material Performance in Benzo[1,2‐b:4,5‐b′]dithiophene–6,7‐Difluoroquinoxaline Small Molecule Donors for BHJ Solar Cells

Well‐defined small molecule (SM) donors can be used as alternatives to π‐conjugated polymers in bulk‐heterojunction (BHJ) solar cells with fullerene acceptors (e.g., PC₆₁/₇₁BM). Taking advantage of their synthetic tunability, combinations of various donor and acceptor motifs can lead to a wide range of optical, electronic, and self‐assembling properties that, in turn, may impact material performance in BHJ solar cells. In this report, it is shown that changing the sequence of donor and acceptor units along the π‐extended backbone of benzo[1,2‐b:4,5‐b′]dithiophene–6,7‐difluoroquinoxaline SM donors critically impacts (i) molecular packing, (ii) propensity to order and preferential aggregate orientations in thin‐films, and (iii) charge transport in BHJ solar cells. In these systems ( SM1‐3 ), it is found that 6,7‐difluoroquinoxaline ([2F]Q) motifs directly appended to the central benzo[1,2‐b:4,5‐b′]dithiophene (BDT) unit yield a lower‐bandgap analogue ( SM1 ) with favorable molecular packing and aggregation patterns in thin films, and optimized BHJ solar cell efficiencies of ≈6.6%. ¹H‐¹H DQ‐SQ NMR analyses indicate that SM1 and its counterpart with [2F]Q motifs substituted as end‐group SM3 possess distinct self‐assembly patterns, correlating with the significant charge transport and BHJ device efficiency differences observed for the two analogous SM donors (avg. 6.3% vs 2.0%, respectively).     

Influence of Hole‐Transport Layers and Donor Materials on Open‐Circuit Voltage and Shape of I–V Curves of Organic Solar Cells

The effect of injection and extraction barriers on flat heterojunction (FHJ) and bulk heterojunction (BHJ) organic solar cells is analyzed. The barriers are realized by a combination of p‐type materials with HOMOs varying between –5.0 and –5.6 eV as hole‐transport layer (HTL) and as donor in vacuum‐evaporated multilayer p‐i‐metal small‐molecule solar cells. The HTL/donor interface can be seen as a model for the influence of contacts in organic solar cells in general. Using drift‐diffusion simulations we are well able to reproduce and explain the experimental I–V curves qualitatively. In FHJ solar cells the open‐circuit voltage (V_oc) is determined by the donor and is independent of the HTL. In BHJ solar cells, however, V_oc decreases if injection barriers are present. This different behavior is caused by a blocking of the charge carriers at a spatially localized donor/acceptor heterojunction, which is only present in the FHJ solar cells. The forward current is dominated by the choice of HTL. An energy mismatch in the HOMOs leads to kinks in the I–V curves in the cases for which V_oc is independent of the HTL.     

Synthesis and Structure–Property Correlations of Dicyanovinyl‐Substituted Oligoselenophenes and their Application in Organic Solar Cells

The convergent synthesis of a series of acceptor–donor–acceptor (A‐D‐A) type dicaynovinyl (DCV)‐substituted oligoselenophenes DCVnS (n = 3–5) is presented. Trends in thermal and optoelectronic properties are studied, in dependence on the length of the conjugated backbone. Optical measurements reveal red‐shifted absorption spectra and electrochemical investigations show lowering of the lowest unoccupied molecular orbital (LUMO) energy levels for DCVnS compared to the corresponding thiophene analogs DCVnT. As a consequence, a lowering of the bandgap is observed. Single crystal X‐ray structure analysis of tetramer DCV4S provides important insight into the packing features and intermolecular interactions of the molecules, further corroborating the importance of the DCV acceptor groups for the molecular ordering. DCV4S and DCV5S are used as donor materials in planar heterojunction (PHJ) and bulk‐heterojunction (BHJ) organic solar cells. The devices show very high fill factors (FF), a high open circuit voltage, and power conversion efficiencies (PCE) of up to 3.4% in PHJ solar cells and slightly reduced PCEs of up to 2.6% in BHJ solar cells. In PHJ devices, the PCE for DCV4S almost doubles compared to the PCE reported for the oligothiophene analog DCV4T, while DCV5S shows an about 30% higher PCE than DCV5T.     

Towards Efficient Integrated Perovskite/Organic Bulk Heterojunction Solar Cells: Interfacial Energetic Requirement to Reduce Charge Carrier Recombination Losses

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J_sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J_sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.     

Printable and Large‐Area Organic Solar Cells Enabled by a Ternary Pseudo‐Planar Heterojunction Strategy

Bulk heterojunction (BHJ) processing technology has had an irreplaceable role in the development of organic solar cells (OSCs) in the past decades due to the significant advantages in achieving high‐power conversion efficiency (PCE). However, the difficulty in exploring and regulating morphology makes it inadequate for upscaling large‐area OSCs. In this work, printable high‐performance ternary devices are fabricated by a pseudo‐planar heterojunction (PPHJ) strategy. The fullerene derivative indene‐C₆₀ bisadduct (ICBA) is incorporated into PM6/IT‐4F system to expand the vertical phase separation and facilitate an obvious PPHJ structure. After the addition of ICBA, the IT‐4F enriches on the surface of active layer, while PM6 is accumulated underneath. Furthermore, it increases the crystallinity of PM6, which facilitates exciton dissociation and charge transfer. Accordingly, 1.05 cm² devices are fabricated by blade‐coating with an enhanced PCE of 14.25% as compared to the BHJ devices (13.73%). The ternary PPHJ strategy provides an effective way to optimize the vertical phase separation of organic semiconductor during scalable printing methods.     

Highly Efficient Ternary Solar Cells with Efficient Förster Resonance Energy Transfer for Simultaneously Enhanced Photovoltaic Parameters

Introducing a third component into organic bulk heterojunction solar cells has become an effective strategy to improve photovoltaic performance. Meanwhile, the rapid development of non-fullerene acceptors (NFAs) has pushed the power conversion efficiency (PCE) of organic solar cells (OSCs) to a higher standard. Herein, a series of fullerene-free ternary solar cells are fabricated based on a wide bandgap acceptor, IDTT-M, together with a wide bandgap donor polymer PM6 and a narrow bandgap NFA Y6. Insights from the morphological and electronic characterizations reveal that IDTT-M has been incorporated into Y6 domains without disrupting its molecular packing and sacrificing its electron mobility and work synergistically with Y6 to regulate the packing pattern of PM6, leading to enhanced hole mobility and suppressed recombination. IDTT-M further functions as an energy-level mediator that increases open-circuit voltage (V_OC) in ternary devices. In addition, efficient Förster resonance energy transfer (FRET) between IDTT-M and Y6 provides a non-radiative pathway for facilitating exciton dissociation and charge collection. As a result, the optimized ternary device features a significantly improved PCE up to 16.63% with simultaneously enhanced short-circuit current (J_SC), V_OC, and fill factor (FF).     

Comparative Studies on Optical,Redox, and Photovoltaic Properties of a Series of D–A–D and Analogous D–A Chromophores

A series of new symmetrical donor‐acceptor‐donor (D?A?D) dyes based on s‐indacene‐1,3,5,7(2H,6H)‐tetraone as an acceptor unit containing varying electron donating moieties and analogous donor‐acceptor (D?A) chromophores with indane‐1,3‐dione as an acceptor are synthesized. By employing these two sets of dyes, the influence of a scaffold change from unsymmetric push‐pull (D?A) to symmetrical (D?A?D) systems on optical, electrochemical, and photovoltaic properties are explored. Detailed comparative studies reveal favorable optical characteristics and considerably decreased bandgaps for the D?A?D dyes compared to those of the reference D?A chromophores. Accordingly, the evaluation of the present dyes as donor materials in bulk heterojunction (BHJ) solar cells in combination with fullerene derivatives PC₆₁BM or PC₇₁BM as acceptors afforded significantly improved performance for devices based on D?A?D blends (up to a factor of 4 compared to the respective D‐A reference) with power conversion efficiencies of up to 2.8%. In less polar solvents such as toluene, some of the novel D?A?D chromophores exhibit unexpectedly high fluorescence quantum yields Φ_em of up to unity, in striking contrast to their weakly fluorescent D‐A counterparts.     

Structural Origins for Tunable Open‐Circuit Voltage in Ternary‐Blend Organic Solar Cells

Ternary‐blend bulk‐heterojunction solar cells have provided a unique opportunity for tuning the open‐circuit voltage (V_oc) as the “effective” highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO) energy levels shift with active‐layer composition. Grazing‐incidence X‐ray diffraction (GIXD) measurements performed on such ternary‐blend thin films reveal evidence that the two polymer donors interact intimately; their ionization potentials are thus reflections of the blend compositions. In ternary‐blend thin films in which the two polymer donors do not interact physically, the polymer donors each retain their molecular electronic character; solar cells constructed with these ternary blends thus exhibit V_ocs that are pinned to the energy level difference between the highest of the two lying HOMO and the LUMO of the electron acceptor. These observations are consistent with the organic alloy model proposed earlier. Quantification of the square of the square‐root differences of the surface energies of the components provides a proxy for the Flory–Huggins interaction parameter for polymer donor pairs in these ternary‐blend systems. Of the three ternary‐blend systems examined herein, this quantity has to be below 0.094 in order for ternary‐blend solar cells to exhibit tunable V_oc.     

Fullerene Adducts Bearing Cyano Moiety for Both High Dielectric Constant and Good Active Layer Morphology of Organic Photovoltaics

Power conversion efficiency (PCE) of organic photovoltaics (OPVs) lags behind of inorganic photovoltaics due to low dielectric constants (ε _r) of organic semiconductors. Although OPVs with high ε _r are attractive in theory, practical demonstration of efficient OPV devices with high‐ε _r materials is in its infancy. This is largely due to the contradiction between the requirements of high ε _r and good donor:acceptor blend morphology in the bulk heterojunction. Herein, a series of fullerene acceptors is reported bearing a polar cyano moiety for both high ε _r and good donor:acceptor blend morphology. These cyano‐functionalized acceptors (ε _r = 4.9) have higher ε _r than that of the widely used acceptor, [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) (ε _r = 3.9). The high ε _r is realized without decrease of electron mobility and change of the lowest unoccupied molecular orbital/highest occupied molecular orbital (LUMO/HOMO) energy levels. Although the cyano‐functionalized acceptors have increased polarity, they still exhibit good compatibility with the typical donor polymer. Polymer solar cells based on the cyano‐functionalized acceptors exhibit good active layer morphology and show better device performance (PCE = 5.55%) than that of PC₆₁BM (PCE = 4.56%).     

Additive‐Morphology Interplay and Loss Channels in “All‐Small‐Molecule” Bulk‐heterojunction (BHJ) Solar Cells with the Nonfullerene Acceptor IDTTBM

Achieving efficient bulk‐heterojunction (BHJ) solar cells from blends of solution‐processable small‐molecule (SM) donors and acceptors is proved particularly challenging due to the complexity in obtaining a favorable donor–acceptor morphology. In this report, the BHJ device performance pattern of a set of analogous, well‐defined SM donors— DR3TBDTT ( DR3 ), SMPV1 , and BTR —used in conjunction with the SM acceptor IDTTBM is examined. Examinations show that the nonfullerene “All‐SM” BHJ solar cells made with DR3 and IDTTBM can achieve power conversion efficiencies (PCEs) of up to ≈4.5% (avg. 4.0%) when the solution‐processing additive 1,8‐diiodooctane (DIO, 0.8% v/v) is used in the blend solutions. The figures of merit of optimized DR3:IDTTBM solar cells contrast with those of “as‐cast” BHJ devices from which only modest PCEs <1% can be achieved. Combining electron energy loss spectrum analyses in scanning transmission electron microscopy mode, carrier transport measurements via “metal‐insulator‐semiconductor carrier extraction” methods, and systematic recombination examinations by light‐dependence and transient photocurrent analyses, it is shown that DIO plays a determining role—establishing a favorable lengthscale for the phase‐separated SM donor–acceptor network and, in turn, improving the balance in hole/electron mobilities and the carrier collection efficiencies overall.     

Nanoscale Phase Separation and High Photovoltaic Efficiency in Solution‐Processed,Small‐Molecule Bulk Heterojunction Solar Cells

Research relating to organic solar cells based on solution‐processed, bulk heterojunction (BHJ) films has been dominated by polymeric donor materials, as they typically have better film‐forming characteristics and film morphology than their small‐molecule counterparts. Despite these morphological advantages, semiconducting polymers suffer from synthetic reproducibility and difficult purification procedures, which hinder their commercial viability. Here, a non‐polymeric, diketopyrrolopyrrole‐based donor material that can be solution processed with a fullerene acceptor to produce good quality films is reported. Thermal annealing leads to suitable phase separation and material distribution so that highly effective BHJ morphologies are obtained. The frontier orbitals of the material are well aligned with those of the fullerene acceptor, allowing efficient electron transfer and suitable open‐circuit voltages, leading to power conversion efficiencies of 4.4 ± 0.4% under AM1.5G illumination (100 mW cm^?2). Small molecules can therefore be solution processed to form high‐quality BHJ films, which may be used for low‐cost, flexible organic solar cells.     

Quantifying interface states and bulk defects in high‐efficiency solution‐processed small‐molecule solar cells by impedance and capacitance characteristics

The AC properties of high‐efficiency (η = 8.01% under standard 100 mW/cm² AM1.5 illumination) small‐molecule bulk heterojunction (SM BHJ) solar cells (p‐DTS(FBTTh₂)₂/PC₇₀BM) at different DC biases and frequencies of small amplitude (±10 mV) AC signal in the dark at room temperature were investigated in details. We showed the presence of interface states at the heterojunction interface and determined their parameters from the analysis of spectral distributions of real and imaginary components of the measured impedance. The dielectric constant of BHJ ε_BHJ = 2.9 was determined from the geometrical capacitance of totally depleted BHJ layer. We explained quantitatively the effect of interface states and series resistance on the measured C‐V characteristics of the SM BHJ solar cells at both low and high frequencies. The quantitative value of the density of defect states in the bulk N = 1.05 × 10¹⁶ cm⁻³ was determined from the high frequency C‐V characteristic corrected by the effect of the series resistance. Copyright © 2015 John Wiley & Sons, Ltd.     

Spiro Linkage as an Alternative Strategy for Promising Nonfullerene Acceptors in Organic Solar Cells

This work focuses on developing diketopyrrolopyrrole (DPP)‐based small molecular nonfullerene acceptors for bulk heterojunction (BHJ) organic solar cells. The materials, SF‐DPP s, have an X‐shaped geometry arising from four DPP units attached to a spirobifluorene (SF) center. The spiro‐dimer of DPP‐fluorene‐DPP is highly twisted, which suppresses strong intermolecular aggregation. Branched 2‐ethylhexyl (EH), linear n‐octyl (C8), and n‐dodecyl (C12) alkyl sides are chosen as substituents to functionalize the N,N‐positions of the DPP moiety to tune molecular interactions. SF‐DPPEH , the best candidate in SF‐DPP s family, when blended with poly(3‐hexylthiophene) (P3HT) showed a moderate crystallinity and gives a J_sc of 6.96 mA cm^?2, V_oc of 1.10 V, a fill factor of 47.5%, and a power conversion efficiency of 3.63%. However, SF‐DPPC8 and SF‐DPPC12 exhibit lower crystallinity in their BHJ blends, which is responsible for their reduced J_sc. Coupling DPP units with SF using an acetylene bridge yields SF‐A‐DPP molecules. Such a small modification leads to drastically different morphological features and far inferior device performance. These observations demonstrate a solid structure–property relationship by topology control and material design. This work offers a new molecular design approach to develop efficient small molecule nonfullerene acceptors.     

Solution‐Processed Bulk‐Heterojunction Solar Cells Based on Monodisperse Dendritic Oligothiophenes

A novel family of soluble conjugated dendritic oligothiophenes (DOTs) as monodisperse 3D macromolecular architectures was characterized with respect to optical and redox properties in solution and in solid films. Band gaps of 2.5–2.2 eV, typical for organic semiconductors, were determined as well as HOMO/LUMO energy levels ideal for efficient electron transfer to acceptors such as [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) identifying them as suitable materials for solar cell applications. Solution‐processed bulk‐heterojunction solar cells using DOTs as electron donor and PCBM as acceptor were prepared and investigated. High open‐circuit voltages V_OC of 1.0 V and power‐conversion efficiencies up to 1.72% were obtained for the DOT‐based devices. The higher generations DOTs provide the highest efficiencies. Based on the monodispersity of the DOTs, an analysis of the molar ratio between donor and acceptor in the blended film was possible leading to an optimal value of five to six thiophene units per PCBM.     

Improving charge transport and suppressing charge recombination in small molecule ternary solar cells via incorporating Bis-PC71BM as a cascade material

The development of small molecule organic solar cells (SMOSCs) has attracted considerable attention and achieved comparable power conversion efficiency (PCE) with polymer solar cells. Here, we demonstrate a bulk heterojunction (BHJ) small molecular solar cell with PCE of 5.31% by incorporating Bisadduct of phenyl-C₇₁-butyric acid methyl ester (Bis-PC₇₁BM) as an additional acceptor material into the host binary blend of 2-[4-(N-butyl-N-phenylamino)-2,6-dihydroxyphenyl]-4-[(4-(N-butyl-N-phenylamino)-2,6-dihydroxyphenyl)-2,5-dien-1-ylidene]-3-oxocyclobut-1-en-1-olate (SQ-BP): [6,6]-phenyl C₇₁ butyric acid methyl ester (PC₇₁BM). The short circuit current (J_SC) and the fill factor (FF) of ternary SMOSCs are improved by decreasing the carrier recombination loss, increasing exciton dissociation and enhancing the carrier transport. The transient photovoltage (TPV) measurement indicates that the gradient HOMO energy alignment suppresses the charge recombination and leads to the increased charge carrier lifetime in ternary SMOSCs. As a result, the PCE of ternary devices with 5 wt% Bis-PC₇₁BM is about 20% greater than that of SQ-BP: PC₇₁BM based binary SMOSCs.     

Functionalized Graphene as an Electron‐Cascade Acceptor for Air‐Processed Organic Ternary Solar Cells

Functionalized graphene nanoflakes (GNFs) are used as an electron‐cascade acceptor material in air‐processed organic ternary bulk heterojunction solar cells. The functionalization is realized via the attachment of the ethylenedinitrobenzoyl (EDNB) molecule to the GNFs. Simulation and experimental results show that such nanoscale modification greatly influences the density of states near the Fermi level. Consequently, the GNF‐EDNB blend presents favorable highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels to function as a bridge structure between the poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] (PCDTBT) and the [6,6]‐phenyl‐C71‐butyric‐acid‐methyl‐ester (PC₇₁BM). The improved exciton dissociation and charge transport are associated with the better energy level alignment of the ternary blend and the high electrical conductivity of the GNFs, which act as additional electron transport channels within the photoactive layer. The resulting PCDTBT/GNF‐EDNB/PC₇₁BM ternary organic solar cells, fabricated entirely under ambient conditions, exhibit an average power conversion efficiency enhancement of ≈18% as compared with the binary blend PCDTBT/PC₇₁BM.     

Silaindacenodithiophene‐Based Low Band Gap Polymers – The Effect of Fluorine Substitution on Device Performances and Film Morphologies

Silaindacenodithiophene is copolymerized with benzo[c][1,2,5]thiadiazole ( BT ) and 4,7‐di(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole ( DTBT ), respectively their fluorinated counter parts 5,6‐difluorobenzo[c][1,2,5]thiadiazole ( 2FBT ) and 5,6‐difluoro‐4,7‐di(thiophen‐2‐yl) benzo[c][1,2,5]thiadiazole ( 2FDTBT ). The influence of the thienyl spacers and fluorine atoms on molecular packing and active layer morphology is investigated with regard to device performances. bulk heterojunction (BHJ) solar cells based on silaindacenodithiophene donor‐acceptor polymers achieved PCE's of 4.5% and hole mobilities of as high as 0.28 cm²/(V s) are achieved in an organic field‐effect transistor (OFET).     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

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.