Tuning the Morphology and Performance of Low Bandgap Polymer:Fullerene Heterojunctions via Solvent Annealing in Selective Solvents

Low bandgap polymer (LBG):fullerene mixtures are some of the most promising organic photovoltaic active layers. Unfortunately, there are no post‐deposition treatments available to rationally improve the morphology and performance of as‐cast LBG:fullerene OPV active layers, where thermal annealing usually fails. Therefore, there is a glaring need to develop post‐deposition methods to guide the morphology of LBG:fullerene bulk heterojunctions towards targeted structures and performance. In this paper, the structural evolution of PCPDTBT:PCBM mixtures with solvent annealing (SA) is examined, focusing on the effect of solvent quality of the fullerene and polymer in the annealing vapor on morphological evolution and device performance. The results indicate that exposure of this active layer to the solvent vapor controls the ordering of PCPDTBT and PCBM phase separation very effectively, presumably by inducing component mobility as the solvent plasticizes the mixture. These results also unexpectedly indicate that solvent annealing in a selective solvent provides a method to invert the morphology of the LBG:fullerene mixture from a polymer aggregate dispersed in a polymer:fullerene matrix to fullerene aggregates dispersed in a polymer:fullerene matrix. The judicious choice of solvent vapor, therefore, provides a unique method to exquisitely control and optimize the morphology of LBG conjugated polymer/fullerene mixtures.     

Distinguishing the Importance of Fullerene Phase Separation from Polymer Ordering in the Performance of Low Band Gap Polymer:Bis‐Fullerene Heterojunctions

One way to improve power conversion efficiency (PCE) of polymer based bulk‐heterojunction (BHJ) photovoltaic cells is to increase the open circuit voltage (V _oc). Replacing PCBM with bis‐adduct fullerenes significantly improves V _oc and the PCE in devices based on the conjugated polymer poly(3‐hexyl thiophene) (P3HT). However, for the most promising low band‐gap polymer (LBP) system, replacing PCBM with ICBA results in poor short‐circuit current (J _sc) and PCE although V _oc is significantly improved. The optimization of the morphology of as‐cast LBP/bis‐fullerene BHJ photovoltaics is attempted by adding a co‐solvent to the polymer/fullerene solution prior to film deposition. Varying the solubility of polymer and fullerene in the co‐solvent, bulk heterojunctions are fabricated with no change of polymer ordering, but with changes in fullerene phase separation. The morphologies of the as‐cast samples are characterized by small angle neutron scattering and neutron reflectometry. A homogenous dispersion of ICBA in LBP is found in the samples where the co‐solvent is selective to the polymer, giving poor device performance. Aggregates of ICBA are formed in samples where the co‐solvent is selective to ICBA. The resultant morphology improves PCE by up to 246%. A quantitative analysis of the neutron data shows that the interfacial area between ICBA aggregates and its surrounding matrix is improved, facilitating charge transport and improving the PCE.     

Highly Efficient Indoor Organic Photovoltaics with Spectrally Matched Fluorinated Phenylene‐Alkoxybenzothiadiazole‐Based Wide Bandgap Polymers

The unique electro‐optical features of organic photovoltaics (OPVs) have led to their use in applications that focus on indoor energy harvesters. Various adoptable photoactive materials with distinct spectral absorption windows offer enormous potential for their use under various indoor light sources. An in‐depth study on the performance optimization of indoor OPVs is conducted using various photoactive materials with different spectral absorption ranges. Among the materials, the fluorinated phenylene‐alkoxybenzothiadiazole‐based wide bandgap polymer—poly[(5,6‐bis(2‐hexyldecyloxy)benzo[c][1,2,5]thiadiazole‐4,7‐diyl)‐alt‐(5,50‐(2,5‐difluoro‐1,4‐phenylene)bis(thiophen‐2‐yl))] (PDTBTBz‐2F_anti)‐contained photoactive layer—exhibits a superior spectrum matching with indoor lights, particularly a light‐emitting diode (LED), which results in an excellent power absorption ratio. These optical properties contribute to the state‐of‐the‐art performance of the PDTBTBz‐2F_anti:[6,6]‐phenyl‐C₇₁ butyric acid methyl ester (PC₇₁BM)‐based OPV with an unprecedented high power‐conversion efficiency (PCE) of 23.1% under a 1000 lx LED. Finally, its indoor photovoltaic performance is observed to be better than that of an interdigitated‐back‐contact‐based silicon photovoltaic (PCE of 16.3%).     

Solvent‐Induced Morphology in Polymer‐Based Systems for Organic Photovoltaics

Studies on the influence of four different solvents on the morphology and photovoltaic performance of bulk‐heterojunction films made of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) via spin‐coating for photovoltaic applications are reported. Solvent‐dependent PCBM cluster formation and P3HT crystallization during thermal annealing are investigated with optical microscopy and grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and are found to be insufficient to explain the differences in device performance. A combination of atomic force microscopy (AFM), X‐ray reflectivity (XRR), and grazing‐incidence small‐angle X‐ray scattering (GISAXS) investigations results in detailed knowledge of the inner film morphology of P3HT:PCBM films. Vertical and lateral phase separation occurs during spin‐coating and annealing, depending on the solvent used. The findings are summarized in schematics and compared with the IV characteristics. The main influence on the photovoltaic performance arises from the vertical material composition and the existence of lateral phase separation fitting to the exciton diffusion length. Absorption and photoluminescence measurements complement the structural analysis.     

Wide Bandgap Polymer with Narrow Photon Harvesting in Visible Light Range Enables Efficient Semitransparent Organic Photovoltaics

Wide bandgap polymer D18 with narrow photon harvesting in visible light range and small molecule N3 with near-infrared photon harvesting are adopted for building semitransparent organic photovoltaics (OPVs). To find out the optimal D18:N3 weight ratio for semitransparent OPVs, series of opaque OPVs are built with a varied D18:N3 weight ratio. The power conversion efficiency (PCE) and fill factor can be maintained over 16% and 77% in the D18:N3 (0.7:1.6, wt/wt) based opaque OPVs, respectively. The average visible transmittance (AVT) of the corresponding blend films can be achieved over 50%, demonstrating the great potential in fabricating efficient semitransparent OPVs. The semitransparent OPVs based on D18:N3 (0.7:1.6, wt/wt) are fabricated by using 1 nm Au/(10, 15, 20 nm) Ag as cathode. The thickness of Ag layers is varied to balance the optical properties and electrical properties of semitransparent top electrode. The semitransparent OPVs with 10 nm Ag achieve the highest light utilization efficiency of 2.90% with a PCE of 12.91% and an AVT of 22.49%, which should be among the best performance of reported semitransparent OPVs. This work demonstrates that the wide bandgap polymer donor with narrow photon harvesting in visible light range has great potential in preparing efficient semitransparent OPVs.     

Tuning the Polarizability in Donor Polymers with a Thiophenesaccharin Unit for Organic Photovoltaic Applications

This paper describes the synthesis of low bandgap copolymers incorporating an artificial sweetener derivative, N‐alkyl, 3‐oxothieno[3,4‐d]isothiazole 1,1‐dioxide (TID). This new TID unit is identical to the well‐known thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) unit except that one carbonyl has been replaced by a sulfonyl group. Semi‐empirical calculations on the local dipole moment change between ground and excited states (Δμ_ge) in the repeating units of the new polymer indicate that the replacement of the carbonyl by a sulfonyl group leads to larger Δμ_ge values. The resulting polymers exhibit a diminished power‐conversion efficiency (PCE) compared to a bulk heterojunction (BHJ) solar cells with PC₇₁BM as an acceptor, which extends the correlation between PCE and Δμ_ge of single repeating units in p‐type polymers to a new regime. Detailed studies show that the strongly electron‐withdrawing sulfonyl group is detrimental to charge separation in alternating copolymers containing a TID unit.     

A Versatile Fluoro‐Containing Low‐Bandgap Polymer for Efficient Semitransparent and Tandem Polymer Solar Cells

The versatility of a fluoro‐containing low band‐gap polymer, poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b’]dithiophene)‐alt‐4,7‐(5‐fluoro‐2,1,3‐benzothia‐diazole)] (PCPDTFBT) in organic photovoltaics (OPVs) applications is demonstrated. High boiling point 1,3,5‐trichlorobenzene (TCB) is used as a solvent to manipulate PCPDTFBT:[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) active layer morphology to obtain high‐performance single‐junction devices. It promotes the crystallization of PCPDTFBT polymer, thus improving the charge‐transport properties of the active layer. By combining the morphological manipulation with interfacial optimization and device engineering, the single‐junction device exhibits both good air stability and high power‐conversion efficiency (PCE, of 6.6%). This represents one of the highest PCE values for cyclopenta[2,1‐b;3,4‐b’]dithiophene (CPDT)‐based OPVs. This polymer is also utilized for constructing semitransparent solar cells and double‐junction tandem solar cells to demonstrate high PCEs of 5.0% and 8.2%, respectively.     

High‐Performance Near‐IR Photodetector Using Low‐Bandgap MA0.5FA0.5Pb0.5Sn0.5I3 Perovskite

Photodetectors with ultrafast response are explored using inorganic/organic hybrid perovskites. High responsivity and fast optoelectronic response are achieved due to the exceptional semiconducting properties of perovskite materials. However, most of the perovskite‐based photodetectors exploited to date are centered on Pb‐based perovskites, which only afford spectral response across the visible spectrum. This study demonstrates a high‐performance near‐IR (NIR) photodetector using a stable low‐bandgap Sn‐containing perovskite, (CH₃NH₃)_0.5(NH₂CHNH₂)_0.5Pb_0.5Sn_0.5I₃ (MA_0.5FA_0.5Pb_0.5Sn_0.5I₃), which is processed with an antioxidant additive, ascorbic acid (AA). The addition of AA effectively strengthens the stability of Sn‐containing perovskite against oxygen, thereby significantly inhibiting the leakage current. Consequently, the derived photodetector shows high responsivity with a detectivity of over 10¹² Jones ranging from 800 to 970 nm. Such low‐cost, solution processable NIR photodetectors with high performance show promising potential for future optoelectronic applications.     

Direct Arylation Polycondensation: A Promising Method for the Synthesis of Highly Pure,High‐Molecular‐Weight Conjugated Polymers Needed for Improving the Performance of Organic Photovoltaics

Alternating conjugated polymers of ethylenedioxythiophene and fluorene are prepared using three different synthetic methods to investigate the effects of these synthetic methods on the purity, field‐effect transistor (FET) performance, and organic photovoltaic (OPV) performance of the polymer. In this study, microwave‐assisted direct arylation polycondensation is used to obtain a high‐purity, high‐molecular‐weight (147 kDa) polymer. This pure polymer exhibits a high FET hole mobility of 1.2 × 10^?3 cm² V^?1 s^?1 and high OPV performance with a power conversion efficiency of 4%, even though the polymer forms an amorphous film, which absorbs in a limited region of the spectrum.     

Fluorous Metal–Organic Frameworks and Nonporous Coordination Polymers as Low‐κ Dielectrics

A fluorous metal–organic framework [Cu(FBTB)(DMF)] (FMOF‐3) [H₂FBTB = 1,4‐bis(1‐H‐tetrazol‐5‐yl)tetrafluorobenzene] and fluorous nonporous coordination polymer [Ag₂(FBTB)] (FN‐PCP‐1) are synthesized and characterized as for their structural, thermal, and textural properties. Together with the corresponding nonfluorinated analogues lc‐[Cu(BTB)(DMF)] and [Ag₂(BTB)], and two known (super)hydrophobic MOFs, FMOF‐1 and ZIF‐8, they have been investigated as low‐dielectric constant (low‐κ) materials under dry and humid conditions. The results show that substitution of hydrogen with fluorine or fluoroalkyl groups on the organic linker imparts higher hydrophobicity and lower polarizability to the overall material. Pellets of FMOF‐1, FMOF‐3, and FN‐PCP‐1 exhibit κ values of 1.63(1), 2.44(3), and 2.57(3) at 2 × 10⁶ Hz, respectively, under ambient conditions, versus 2.94(8) and 3.79(1) for lc‐[Cu(BTB)(DMF)] and [Ag₂(BTB)], respectively. Such low‐κ values persist even upon exposure to almost saturated humidity levels. Correcting for the experimental pellet density, the intrinsic κ for FMOF‐1 reaches the remarkably low value of 1.28, the lowest value known to date for a hydrophobic material.     

Optimization of Solubility,Film Morphology and Photodetector Performance by Molecular Side‐Chain Engineering of Low‐Bandgap Thienothiadiazole‐Based Polymers

A series of donor–acceptor (D‐A) type low‐bandgap polymers containing the terthiophene and thieno[3,4‐b]thiadiazole units in the main chain but different numbers of identical side chains are designed and synthesized in order to study the effect of side chain on the polymer properties and optimize the performance of polymer photodetectors. Variation in the side chain content can influence the polymer solubility, molecular packing, and film morphology, which in turn affects the photodetector performance, particularly with regard to the photoresponsivity and dark current. X‐ray diffraction patterns indicate that molecular ordering increases with more side chains. Atomic force microscopy shows that appropriate morphology of the active layer in the polymer photodetector is necessary for high photocurrent and low dark current. Using BCP as a hole blocking layer (10 nm), the photodetector based on P4 exhibits the optimized performance with specific detectivity of 1.4 × 10¹² Jones at 800 nm, which is among the best reported values for polymer photodetectors and even comparable to that of a silicon photodetector.     

Correlated In Situ Low‐Frequency Noise and Impedance Spectroscopy Reveal Recombination Dynamics in Organic Solar Cells Using Fullerene and Non‐Fullerene Acceptors

Non‐fullerene acceptors based on perylenediimides (PDIs) have garnered significant interest as an alternative to fullerene acceptors in organic photovoltaics (OPVs), but their charge transport phenomena are not well understood, especially in bulk heterojunctions (BHJs). Here, charge transport and current fluctuations are investigated by performing correlated low‐frequency noise and impedance spectroscopy measurements on two BHJ OPV systems, one employing a fullerene acceptor and the other employing a dimeric PDI acceptor. In the dark, these measurements reveal that PDI‐based OPVs have a greater degree of recombination in comparison to fullerene‐based OPVs. Furthermore, for the first time in organic solar cells, 1/f noise data are fit to the Kleinpenning model to reveal underlying current fluctuations in different transport regimes. Under illumination, 1/f noise increases by approximately four orders of magnitude for the fullerene‐based OPVs and three orders of magnitude for the PDI‐based OPVs. An inverse correlation is also observed between noise spectral density and power conversion efficiency. Overall, these results show that low‐frequency noise spectroscopy is an effective in situ diagnostic tool to assess charge transport in emerging photovoltaic materials, thereby providing quantitative guidance for the design of next‐generation solar cell materials and technologies.     

Broadband Finite‐Difference Time‐Domain Modeling of Plasmonic Organic Photovoltaics

We develop accurate finite‐difference time‐domain (FDTD) modeling of polymer bulk heterojunction solar cells containing Ag nanoparticles between the hole‐transporting layer and the transparent conducting oxide‐coated glass substrate in the wavelength range of 300 nm to 800 nm. The Drude dispersion modeling technique is used to model the frequency dispersion behavior of Ag nanoparticles, the hole‐transporting layer, and indium tin oxide. The perfectly matched layer boundary condition is used for the top and bottom regions of the computational domain, and the periodic boundary condition is used for the lateral regions of the same domain. The developed FDTD modeling is employed to investigate the effect of geometrical parameters of Ag nanospheres on electromagnetic fields in devices. Although negative plasmonic effects are observed in the considered device, absorption enhancement can be achieved when favorable geometrical parameters are obtained.     

Charge Transfer Excitons in Polymer/Fullerene Blends: The Role of Morphology and Polymer Chain Conformation

Here, it is shown how carrier recombination through charge transfer excitons between conjugated polymers and fullerene molecules is mainly controlled by the intrachain conformation of the polymer, and to a limited extent by the mesoscopic morphology of the blend. This experimental result is obtained by combining near‐infrared photoluminescence spectroscopy and transmission electron microscopy, which are sensitive to charge transfer exciton emission and morphology, respectively. The photoluminescence intensity of the charge transfer exciton is correlated to the degree of intrachain order of the polymer, highlighting an important aspect for understanding and limiting carrier recombination in organic photovoltaics.     

Durable Ultraflexible Organic Photovoltaics with Novel Metal‐Oxide‐Free Cathode

Flexible and stretchable organic photovoltaics (OPVs) are promising as a power source for wearable devices with multifunctions ranging from sensing to locomotion. Achieving mechanical robustness and high power conversion efficiency for ultraflexible OPVs is essential for their successful application. However, it is challenging to simultaneously achieve these features by the difficulty to maintain stable performance under a microscale bending radius. Ultraflexible OPVs are proposed by employing a novel metal‐oxide‐free cathode that consists of a printed ultrathin metallic transparent electrode and an organic electron transport layer to achieve high electron‐collecting capabilities and mechanical robustness. In fact, the proposed ultraflexible OPV achieves a power conversion efficiency of 9.7% and durability with 74% efficiency retention after 500 cycles of deformation at 37% compression through buckling. The proposed approach can be applied to active layers with different morphologies, thus suggesting its universality and potential for high‐performance ultraflexible OPV devices.     

Temperature‐Dependent Aggregation Donor Polymers Enable Highly Efficient Sequentially Processed Organic Photovoltaics Without the Need of Orthogonal Solvents

The conventional method to prepare bulk‐heterojunction organic photovoltaics (OPVs) is a one‐step method from the blend solution of donor and acceptor materials, known as blend‐casting (BC). Recently, an alternative method was demonstrated to achieve high efficiencies (13%) comparable to state‐of‐the‐art BC devices. This two‐step‐coating method, known as “sequential processing,” (SqP) involves sequential deposition of the donor and then the acceptor from two orthogonal solvents. However, the requirement of orthogonal solvents to process the donor and acceptor constrains the choice of materials and processing solvents. In this paper, an improved version of SqP method without the need for using orthogonal solvents is reported. The success is based on donor polymers with strong temperature‐dependent aggregation properties whose solution can be processed at a high temperature, but the resulting film becomes completely insoluble at room temperature, which allows for the processing of overlying acceptors from a wide range of nonorthogonal solvents. With this approach, efficient SqP OPVs is demonstrated based on a range of donor/acceptor materials and processing solvents, and, in every single case, SqP OPVs can outperform their BC counterparts. The results broaden the solvent choices and open a much larger window to optimize the processing parameters of SqP method.     

Visible‐Near Infrared Absorbing Polymers Containing Thienoisoindigo and Electron‐Rich Units for Organic Transistors with Tunable Polarity

Systematic creation of polymeric semiconductors from novel building blocks is critical for improving charge transport properties in organic field‐effect transistors (OFETs). A series of ultralow‐bandgap polymers containing thienoisoindigo (TIIG) as a thiophene analogue of isoindigo (IIG) is synthesized. The UV‐Vis absorptions of the TIIG‐based polymers ( PTIIG‐T , PTIIG‐Se , and PTIIG‐DT ) exhibit broad bands covering the visible to near‐infrared range of up to 1600 nm. All the polymers exhibit unipolar p‐channel operations with regard to gold contacts. PTIIG‐DT with centrosymmetric donor exhibits a maximum mobility of 0.20 cm² V^?1 s^?1 under gold contacts, which is higher than those of the other polymers containing axisymmetric donors. Intriguingly, OFETs fabricated with aluminum electrodes show ambipolar charge transport with hole and electron mobilities of up to 0.28 ( PTIIG‐DT ) and 0.03 ( PTIIG‐T ) cm² V^?1 s^?1, respectively. This is a record value for the hitherto reported TIIG‐based OFETs. The finding demonstrates that TIIG‐based polymers can potentially function as either unipolar or ambipolar semiconductors without reliance on the degree of electron affinity of the co‐monomers.